Petroleum Assignment - UOP Q-Max Cumene Process (FULL)

UNIVERSITY MALAYSIA SABAH
SCHOOL OF ENGINEERING & INFORMATION TECHNOLOGY

HK03 CHEMICAL ENGINEERING PROGRAMME
SEMESTER II, 2012 / 2013
KC41803 PETROLEUM PROCESSING
GROUP ASSIGNMENT TITLE:
UOP Q-MAX CUMENE PROCESS

GROUP MEMBERS:
KENNY THEN SOON HUNG (BK09110098)
LEE CHEE HOE (BK09110001)
DATE OF SUBMISSION:
29
TH
MAY 2013
LECTURER:
ASSOC. PROF. IR. OTHMAN BIN ABDUL HAMID
THE PROJECT: UOP Q-MAX CUMENE PRODUCTION PROCESS

KC41803 PETROLEUM PROCESSING: GROUP ASSIGNMENT

TABLE OF CONTENTS:

1.0 HISTORY ON PETROLEUM REFINING ..................................................... 1
1.1 The Malaysian Oil And Gas Industry: An Overview ......................................... 3
1.2 Flow Diagram of Typical Refinery ............................................................... 10
1.3 Introduction On Cumene ........................................................................... 12
1.4 Cumene Production ................................................................................... 15
1.5 Cumene Properties .................................................................................... 16
1.6 Cumene Process ........................................................................................ 19
1.8 Cumene Chemical Properties ...................................................................... 21
1.9 Uses Of Cumene ....................................................................................... 24
1.10 Description On Q-Max Process .................................................................. 25

2.0 REFINERY BALANCE ............................................................................. 27
2.1 Introduction .............................................................................................. 27
2.2 The Abu Dhabi Oil Refining Company (Takreer) .......................................... 28
2.3 Refinery Installations ................................................................................. 32
2.3.1 Refinery Units ..................................................................................... 33
2.3.2 Utilities, Off-sites, Terminal & ADR Technology ..................................... 36
2.4 Mass Balance Based 400,000 BPD of Middle East Heavy Crude ..................... 40
2.4.1 Mass Balance by Assumed Proportion of Refining Products is Double ...... 41
2.4.2 Mass Balance by Fraction Method ......................................................... 44
2.4.3 Mass Balance based on Total Production from while Middle East Countries
.................................................................................................................. 46
2.5 Conclusion ................................................................................................ 51

3.0 GROUP PROJECT ................................................................................... 53
3.1 Introduction To Cumene Production ........................................................... 53
3.1.1 Cumene Project Definition .................................................................... 53
3.1.2 Cumene Manufacturing Routes ............................................................. 55
3.1.3 General Overall Material Balance for Cumene Process ............................ 58
3.1.4 Physical Properties .............................................................................. 59
3.2 Cumene Process ........................................................................................ 60


3.3.1 Technical Description ........................................................................... 61
3.2.1 Cumene Chemical Properties ................................................................ 62
3.3 Chemical Reaction Network ........................................................................ 64
3.4 Various Processes of Manufacture .............................................................. 67
3.4.1 UOP Cumene Process .......................................................................... 67
3.4.2 Badger Cumene Process ...................................................................... 71
3.4.3 MONSANTO LUMMUS CREST Cumene Process ................................... 74
3.4.4 CDTECH & ABB Lummus Global ............................................................ 75
3.4.5 Q-MAX Process .................................................................................... 82
3.5 Description On Q-Max Process ................................................................... 85
3.6 Description On Process Flow ...................................................................... 87
3.7 Process Chemistry Chemical Reactions........................................................ 89
3.7.1 Transalkylation Of DIPB ................................................................... 91
3.7.2 Side Reactions .................................................................................... 92
3.8 Process Flow Diagram (PFD) .................................................................. 94
3.9 Description ............................................................................................... 97
3.10 Cumene Plant Section .............................................................................. 98
3.10.1 Storage and pumping section ............................................................. 98
3.10.2 Preheating and vaporization section .................................................... 98
3.10.3 Reactor section ................................................................................. 99
3.10.4 Separation and purification section ..................................................... 99
3.11 Current Industrial Cumene Production Process: UOP Process ................... 100
3.12 UOP Process Description For Cumene Production .................................... 101
3.13 Description Of Process Units .................................................................. 103
3.13.1 V-201 Vaporizer ............................................................................... 104
3.13.2 R-201 Reactor ................................................................................. 104
3.13.3 S-201 Separator .............................................................................. 104
3.13.4 T-201 Distillation Tower No. 1 .......................................................... 104
3.13.5 T-202 Distillation Tower No. 2 .......................................................... 104
3.14 Description Of Process Streams .............................................................. 105
3.14.1 Stream 1 ......................................................................................... 105
3.14.2 Stream 2 ......................................................................................... 105
3.14.3 Stream 3 ......................................................................................... 105


3.14.4 Stream 4 ......................................................................................... 105
3.14.5 Stream 5 ......................................................................................... 105
3.14.6 Stream 6 ......................................................................................... 105
3.14.7 Stream 7 ......................................................................................... 106
3.14.8 Stream 8 ......................................................................................... 106
3.14.9 Stream 9 ......................................................................................... 106
3.14.10 Stream 10 ..................................................................................... 106
3.15 Reaction Mechanism And Kinetics Of Cumene Production ......................... 107

4.0 CAPACITY CALCULATION ................................................................... 108
4.1 Mass Balance .......................................................................................... 108
4.1.1 Introduction to Mass Balance ............................................................. 108
4.1.2 Material Balance of Major Equipment - Reactor ................................... 111
4.1.3 Material Balance of Propane Column ................................................... 117
4.1.4 Material Balance of Minor Equipment - Benzene Column ...................... 118
4.1.5 Material Balance of Minor Equipment Cumene Column ...................... 121
4.2 Heat Balance .......................................................................................... 124
4.2.1 Introduction to Heat Balance .............................................................. 124
4.2.2 Heat Balance for Major Equipment - Reactor ....................................... 128
4.2.3 Heat Balance for Propane Column ...................................................... 138
4.2.4 Heat Balance for Minor Equipment - Benzene Column .......................... 144
4.2.5 Heat Balance for Minor Equipment - Cumene Column ......................... 149
4.2.6 Product Yield ..................................................................................... 154
4.3 Flow Summary for Cumene Production at Design Conditions ...................... 157
4.4 Flow Summary for Utility Streams ............................................................ 160
4.4 Equipment Summary with Capacity for Cumene Producition Process ........... 161

5.0 BEHAVIOUR OF CATALYSTS/SOLVENTS............................................. 164
5.1 Feedstock Considerations ........................................................................ 164
5.1.1 Impact Of Feedstock Contaminants On Cumene Purity ..................... 164
5.1.2 Impact of Catalyst Poisons On Catalyst Performance ........................ 168
5.2 Process Performance ............................................................................... 170


5.3 Production Of Cumene Using Zeolite Catalysts .......................................... 172
5.3.1 Unocals technology is based on a conventional fixed-bed system ......... 172
5.3.2 The second zeolite process, which was developed by CR&L ................. 172
5.4 Disadvantages Of Using Solid Phosphoric Acid (SPA) Process ..................... 173
5.5 Disadvantages of Using Aluminum Chloride As Catalyst ............................. 173
5.6 Catalysts in Cumene Production Process ................................................... 174
5.7 Catalysts And Reactions ........................................................................... 176
5.8 Cumene Process And Catalysts ................................................................. 179
5.8.1 SPA Catalyst...................................................................................... 180
5.8.2 AlCl3 and Hydrogen Chloride Catalyst .................................................. 181
5.8.3 Zeolite Catalysts ................................................................................ 182
5.9 Future Technology Trends ....................................................................... 194
5.9.1 Catalysts. .......................................................................................... 194

6.0 PROCESS AND INSTRUMENTATION DIAGRAM .................................. 196
6.1 Introduction To P&ID .............................................................................. 196
6.2 P&ID Diagram ......................................................................................... 197
6.2.1 Symbols and layout ........................................................................... 198
6.2.2 List Of Pid Items ................................................................................ 199
6.2.3 Basic symbols.................................................................................... 200
6.3 Introduction to Valve ............................................................................... 204
6.3.1 Type of Valve .................................................................................... 207
6.3.2 Multi-Turn Valve ................................................................................ 208
6.3.3 Quarter-Turn Valve ............................................................................ 221
6.4 Introduction to Safety Valve and Relief Valve ............................................ 239
6.5 Relief Concepts ....................................................................................... 241
6.6 Location of Reliefs ................................................................................... 241
6.7 Relief Types ............................................................................................ 243
6.7.1 Spring-Operated Valves ...................................................................... 244
6.7.2 Balanced-Bellows ............................................................................... 244
6.7.3 Rupture Discs ................................................................................... 245
6.8 P&ID for Reactor (Major Equipment) ........................................................ 248
6.8.1 P&ID for Reactor (Major Equipment) ................................................... 248


6.8.2 Justification of The Control System Applied to the Reactor (Major) ....... 249
6.8.3 Justification of the Selection of the Type of Valve and Safety Valve to the
Reactor (Major Equipment) ................................................................ 250
6.9 P&ID For Cumene Column (Minor Equipment) ........................................... 253
6.9.1 P&ID For Cumene Column (Minor Equipment) ..................................... 253
6.9.2 Justification Of The Control System Applied To The Cumene Column .... 254
6.9.3 Justification Of The Selection Of The Type Of Valve And Safety Valve To
The Cumene Column (Minor) ............................................................ 255

7.0 HAZOP ANALYSIS ............................................................................... 258
7.1 HAZOP Analysis For Major Equipment - Reactor ........................................ 258
7.1.1 Recommendation HAZOP For Reactor ................................................. 271
7.2 HAZOP Analysis For Minor Equipment - Cumene Column ........................... 272
7.2.1 Recommendation HAZOP For Cumene Column .................................... 285

8.0 EXPLOSION ANALYSIS ....................................................................... 286
8.1 Introduction to Fire and explosions ........................................................... 286
8.2 Distinction Between Fires And Explosions .................................................. 287
8.3 Mechanism Of Fire And Explosion ............................................................. 288
8.4 Fire Triangle ........................................................................................... 289
8.5 Sources And Causes Of Fire And Explosion In Cumene Plant ...................... 291
8.5.1 Sources Of Fuel ................................................................................. 291
8.5.2 Sources Of Ignition ............................................................................ 292
8.5.3 Sources of Oxygen ......................................................................... 294
8.6 How To Identify Potential Fire And Explosion Sources ................................ 295
8.6.1 Fuel-Hydrocarbon Sources: Identifying And Documenting Hazards ....... 298
8.6.2 Oxygen Sources: Identifying And Documenting Hazards ...................... 300
8.6.3 Energy-Ignition Sources: Identifying And Documenting Hazards ........... 301
8.7 Reasons Why It Is Not Possible To Eliminate All Sources In Fire Triangle .... 304
8.8 Factors Affecting Ignitability Of Flammable Mixtures .................................. 307
8.9 Type Of Explosion Normally Happened In Cumene Plant ............................ 309
8.10 Fire And Explosion Analysis For Major Equipments ................................... 310
8.10.1 Fire And Explosion Analysis For Reactor ............................................ 312


8.10.2 Fire And Explosion Analysis For Cumene Column ............................... 313
8.11 Identify Flammable Inventories And Locations In Cumene Plant ............. 314
8.11.1 Flammable Inventory: Propylene ...................................................... 314
8.11.2 Flammable Inventory: Benzene ........................................................ 316
8.11.3 Flammable Inventory: Di-Isoproply Benzene ..................................... 317
8.11.4 Flammable Inventory: Cumene ......................................................... 318
8.11.5 Flammable Inventory: Propane ......................................................... 319
8.12 Consequence Of Fire And Explosion Events ............................................. 320
8.13 Fire And Explosion Prevention And Control .............................................. 321
8.13.2 Minimization of Potential Amount Of Fuel .......................................... 322
8.13.2 Minimization Of Potential Sources Of Ignition .................................... 323
8.14 Additional Control Measures ................................................................... 325
8.15 Dust Control .......................................................................................... 326
8.16 Ignition Control ..................................................................................... 327
8.17 Damage Control .................................................................................... 328
8.18 Training Of Employees ........................................................................... 329
8.19 Management team ................................................................................ 329

9.0 ENVIRONMENT ANALYSIS .................................................................. 330
9.1 Introduction ............................................................................................ 330
9.2 Analytical Methods .................................................................................. 332
9.3 Emission Sources Of Cumene ................................................................... 333
9.3.1 Anthropogenic Sources ...................................................................... 335
9.4 Environmental Transport, Distribution, And Transformation ....................... 336
9.4.1 Cumene In Atmosphere ..................................................................... 336
9.4.2 Cumene In Water .............................................................................. 337
9.4.3 Cumene In Soil ................................................................................. 339
9.5 Environmental Levels And Human Exposure .............................................. 341
9.5.1 Environmental Levels ......................................................................... 341
9.5.2 Human Exposure ............................................................................... 344
9.6 Comparative Kinetics And Metabolism In Laboratory Animals And Humans . 346
9.7 Effects On Humans, Animals And Vegetation ............................................. 349
9.7.1 Overview of Chemical Disposition ....................................................... 350


9.7.2 Genotoxicity ...................................................................................... 352
9.7.3 Acute and Sub-Acute Effects .............................................................. 353
9.7.4 Sub-Chronic and Chronic Effects ......................................................... 358
9.7.5 Summary of Adverse Health Effects of Cumene Inhalation ................... 365
9.7.6 Effects on Vegetation......................................................................... 368

10.0 COMMERCIAL VALUE ........................................................................ 370
10.1 Cumene Market Survey .......................................................................... 370
10.1.1 Cumene Market Overview ................................................................ 370
10.1.1 Market Survey In Year 2010 (Price Report) ....................................... 371
10.2 Cost Estimation & Economics ................................................................. 375
10.2.1 Background & Objectives ................................................................. 375
10.2.2 Cost Evaluation ............................................................................... 375
10.2.3 Investment ..................................................................................... 377
10.2.4 Project Economic Evaluation ............................................................. 385
10.3 Cumene Commercial Value Report .......................................................... 389
10.3.1 US October cumene prices remain stable amid quiet trade ................. 389
10.3.2 US benzene and RGP markets are quiet ............................................ 390
10.4 Cumene Value Chain ............................................................................. 391
10.5 World Demand Of Cumene .................................................................... 393
10.6 Current Market Situation ........................................................................ 395
10.7 Cumene Market Outlook ........................................................................ 397
10.8 Petrochemicals: Global Markets .............................................................. 398
10.9 Feedstock Requirements ........................................................................ 399
10.10 Case Study .......................................................................................... 402
10.11 Commercial Experience ........................................................................ 404

11.0 CONCLUSION AND RECOMMENDATIONS ......................................... 405

REFERENCES


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1.0 HISTORY ON PETROLEUM REFINING
Prior to the 19th century, petroleum was known and utilized in various fashions
in Babylon, Egypt, China, Persia, Rome and Azerbaijan. However, the modern history
of the petroleum industry is said to have begun in 1846 when Abraham Gessner
of Nova Scotia, Canada discovered how to produce kerosene from coal. Shortly
thereafter, in 1854, Ignacy Lukasiewicz began producing kerosene from hand-dug oil
wells near the town of Krosno, now in Poland. The first large petroleum refinery was
built in Ploesti, Romania in 1856 using the abundant oil available in Romania.
In North America, the first oil well was drilled in 1858 by James Miller Williams
in Ontario, Canada. In the United States, the petroleum industry began in 1859
when Edwin Drake found oil near Titusville, Pennsylvania. The industry grew slowly
in the 1800s, primarily producing kerosene for oil lamps. In the early 1900's, the
introduction of the internal combustion engine and its use in automobiles created a
market for gasoline that was the impetus for fairly rapid growth of the petroleum
industry. The early finds of petroleum like those in Ontario and Pennsylvania were
soon outstripped by large oil "booms" in Oklahoma, Texas and California.
Prior to World War II in the early 1940s, most petroleum refineries in
theUnited States consisted simply of crude oil distillation units (often referred to as
atmospheric crude oil distillation units). Some refineries also had vacuum distillation
units as well as thermal cracking units such as visbreakers (viscosity breakers, units
to lower the viscosity of the oil). All of the many other refining processes discussed
below were developed during the war or within a few years after the war. They

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became commercially available within 5 to 10 years after the war ended and the
worldwide petroleum industry experienced very rapid growth. The driving force for
that growth in technology and in the number and size of refineries worldwide was
the growing demand for automotive gasoline and aircraft fuel.
In the United States, for various complex economic reasons, the construction
of new refineries came to a virtual stop in about the 1980's. However, many of the
existing refineries in the United States have revamped many of their units and/or
constructed add-on units in order to: increase their crude oil processing capacity,
increase the octane rating of their product gasoline, lower the sulfur content of their
diesel fuel and home heating fuels to comply with environmental regulations and
comply with environmental air pollution and water pollution requirements.


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1.1 The Malaysian Oil And Gas Industry: An Overview
The Oil & Gas (O&G) industry has seen no small amount of attention during recent
months. One item attracting attention is crude prices rising above USD50 per barrel
(0.159m3) and the simultaneous rise of petrol prices due to reduction in government
subsidies.
News of discoveries of new potentially producing fields has increased interest
in O&G related stocks, whether in suppliers to the industry or oil refineries. To
encourage and maintain this level of interest, IEM held a symposium in July 2004,
attempting to put forward a forum where people outside the O&G industry could be
exposed to issues within the industry.
Petroleum exploration in Malaysia started at the beginning of the 20
th
century
in Sarawak, where oil was first discovered in 1909 and first produced in 1910. Prior
to 1975, petroleum concessions were granted by state governments, where oil
companies have exclusive rights to explore and produce resources.
The companies then paid royalties and taxes to the government. This state of
affairs ceased on April 1, 1975 as a result of the Petroleum Development Act,
whereby PETRONAS became the custodian of petroleum resources with rights to
explore and produce resources. The national oil company retains ownership and
management control in exploration, development and production of oil resources.
Expenditure and profits are managed under instruments called Production Sharing
Contracts (PSCs). The Production Sharing Contractor assumes all risks and sources

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all funds for all petroleum operations. The Contractor receives an entitlement
through production.

Figure 1.1 Production Sharing Contractor Entitlement
Each PSC may have different terms and conditions. For example, different
time periods are allowed for exploration of acreage, developing and installing
infrastructure to produce any hydrocarbons discovered, and the actual production
period.
Malaysia has the 25th largest oil reserves and the 14th largest gas reserves in
the world. The total reserves is of the order of 18.82 billion barrels oil equivalent
(boe), with a crude production rate of 600 thousand barrels per day.

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Figure 1.2 Historical Crude Oil Production (bbls : barrels per day. SB :
Sabah contribution. SK : Sarawak Contribution, PM : Peninsular
contribution.)
The average natural gas production stands at approximately 5.7 billion
standard cubic feet per day. Malaysia has 494,183km
2
of acreage available for oil
and gas exploration, with 337,167 km
2
in the offshore continental shelf area, and
63,968km2 in deepwater.
The acreage is split into 54 blocks, out of which 28 (a total of 205,500km2)
are currently operated by Petronas Carigali Sdn. Bhd. plus seven other multinational
oil companies.

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Figure 1.3 Historical Natural Gas Production


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Figure 1.4 Increased production through rejuvenation
There is also an opportunity to increase production by rejuvenation of existing
production facilities. This concept can be applied both to topside and subsurface
facilities. As an example, more than 50% of Malaysian assets have been producing
for longer than 15 years. There are definite opportunities to debottleneck facilities,
looking at design and current operating conditions, and maximising the use of
existing equipment. New technologies may be retrofitted into existing equipment,
increasing capacity at an acceptable cost.

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Figure 1.5 Competitiveness of the Industry
Although there are few lower cost centres in this region, the international
clients still prefer Malaysia due to its high quality engineering produced and
availability of up to date technology knowledge. The Oil and Gas industry can be
split into upstream and downstream sectors. The upstream sector includes the
exploration and the extraction of crude oil.
In the Malaysian Oil and Gas sector, it has been the upstream sector that has
traditionally been developed. The Petroleum Development Act 1974 governs the
upstream and the downstream sectors of the petroleum industry under which
Petronas is party of. Petronas has a licensing system. All work which is contracted
out in the upstream sector is through licensed contractors. One of the objectives of

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the Act was to make sure local players were involved. One of the requirements to
obtain a licence is being a local company. It is because of this that the oil and gas
engineering industry was fully developed by the mid 80s. From the mid 80s to late
80s, all engineering design work had to be done locally.
According to Ir. Dr Torkil Ganendra, Secretary of MOGEC and Director of Aker
Kvaerner Asia Pacific, the Oil and Gas industry in Malaysia is a regulated industry,
thus all upstream engineering works have to be performed locally if there was local
technical capability. Some specialised areas are done overseas.


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1.2 Flow Diagram of Typical Refinery
The image below is a schematic flow diagram of a typical oil refinery that depicts the
various unit processes and the flow of intermediate product streams that occurs
between the inlet crude oil feedstock and the final end products.
The diagram depicts only one of the literally hundreds of different oil refinery
configurations. The diagram also does not include any of the usual refinery facilities
providing utilities such as steam, cooling water, and electric power as well as storage
tanks for crude oil feedstock and for intermediate products and end products.
There are many process configurations other than that depicted above. For
example, the vacuum distillation unit may also produce fractions that can be refined
into end products such as: spindle oil used in the textile industry, light machinery oil,
motor oil, and various waxes.

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Figure 1.6 Schematic Flow Diagram of typical oil refinery
(Source: http://en.wikipedia.org/wiki/Oil_refinery)


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1.3 Introduction On Cumene
The cumene molecule can be visualized as a straight-chain propylene group
having a benzene ring attached at the middle carbon , C6H5CH(CH3)2 . It is a
colourless liquid , bp 152.4
0
C having a characteristic aromatic odor . It is isomeric
with n-propylbenzene , ethyltoluene and trimethylbenzene.

Figure 1.7 Chemical Structure Of Cumene
(Source: http://en.wikipedia.org/wiki/Cumene)
Cumene is the common name for isopropylbenzene, an organic
compound that is an aromatichydrocarbon. It is a constituent of crude oil and
refined fuels. It is a flammable colorless liquid that has a boiling point of 152 C.
Nearly all the cumene that is produced as a pure compound on an industrial scale is

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converted to cumene hydroperoxide, which is an intermediate in the synthesis of
other industrially important chemicals, primarily phenol andacetone.
Thus cumene is also named as 1-methylethyl benzene or 2-phenyl-propane or
isopropylbenzene. Cumene (C9H12) is a substituted aromatic compound in the
benzene , toluene and ethylbenzene series.
Cumene is a clear liquid at ambient conditions. High purity cumene is
normally manufactured from propylene and benzene and is a minor constituent of
most gasolines. It is the principal chemical used in the world wide production of
phenol and its co-product acetone.
Many consumer or industrial products such as plywood and composition board
banded with phenolic resins, nylon-6, epoxy and polycarbonate resins and solvents,
have origins that can be traud to cumene.
Cumene processes were originally developed between 1939 and 1945 to meet
the demand for high octane aviation gasoline during world war-II. In 1989 about
95% of cumene demand was as an intermediate for the production of phenol and
acetone. A small percentage is used for the production of -Methylstyrene.
Before the devolopement of the cumene route to phenol and acetone,
cumene had been used extensively during warld war2. It is a curious fact that
although propylation of benzene by means of phosphoric acid and aluminium
chloride have been the standard methods of manufacture for many years ,the first

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plan used sulphuric acid as a catalyst. This was a war time expedient arising from
uncertainity over phosphoric acid supplies.
Almost all the worlds supply of cumene is now produced as an intermediate for
phenol and acetone manufacture. Some refinery units still produce cumene for use
as an antiknock constituent of gasoline but it is doubtful whether new plants would
be constructed for this purpose .
Neither does it seem likely that any large scale plant would be installed for
manufacturing the hydroperoxide, methylstyrene ,diisopropylebenzene,or
acetophenone ,although these cumene derived compounds are of considerable
commercial importance. They occur as byproducts during cumene and phenol
production, and are usually marketed by manufacturers .


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1.4 Cumene Production
Commercial production of cumene is by FriedelCrafts alkylation of
benzene with propylene. Previously, solid phosphoric acid (SPA) supported
on alumina was used as the catalyst. Since the mid-1990s, commercial production
has switched to zeolite-based catalysts.
Isopropyl benzene is stable, but may form peroxides in storage if in contact
with the air. It is important to test for the presence of peroxides before heating or
distilling. The chemical is also flammable and incompatible with strong oxidizing
agents. Environmental laboratories commonly test isopropyl benzene using a Gas
chromatographymass spectrometry (GCMS) instrument.


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1.5 Cumene Properties
Cumene

IUPAC name
(1-methylethyl)benzene
Other names
isopropylbenzene
2-phenylpropane
Identifiers
CAS number 98-82-8

PubChem 7406
ChemSpider 7128

UNII 8Q54S3XE7K


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KEGG C14396

ChEBI CHEBI:34656

RTECS number GR8575000
Jmol-3D images Image 1
Properties
Molecular formula C9H12
Molar mass 120.19 g mol
1

Appearance colorless liquid
Density 0.862 g cm
3
, liquid
Melting point
96 C, 177 K, -141 F
Boiling point
152 C, 425 K, 306 F
Solubility in water Insoluble
Viscosity 0.777 cP at 21 C
Hazards
R-phrases R10,R37,R51/53,R65

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S-phrases S24,S37,S61,S62
Main hazards Flammable
Flash point 43 C
Related compounds
Related compounds ethylbenzene, toluene, benzene


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1.6 Cumene Process
The Cumene process (Cumene-phenol process, Hock process) is
an industrial process for developing phenol & acetone from benzene and propylene.
The term stems from cumene (isopropyl benzene), the intermediate material during
the process. It was invented by Heinrich Hock in 1944

and independently by R. dris
and P. Sergeyev in 1942 (USSR).

This process converts two relatively cheap starting
materials, benzene and propylene, into two more valuable ones, phenol and acetone.
Other reactants required are oxygen from air and small amounts of a radical initiator.
Most of the worldwide production of phenol and acetone is now based on this
method. In 2003, nearly 7 billion kg of phenol was produced by the Hock Process.

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1.7 Technical Description
Benzene and propylene are compressed together to a pressure of 30 standard
atmospheres at 250 C (482 F) in presence of a catalytic Lewis acid. Phosphoric
acid is often favored over aluminium halides. Cumene is formed in the gas-
phase Friedel-Crafts alkylation of benzene by propylene:

Cumene is oxidized in air which removes the tertiary benzylic hydrogen from
cumene and hence forms a cumene radical:


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1.8 Cumene Chemical Properties
Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and
benzene. It is insoluble in water. Cumene is oxidized in air which removes the
tertiary benzylic hydrogen from cumene and hence forms a cumene radical:

This cumene radical then bonds with an oxygen molecule to give
cumene hydroperoxide radical, which in turn forms cumene
hydroperoxide (C6H5C(CH3)2-O-O-H) by abstracting benzylic hydrogen from another
cumene molecule.
This latter cumene converts into cumene radical and feeds back into
subsequent chain formations of cumene hydroperoxides. A pressure of 5 atm is used
to ensure that the unstable peroxide is kept in liquid state.

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Cumene hydroperoxide is then hydrolysed in an acidic medium (the Hock
rearrangement) to givephenol and acetone. In the first step, the terminal
hydroperoxy oxygen atom is protonated.
This is followed by a step in which the phenyl group migrates from the benzyl
carbon to the adjacent oxygen and a water molecule is lost, producing
a resonance stabilized tertiary carbocation.
The concerted mechanism of this step is similar to the mechanisms of
the Baeyer-Villiger oxidationand also the oxidation step of hydroboration-
oxidation.
[6]
In 2009, an acidified bentonite clay was proven to be a more
economical catalyst than sulfuric acid as the acid medium.

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As shown below, the resulting carbocation is then attacked by water, a proton
is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion
falls apart into phenol and acetone.

The products are extracted by distillation.


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1.9 Uses Of Cumene
1. As feed back for the production of Phenol and its co-product acetone
2. The cumene oxidation process for phenol synthesis has been growing in
popularity since the 1960s and is prominent today. The first step of this
process is the formation of cumene hydroperoxide. The hydroperoxide is
then selectively cleaved to Phenol and acetone.
3. Phenol in its various formaldehyde resins to bond construction materials like
plywood and composition board (40% of the phenol produced) for the
bisphenol A employed in making epoxy resins and polycarbonate (30%) and
for caprolactum, the starting material for nylon-6 (20%). Minor amounts are
used for alkylphenols and pharmacuticals.
4. The largest use for acetone is in solvents although increasing amounts are
used to make bisphenol A and methylacrylate.
5. - Methylstyrene is produced in controlled quantities from the cleavage of
cumene hydroperoxide, or it can be made directly by the dehydrogenation
of cumene.
6. Cumene in minor amounts is used as a thinner for paints, enamels and
lacquers and to produce acetophenone, the chemical intermediate
dicumylperoxide and diiso propyl benzene.
7. Cumene is also used as a solvent for fats and raisins.


25 | P a g e
1.10 Description On Q-Max Process
The most promising materials were modified to improve their selectivity and then
subjected to more-rigorous testing. By 1992, UOP had selected the most promising
catalyst based on beta-zeolite for cumene production and then began to optimize
the process design around this new catalyst. The result of this work is the Q-Max
process and the QZ- 2000 catalyst system.
1. Raw material propylene and benzene are used for the production of cumene.
2. These are stored in the respective storage tanks of 500MT capacity in the
storage yard pumped to the unit by the centrifugal pumps.
3. Benzene pumped to the feed vessel which mixes with the recycled benzene.
Benzenestream is pumped through the vaporizer with 25 atm pressure and
vaporized to the temperature of 243degC, mixed with the propylene which is
of same and temperature and pressure of benzene stream.
4. This reactant mixture passed through a fired super heater where reaction
temperature 350degC is obtained.
5. The vapor mixture is sent to the reactor tube side which is packed with the
solid phosphoric acid catalyst supported on the kieselguhr the exothermal
heat is removed by the pressurized water which is used for steam production
and the effluent from the reactor i.e., cumene, p-DIPB, unreacted benzene,
propylene and propane with temperature 350
o
C is used as the heating media
in the vaporizer which used for the benzene vaporizing and cooled to 40
o
C in
a water cooler, propylene and propane are separated from the liquid mixture
of cumene, p-DIPB, benzene in a separator operating slightly above atm and

26 | P a g e
the pressure is controlled by the vapor control value of the separator, the fuel
gas is used as fuel for the furnace also.
6. The liquid mixture is sent to the benzene distillation column which operates at
1 atm pressure, 98.1% of benzene is obtained as the distillate and used as
recycle and the bottom liquid mixture is pumped at bubble point to the
cumene distillation column where distillate 99.9% cumene and bottom pure
p-DIPB is obtained.
7. The heat of bottom product p-DIPB is used for preheating the benzene
column feed, All the utility as cooling water, electricity, steam from the boiler,
pneumatic air are supplied from the utility section
8. The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %
of diiso propylbenzene. The remaining 2.1 % is primarily heavy aromatics.
9. This high yield of cumene is achieved without transalkylation of diiso
propylbenzene and is unique to the solid phosphoric acid catalyst process.
10. The cumene product is 99.9 Wt. % pure and the heavy aromatics, which have
an octane number of 109, can either be used as high octane gasoline
blending components or combined with additional benzene and sent to a
transalkylation section of the plant where diiso propylbenzene is converted to
cumene.
11. The overall yields of cumene for this process are typically 97-98 Wt. % with
transalkylation and 94-96 Wt. % without transalkylation.


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2.0 REFINERY BALANCE
2.1 Introduction
Changes such as structural and cyclical in our business environment have keep us on
our toes. Our core businesses are changing in our historic home of Europe. The
Consumption of both chemicals and petroleum products is down and new demands
for more diesel and less gasoline, greener products and so on which are taking shape
currently.
We are not surprise to any changes that come to us. Since we had foreseen
most of them and are now adjusting our production base accordingly, while deploying
all our innovation capabilities to create a line of products in sync with our customers
expectations.
In addition, we are setting the stage for our expansion in regions of strong
economic growth at the same time such as Asia, the Middle East and Africa, and
adapting to the specific needs of those markets, by leveraging solid partnerships and
the remarkable agility of all our activities.
Total (37.5%) and Saudi Aramco (62.5%) are partners in SATORP, the
company building the Jubail refinery in Saudi Arabia. This strategically important
project will allow us to move closer to oil and gas fields and consumers.


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2.2 The Abu Dhabi Oil Refining Company (Takreer)
Basically, The Abu Dhabi Oil Refining Company (Takreer) was established in 1999 in
order to take over the responsibility of refining operations previously undertaken by
the Abu Dhabi National Oil Company (ADNOC). There are several companys areas of
operation which include the refining of crude oil and condensate, supply of petroleum
products and production of granulated Sulphur in compliance with domestic and
international specifications. Moreover, this refinery can work for 85,000 bbl/day
capacity.

Figure 2.1: The PMC contract is for the EPC phase of the base oils plant in
Ruwais Industrial Complex.

29 | P a g e

Today, The Shaw Group Inc. had announced that their company has been
awarded a contract by The Abu Dhabi Oil Refining Company (Takreer) to provide
project management consultancy services during the engineering, procurement and
construction phase of a base oils plant at the Ruwais Industrial Complex in Abu Dhabi.
Basically, the planned facility will be capable of producing 500,000 tons/year of
Group III base oils, as well as 100,000 tons/year of Group II base oils, and is scheduled
to begin commercial production in 2013. Group II and III base oils are used for
blending top-tier lubricants for car engines.
Besides, an announcement was made by UOP LLC, a Honeywell company, that
they have been selected by the Abu Dhabi Oil Refining Company, also known as
Takreer, with the aim to supply technology and engineering services for an expansion
at its Ruwais Refinery in the United Arab Emirates.


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The history of the refineries in Abu Dhabi Refinery which consists of
85000bbl/day is shown in Figure 2.2 below:

Figure 2.2: history of the refineries in Abu Dhabi Refinery which consists
of 85000bbl/day

1996
Plant Expansion 85,000 BBL/day
1983
New Refinery 60,000 BBL/day
1976
Original Plant 15,000 BBL/day

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The history of the refineries in Ruwais Refinery which consists of 40000bbl/day
is shown in below:

Figure 2.3: History of the refineries in Ruwais Refinery which consists of
40000bbl/day
There are other facilities such as below:
Power Geeration 660MW
Water Desalination 14.0 MM Gallons/ day
Hazardous Material Treatment, 26MMT/Year

2006
Gasoline Units
2000
Condensate units 280,000 BBL/day
1985
Hydrocracker units
1981
Hydro-skimmer units 120,000BBL/day

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2.3 Refinery Installations
After the discovery of oil in Abu Dhabi in year 1958 and the first export shipments of
Crude in year 1962, there are a plans to build a glass root Refinery with a capacity of
15,000 barrels per stream day (BPSD) to meet a growing local need for petroleum
products. Basically, the construction work has begun in year 1973. This work cost
around initial $45 million and this plant was inaugurated in the April of 1976.
Therefore, we can see that the demand for oil products were grow rapidly.
However, the work began almost on installing a new Refinery to process a further
60,000 BPSD and this was commissioned in year 1983.
So, requirements has continued to grow in the fast-developing Emirate and
ADNOC has decided to expand the capacity yet again with environmental
considerations in mind and to include additional units for Gas Oil Desulphurization and
Sulphur recovery. Therefore, the expanded Refinery with a capacity rate of 85,000
BPSD has been started up in December 1992.
On the other hand, a Salt and Chlorine Plant has been commissioned at Umm
Al Nar in the year of 1981 which was merged with the Refinery in year 1990 in order
to form the Abu Dhabi Refinery and Chlorine Division.
On 30
th
November 2001, it was permanently shut down. Two power plants,
owned and operated by Umm Al Nar Power Company, and a Lube oil blending/filling
plant, owned and operated by ADNOC Distribution, are located adjacent to the
Refinery.

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The refinery is a Hydro Skimming Complex designed to process Bab Crude as
well as a mixture of Asab-Sahil, Shah and Thammama Condensate. Finished products
from the Refinery are as follows: Liquefied Petroleum Gases, Naphtha, Unleaded
Gasoline, Aviation Turbine Kerosene, Domestic Kerosene, Gas Oil, Straight Run
Residue, Liquid Sulphur.
2.3.1 Refinery Units
Therefore, the refinery unit including:
1. Crude Distillation Unit (85,000 BPSD)
2. Naphtha Hydrodesulphuriser Unit (22,795 BPSD)
3. Kerosene Merox Unit (21,250 BPSD)
4. Catalytic Reformer Unit (14,000 BPSD)
5. Gas Oil Hydrodesulphuriser Unit (22,500 BPSD)
6. LPG Treating and Recovery Unit (3,480 BPSD)
7. Excess Naphtha Stabilizer Unit (3,325 BPSD)
8. Gas Sweetening Unit (35 tons/day H2S Removal)
9. Sulphur Recovery Unit (35 tons/day)
10. Jarn Yaphour Crude Oil Stabilization Plant (10,000 BPSD)


34 | P a g e

2.3.1.1 Crude Distillation Unit (85,000 BPSD)
For initial step, prior to the actual distillation process, Crude Oil is passed
through a Desalter Unit to remove the undesirable salts, water and sludge
which are generally associated with any type of crude.
After final heating in a furnace, the Crude is then fractionated in the
Atmospheric Distillation Column into the basic raw petroleum fractions of
Naphtha, kerosene, Gas Oil and Straight Run Residue.

2.3.1.2 Naphtha Hydrodesulphuriser Unit (22,795 BPSD)
The Naphtha Hydrodesulphuriser sweetens the Straight Run Naphtha from
Crude Unit.
This unit has produced three products namely: Heavy Naphtha, Light Naphtha
and Sour Liquefied Petroleum Gases.

2.3.1.3 Kerosene Merox Unit (21,250 BPSD)
Mercaptans was converted by the unit in the straight run kerosene into
disulphine in order to meet the final product quality for aviation kerosene.

2.3.1.4 Catalytic Reformer Unit (14,000 BPSD)
The Reformer processes the Heavy Naphtha cut to improve its anti-knock
properties prior to using it as a Gasoline blending component.

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2.3.1.5 Gas Oil Hydrodesulphuriser Unit (22,500 BPSD):
Gas oil sulphur content has been reduced by the Gas Oil Hydrodesulphurise to
0.15 wt% in order to improve the product quality.

2.3.1.6 LPG Treating and Recovery Unit (3,480 BPSD):
In this unit, raw LPG from Naphtha Hydrodesulphuriser and Catalytic Reformer
Unit are processed.
The butane that produced in this unit is used as a blending component in
Gasoline.
Besides that, the butane also can blended with Propane in order to form LPG
for domestic use.

2.3.1.7 Excess Naphtha Stabilizer Unit (3,325 BPSD):
Excess Naphtha from Crude Unit is stabilized.

2.3.1.8 Gas Sweetening Unit (35 tons/day H2S Removal):
Amine solution was used to sweetens the sour gas that produced in the refinery
facilities so that to remove any hydrogen sulphide inn order to minimize sulphur
oxide emissions.

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2.3.1.9 Sulphur Recovery Unit (35 tons/day):
The acid gases produced from Gas Sweetening Unit are converted to liquid
sulphur.

2.3.1.10 Jarn Yaphour Crude Oil Stabilization Plant (10,000 BPSD):
The Oil/Gas Separation Plant is designed to stabilize Crude from Jarn Yaphour
Wells, located some 30 kilometers from Abu Dhabi.
The separated gas is further treated to remove hydrogen sulphide, water and
hydrocarbon condensate before it is injected into GASCOs Main Gas Network.

2.3.2 Utilities, Off-sites, Terminal & ADR Technology
Additional Effluent Water Treatment facilities were installed to adhere to rigid oil in
water specification of 10 ppm maximum.

2.3.2.1 Utilities
Power and fresh was supplied from the adjacent plant of the Abu Dhabi Water
and Electricity Authority to the refinery.
Steam, Air, Nitrogen and Sea Water for cooling are all provided by the Refinery's
own facilities.
The Refinerys Fuel Gas supply is supplemented by Natural Gas from the GASCO
Main Network.

37 | P a g e

2.3.2.2 Off-sites
The storage capacity of Abu Dhabi Refinery Tank Farm is 500,000 cubic meters,
which includes facilities for Crude Oil, Intermediate Streams, Semi-Finished
Products, Finished Products and Utility Fuel Oil.
The Residue and Naphtha are shipped to Ruwais Refinery while most of the
Refined Products from Abu Dhabi Refinery are sold in the ever expanding
domestic market.

2.3.2.3 Marine Terminal
The Refinery is served by a two-Berth Marine Terminal on the North Shore of
the Island for loading and unloading of tankers.
Maximum Draft is 9.5 meters; maximum Cargo is 30,000 tons.

2.3.2.4 ADR Technology
Abu Dhabi Refinery completed the process of installing a fully integrated state-
of-the-art Computerized System designed to Modernize Operations in the year
1994.
In January 1993, the first level was achieved with the commissioning of a new
Consolidated Control Room under the overall Refinery expansion project.
The Refinery is equipped with a Distributed Control System (DCS).

38 | P a g e

DCS allowed for the introduction of an Advanced Process Control system as
part of the Process Automation and Computerization project (PACS).
PACS are designed to provide accurate and up-to-the-minute information on
every aspect of the Operations in Support of Operational and Management
Activities.
On the other hand, the second level of the project includes the implementation
of Advanced Process Control (APC) strategies and off-site Automation and
Computerization.
Third level involved the implementation of a plant-wide Data Base and
Communications Network, leading to the use of a Computerized Decision
Support System in laboratory management, Planning, Scheduling, Mass
Balancing, Oil Accounting and Performance Monitoring.


39 | P a g e

CRUDE DISTILLATION UNIT
NAPHTHA
HYDRODESULPHURISER UNIT
KEROSENE MEROX UNIT
CATALYTIC REFORMER UNIT
GAS OIL HYDRODESULPHURISER
UNIT
LPG TREATING AND RECOVERY
UNIT
EXCESS NAPHTHA STABILIZER
UNIT
GAS SWEETENING UNIT
SULPHUR RECOVERY UNIT
CRUDE OIL STABILIZATION
PLANT
85 000 BPSD
From crude oil to fraction of
naphtha, kerosene, gas oil and
straight run residue
22 795 BPSD
From straight run naphtha to heavy
naphtha, light naphtha and sour
liquefied petroleum gaese
21 250 BPSD
From mercaptans to disulphide
14 000 BPSD
From heavy naphtha cut to
gasoline blending component
22 500 BPSD
Product: Reduced sulphur
content of gas oil
3 480 BPSD
Product: Processed LPG
3 325 BPSD
Product: Stabilized naphtha
35 tons/day H2S removal
Product: Sweetened sour gases
35 tons/day
From acid gases to liquid
sulphur
10 000 BPSD
Product: Stabilized crude
ABU DHABI
REFINERY
Figure 2.4: Overall operation in Abu Dhabi Oil Refinery Company

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2.4 Mass Balance Based 400,000 BPD of Middle East Heavy Crude
By referring to US Petroleum Refinery Balance (Millions Barrels Per Day, Except Utilization Factor) as shown below:

Figure 2.5: US Petroleum Refinery Balance (Millions Barrels Per Day, Except Utilization Factor)

41 | P a g e

2.4.1 Mass Balance by Assumed Proportion of Refining Products is Double

Figure 2.6: By referring to the diagram above which consists of 200,000
barrels per day
(Source: Environmental Aspects in Refineries and Projects, 2012)


42 | P a g e

It is found that if the feedstock which is the 400 000 BPD Middle East heavy crude and assumed that the proportion of the refining
products is double and the number of the condensate is 560,000bbl/day, the final product will be shown in Table 2.1 below:
Table 2.1: Calculation of final product from 400 000 BPD Middle East heavy crude
Products
Quantity
(200,000 BPD)
Fraction Percentage (%)
Mass balance
(400,000 BPD)
Gasoline 55000 0.138 13.836478 110000
Fuel oil 31000 0.078 7.798742138 62000
Jet fuel & kerosene 112000 0.2818 28.17610063 224000
Gas oil 89000 0.2239 22.38993711 178000
LPG 16000 0.0403 4.025157233 32000
Naphta 94500 0.2377 23.77358491 189000
Total 397500 1 100 795000

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Figure 2.7: Comparison quantity of product produced

110000
62000
224000
178000
32000
189000
795000
0
100000
200000
300000
400000
500000
600000
700000
800000
900000
Gasoline Fuel oil Jet fuel &
kerosene
Gas oil LPG Naphta Total
Mass balance (400000bbl/d) (BPD)

44 | P a g e

2.4.2 Mass Balance by Fraction Method
Based on the production of Abu Dhabi Oil Refining Company (refinery plant) at the
year of 1996, the mass balance is done using fraction method.
Table 2.2: Calculation of final product from 400 000 BPD Middle East
heavy crude
Products
Quantity
(BPD)
Fraction
Percentage
(%)
Mass balance
(BPD)
Gasoline 46100 0.199222 19.92 79688.85048
Fuel oil 67000 0.289542 28.95 115816.7675
Jet fuel & kerosene 36200 0.156439 15.64 62575.62662
Gas oil 70000 0.302506 30.25 121002.5929
LPG 7100 0.030683 3.07 12273.12014
Asphalt 5000 0.021608 2.26 8643.042351
Total 231400 1 100 400 000

** This analysis is done based on a production rate from Abu Dhabi Oil Refining
Company (refinery plant) using heavy crude oil

45 | P a g e

0
20000
40000
60000
80000
100000
120000
140000
Q
U
A
N
T
I
T
Y

(
B
P
D
)
PRODUCT
Gasoline Fuel oil Jet fuel & kerosene Gas oil LPG Asphalt

46 | P a g e

2.4.3 Mass Balance based on Total Production from while Middle East Countries
There can be another analysis based on the total production from whole Middle East countries
MIDDLE EAST COUNTRIES STATISTIC
Table 2.3: Middle East Output of Refined Petroleum Products, 2005 (Thousand Barrels per Day)
Energy Information Administration, International Energy Annual 2006 Table Posted: December 8, 2008
Country
Motor
Gasoline
Jet
Fuel
Kerosene
Distillate
Fuel
Oil
Residual
Fuel
Oil
Liquefied
Petroleum
Gases
Other
Total Output of
Refined Petroleum
Products
Refinery
Fuel and
Loss
Bahrain 17.64 49.45 8.47 91.97 52.13 1.18 47.63 268.47 10.74
Iran 260.67 18.47 127.66 499.57 480.16 135.58 166.82 1,688.93 67.56
Iraq 74.43 12.82 23.19 104.40 152.15 36.61 51.83 455.44 17.52
Israel 63.78 24.16 3.37 62.22 49.95 18.32 23.12 244.90 9.42
Jordan 14.33 7.04 4.89 28.53 27.91 3.87 5.15 91.73 3.53
Kuwait 65.48 50.27 128.30 245.77 179.47 149.41 222.99 1,041.68 40.06
Lebanon 0 0 0 0 0 0 0 0 0

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Oman 14.84 3.69 0.23 14.61 34.92 2.42 0.48 71.20 2.85
Qatar 40.31 20.10 0.08 18.94 14.23 81.83 5.67 181.16 6.97
Saudi Arabia 347.63 143.98 81.51 647.59 487.58 34.90 343.49 2,086.68 83.47
Syria 31.95 4.80 1.14 74.96 88.01 10.77 43.19 254.81 9.80
United Arab Emirates 43.73 117.71 0 87.41 28.67 16.63 93.27 387.42 14.90
Yemen 27.93 8.02 2.31 19.61 8.24 3.09 6.73 75.93 2.92
Middle East 1,002.71 460.50 381.16 1,895.59 1,603.44 494.59 1,010.36 6,848.35 269.73


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Figure 2.9: Fraction of Middle East Output on 2005
motor gasoline
15%
jet fuel
7%
kerosene
5%
fuel oil
28%
fuel oil
23%
petroleum gases
7%
other
15%
Middle East Output of Refined Petroleum Product on 2005
motor gasoline jet fuel kerosene fuel oil fuel oil petroleum gases other

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Table 2.4: Calculation of final product from 400,000 BPD Middle East
heavy crude
Products
Quantity
(BPD)
Fraction
Percentage
(%)
Mass balance
(BPD)
Gasoline 1002.71 0.146416 14.64 58566.51602
Fuel oil 1895.59 0.276795 27.68 110718.0562
Jet fuel 460.5 0.067242 6.72 26896.98979
Kerosene 381.16 0.055657 5.57 22262.88084
LPG 494.59 0.07222 7.22 28888.12634
Asphalt 1010.36 0.147533 14.75 59013.33898
Residual fuel oil 1603.44 0.234135 23.41 93654.09186
TOTAL 6848.35 1 100 400 000


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0
20000
40000
60000
80000
100000
120000
Q
u
a
n
t
i
t
y

(
B
P
D
)
Product
Gasoline Fuel oil Jet fuel Kerosene LPG Asphalt Residual fuel oil

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2.5 Conclusion
With the increasing world energy demand, this situation has pushed the oil producing
countries, Middle East Countries, to start exploiting heavy oil reservoirs, which had
been neglected or little used and to increase the oil exploration activities. Currently,
there are some heavyweight producers such as Saudi Arabia, Venezuela and Iran
produce large quantities of heavy ( API < 20) sour crude with high sulfur content.
However, others such as Nigeria, the United Arab Emirates, Angola and Libya pump a
higher quality, light sweet crude, with low sulfur content.
Since the global energy demand is keep increasing, this has putting up pressure
on the major oil producing countries to increase their production capacities. With
Middle East Countries alone, the production capacity is expected to reach 4 million
barrels per day (MBPD) by the year of 2020 has reach.
It is important for the Middle East Countries to maintain its market share
besides increase production capacity. However, heavy crude oil (API < 20) must be
also used as gap filler.
Basically, these current events are facing the oil industry in Middle East
Countries with many decisions and technological challenges, including counteracting
expected increased risk of corrosion and equipment failures during the production and
refining of heavy crude oil. Inorganic salts, organic chlorides, organic acids, and sulfur
compounds can be consider as the most damaging impurities.


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Things might getting worst when many of the compounds are unstable during
refining operations and they break into smaller components or combine with other
constituents, concentrating corrodants in certain units, such as the breakdown of
sulfur compounds and organic chlorides.
However, most of the world refineries including Kuwait are equipped with alloys
that capable of handling sweet light crude, which is most suitable for refining into
petrol, gas oil and heating oil. On the other hand, refining of heavy crude is difficult
and is associated with operational problems.
Problem can be arise from the increased risk of corrosion, equipment failures,
and downtime of process units. This problem are caused by the high sulfur and salt
contents of these crudes including organic chlorides.


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3.0 GROUP PROJECT
3.1 Introduction To Cumene Production
The commercial production of cumene is by FriedelCrafts alkylation of
benzene with propylene. In previously, solid phosphoric acid (SPA) supported
on alumina was used as the catalyst. Therefore, since the mid-1990s, commercial
production has switched to zeolite-based catalysts.
distilling. The chemical is also flammable and incompatible with strong oxidizing agents.
Environmental laboratories commonly test isopropyl benzene using a Gas
3.1.1 Cumene Project Definition
Isopropylbenzene, also known as cumene, is among the top commodity chemicals,
taking about 7 8% from the total worldwide propylene consumption. Today, the
cumene is used almost exclusively for manufacturing phenol and acetone.
This case study deals with the design and simulation of a medium size plant of
100 kton cumene per year. The goal is performing the design by two essentially
different methods. The first one is a classical approach, which handles the process
synthesis and energy saving with distinct reaction and separation sections. In the
second alternative a more innovative technology is applied based on reactive
distillation.

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Table 3.1 presents the purity specifications. The target of design is achieving
over 99.9% purity. It may be seen that higher alkylbenzenes impurities are undesired.
Ethyl - and butylbenzene can be prevented by avoiding olefi ns and butylenes in the
propylene feed. N - propylbenzene appears by equilibrium between isomers and can
be controlled by catalyst selectivity.
In this project we consider as raw materials benzene of high purity and
propylene with only 10% propane. As an exercise, the reader can examine the impact
of higher propane ratios on design.
Table 3.1: Specifications For Cumene


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3.1.2 Cumene Manufacturing Routes
General information about chemistry, technology and economics can be found in the
standard encyclopaedic material, as well as in more specialized books. The
manufacturing process is based on the addition of propylene to benzene (Alexandre,
2008):

Beside isopropyl benzene (IPB) a substantial amount of polyalkylates is formed
by consecutive reactions, mostly as C6H5 - (C3H7) 2 (DIPB) with some C6H5 - (C3H7)
3 (TPB). The main reaction has a large exothermal effect, of 113 kJ/mol in standard
conditions. The alkylation reaction is promoted by acid - type catalysts.
The synthesis can be performed in gas or liquid phase. Before 1990 gas phase
alkylation processes dominated, but today liquid - phase processes with zeolite
catalysts prevail. Recent developments make use of reactive distillation.
Cumene processes based on zeolites are environmentally friendly, offering high
productivity and selectivity. The most important are listed in Table 3.2. The catalyst
performance determines the type and operational parameters of the reactor and,
accordingly the flowsheet configuration. The technology should find an efficient
solution for using the reaction heat inside the process and and/or making it available
to export. By converting the polyalkylbenzenes into cumene an overall yield of nearly
100% may be achieved.


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Table 3.2: Technologies for cumene manufacturing based on zeolites

Figure 3.1 illustrates a typical conceptual flowsheet. Propylene is dissolved in a
large excess of benzene (more than 5 : 1 molar ratio) at sufficiently high pressure that
ensures only one liquid phase at the reaction temperature, usually between 160 and
240 C. The alkylation reactor is a column filled with fixed-bed catalyst, designed to
ensure complete conversion of propylene. The reactor effluent is sent to the
separation section, in this case a series of four distillation columns: propane (LPG)
recovery, recycled benzene, cumene product and separation of polyisopropylbenzenes.
The flowsheet involves two recycles: nonreacted benzene to alkylation and
polyalkylbenzenes to transalkylation. The minimization of recycle flows and of energy
consumption in distillation are the key objectives of the design.
These can be achieved by employing a highly active and selective catalyst, as
well as by implementing advanced heat integration.

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Figure 3.1: Conceptual Flowsheet for cumene manufacturing by Dow-
kellogg process


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3.1.3 General Overall Material Balance for Cumene Process
Table 3.3 illustrates a typical material balance of a cumene plant using Dow-Kellog
technology. The propylene may contain up to 40% propane, but without ethylene and
butylene. Beside cumene, variable amounts of LPG can be obtained as subproducts.
Energy is also exported as LP steam, although it is consumed as well as other utilities
(fuel, cooling water, electricity).
Table 3.3: Overall Process Material Balance After Dow-Kellog Technology


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3.1.4 Physical Properties
Table 3.4 presents some fundamental physical constants. Critical pressures of propane
and propylene are above 40 bar, but in practice 20 to 30 bar are sufficient to ensure
a high concentration of propylene in the coreactant benzene. From the separation
viewpoint one may note large differences in the boiling points of components and no
azeotrope formation. In consequence, the design of the separation train should not
raise particular problems. Since the liquid mixtures behave almost ideally a deeper
thermodynamic analysis is not necessary. The use of vacuum distillation is expected
because of the high boiling points of the polyalkylated benzenes.
Table 3.4: Basic physical properties of components in the outlet reactor
mixture


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3.2 Cumene Process
The Cumene process (Cumene-phenol process, Hock process) is an industrial
process for developing phenol and acetone from benzene and propylene. The term
stems from cumene (isopropyl benzene), the intermediate material during the process.
It was invented by Heinrich Hock in 1944

and independently by R. dris and P.
Sergeyev in 1942 (USSR).

This process converts two relatively cheap starting
materials, benzene and propylene, into two more valuable ones, phenol and acetone.
Other reactants required are oxygen from air and small amounts of a radical initiator.
Most of the worldwide production of phenol and acetone is now based on this method.
In 2003, nearly 7 billion kg of phenol was produced by the Hock Process.


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3.3.1 Technical Description
Benzene and propylene are compressed together to a pressure of 30 standard
atmospheres at 250 C (482 F) in presence of a catalytic Lewis acid. Phosphoric
acid is often favored over aluminium halides. Cumene is formed in the gas-
phase Friedel-Crafts alkylation of benzene by propylene:

Cumene is oxidized in air which removes the tertiary benzylic hydrogen from
cumene and hence forms a cumene radical:


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3.2.1 Cumene Chemical Properties
Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and
benzene. It is insoluble in water. Cumene is oxidized in air which removes the
tertiary benzylic hydrogen from cumene and hence forms a cumene radical:

This cumene radical then bonds with an oxygen molecule to give cumene
hydroperoxide radical, which in turn forms cumene hydroperoxide (C6H5C(CH3)2-O-O-
H) by abstracting benzylic hydrogen from another cumene molecule.
This latter cumene converts into cumene radical and feeds back into
subsequent chain formations of cumene hydroperoxides. A pressure of 5 atm is used
to ensure that the unstable peroxide is kept in liquid state.


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Cumene hydroperoxide is then hydrolysed in an acidic medium (the Hock
rearrangement) to givephenol and acetone. In the first step, the terminal
hydroperoxy oxygen atom is protonated.
This is followed by a step in which the phenyl group migrates from the benzyl
carbon to the adjacent oxygen and a water molecule is lost, producing
a resonance stabilized tertiary carbocation.
The concerted mechanism of this step is similar to the mechanisms of
the Baeyer-Villiger oxidationand also the oxidation step of hydroboration-
oxidation.
[6]
In 2009, an acidified bentonite clay was proven to be a more economical
catalyst than sulfuric acid as the acid medium.


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As shown below, the resulting carbocation is then attacked by water, a proton
is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion
falls apart into phenol and acetone.

The products are extracted by distillation.
3.3 Chemical Reaction Network
The mechanism of benzene alkylation with propylene involves the protonation of the
catalyst acidic sites [5, 6] leading to isopropylbenzene, and further di-
isopropylbenzenes and tri - isopropylbenzenes. By the isomerization some n -
propylbenzene appears, which is highly undesirable as an impurity. The presence of
stronger acid sites favors the formation of propylene oligomers and other hydrocarbon
species. Therefore, high selectivity of the catalyst is as important as high activity. It is
remarkable that the polyalkylates byproducts can be reconverted to cumene by
reaction with benzene. Below, the chemical reactions of significance are listed:


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3.4 Various Processes of Manufacture
Currently almost all cumene is produced commercially by two processes. The first type
is A fixed bed, Kieselguhr supported phosphoric acid catalyst system developed by
UOP (Universal Oil Products Platforming Process). The second type is A homogeneous
AlCl3 and hydrogen chloride catalyst system developed by Monsanto.
3.4.1 UOP Cumene Process

Figure 3.5: PFD for UOP Cumene Process


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Propylene feed fresh benzene feed and recycle benzene are charged to the upflow
reactor, which operates at 3-4 Mpa and at 200-260C. The solid phosphoric acid
catalyst provides an essentially complete conversion of propylene on a one-pass basis.
The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %
of diiso propylbenzene. The remaining 2.1 % is primarily heavy aromatics. This high
yield of cumene is achieved without transalkylation of diiso propylbenzene and is
unique to the solid phosphoric acid catalyst process.
The cumene product is 99.9 Wt. % pure and the heavy aromatics, which have
an octane number of 109, can either be used as high octane gasoline blending
components or combined with additional benzene and sent to a transalkylation section
of the plant where diiso propylbenzene is converted to cumene.
The overall yields of cumene for this process are typically 97-98 Wt. % with

3.4.1.1 Application
To produce high-quality cumene (isopropylbenzene) by alkylating benzene with
propylene (typically renery or chemical Grade) using liquid-phase Q-Max process
based on zeolitic catalyst Technology.


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3.4.1.2 Description
Benzene is alkylated to cumene over a zeolite catalyst in a fixed-bed, liquid-phase
reactor. Fresh benzene is combined with recycle benzene and fed to the alkylation
reactor (1). The benzene feed flows in series through the beds, while fresh propylene
feed is distributed equally between the beds. This reaction is highly exothermic, and
heat is removed by recycling a portion of reactor effluent to the reactor inlet and
injecting cooled reactor effluent between the beds.
In the fractionation section, propane that accompanies the propylene feedstock
is recovered as LPG product from the overhead of the depropanizer column (2),
unreacted benzene is recovered from the overhead of the benzene column (4) and
cumene product is taken as overhead from the cumene column (5). Di-
isopropylbenzene (DIPB) is recovered in the overhead of the DIPB column (6) and
recycled to the transalkylation reactor (3) where it is transalkylated with benzene over
a second zeolite catalyst to produce additional cumene. A small quantity of heavy
byproduct is recovered from the bottom of the DIPB column (6) and is typically
blended to fuel oil. The cumene product has a high purity (99.96 99.97 wt%), and
cumene yields of 99.7 wt% and higher are achieved.
The zeolite catalyst is noncorrosive and operates at mild conditions; thus,
carbon-steel construction is possible. Catalyst cycle lengths are two years and longer.
The catalyst is fully regenerable for an ultimate catalyst life of six years and longer.
Existing plants that use spa or ALCL3 catalyst can be revamped to gain the advantages
of Q-Max cumene technology while increasing plant capacity.

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3.4.1.3 Economics
Basis: ISBL US Gulf Coast

The Q-Max design is typically tailored to provide optimal utility advantage for the plant
site, such as minimizing heat input for stand-alone operation or recovering heat as
steam for usage in a nearby phenol plant.

3.4.1.4 Commercial Plants
Seven Q-Max units are in operation with a total cumene capacity of 2.3 million tpy,
and two additional units are either in design or under construction.


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3.4.2 Badger Cumene Process

Figure 3.6: PFD for Badger Cumene Process

3.4.2.1 Application
To produce cumene from benzene and any grade of Propyleneincluding lower-
quality renery propylene-propane mixturesusing the badger process and a new
generation of zeolite catalysts from Exxonmobil.
3.4.2.2 Description
The process includes: a xed-bed alkylation reactor, a xed-bed transalkylation reactor
and a distillation section. Liquid propylene and benzene are premixed and fed to the

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alkylation reactor (1) where propylene is completely reacted. Separately, recycled
polyisopropylbenzene (PIPB) is premixed with benzene and fed to the transalkylation
reactor (2) where PIPB reacts to form additional cumene. The transalkylation and
alkylation efuents are fed to the distillation section. The distillation section consists
of as many as four columns in series. The depropanizer (3) recovers propane overhead
as LPG. The benzene column (4) recovers excess benzene for recycle to the reactors.
The cumene column (5) recovers cumene product overhead. The PIPB column (6)
recovers PIPB overhead for recycle to the transalkylation reactor.

3.4.2.3 Process features
The process allows a substantial increase in capacity for existing SPA, ALCL3, or other
zeolite cumene plants while improving product purity, feedstock consumption, and
utility consumption. The new catalyst is environmentally inert, does not produce
byproduct oligomers or coke and can operate at the lowest benzene to propylene
ratios of any available technology with proven commercial cycle lengths of over seven
years. Expected catalyst life is well over ve years.

3.4.2.4 Yield and Product Purity
This process is essentially stoichiometric and product purity above 99.97% weight has
been regularly achieved in commercial operation.


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3.4.2.5 Economics
Estimated ISBL investment for a 300,000-MTPY unit on the Us Gulf Coast (2004
construction basis), is US$15 million.
UTILITY REQUIREMENTS, PER TON OF CUMENE PRODUCT:
HEAT, MMKCAL (IMPORT) 0.32
STEAM, TON (EXPORT) (0.60)

The utilities can be optimized for specic site conditions/economics and integrated
with an associated phenol plant.

The rst commercial application of this process came onstream in 1996. At present,
there are 12 plants operating with a combined capacity exceeding 5.2 million mtpy.
In addition, four grassroots plants and an ALCL3 revamp are in the design phase. Fifty
percent of the worldwide and 75% of zeolite cumene production are from plants using
the badger process.


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3.4.3 MONSANTO LUMMUS CREST Cumene Process
Dry benzene, fresh and recycle and propylene are mixed in the alkylation reaction
zone with AlCl3 and hydrogen chloride catalyst at a temperature of less than 135C
and a pressure of less than 0.4 Mpa.
The effluent from the alkylation zone is combined with recycle polyisopropyl
benzene and fed to the transalkylation zone, where polyisopropyl benzenes are
transalkylated to cumene. The strongly acidic catalyst is separated from the organic
phase by washing the reactor effluent with water and caustic.
The distillation system is designed to recover a high purity cumene product.
The unconverted benzene and polyisopropyl benzene are separated and recycled to
the reaction system. Propane in the propylene feed is recovered as liquid petroleum
gas.
The overall yields of cumene for this process can be high as 99 Wt. % based
on benzene and 98 Wt. % based on propylene. But these processes have been used
more extensively for the production of ethylbenzene than for the production of
cumene.


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3.4.4 CDTECH & ABB Lummus Global
3.4.4.1 Overview
The CDCumene process, marketed by ABB, produces ultra high purity cumene using
a proprietary zeolite catalyst that is non-corrosive and environmentally friendly. The
CDCumene technology is one of a family of process technologies developed and
commercialized by Catalytic Distillation Technologies (CDTECH) for license to the
petroleum refining and petrochemical industries. CDTECH is a partnership between
ABB Lummus Global and Chemical Research and Licensing.

3.4.4.2 Application
Advanced technology to produce high-purity cumene from propylene and benzene
using patented catalytic distillation (CD) Technology. The CD cumene process uses a
specially formulated zeolite alkylation catalyst packaged in a proprietary CD structure
and another Specially formulated zeolite transalkylation catalyst in loose form.


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3.4.4.3 Description

Figure 3.7: PFD of CDTECH & ABB LUMMUS GLOBAL
The cd column (1) combines reaction and fractionation in a single-unit operation.
Alkylation takes place isothermally and at low temprature. Cd also promotes the
continuous removal of reaction products from reaction zones. These factors limit
byproduct impurities and enhance product purity and yield. Low operating
temperatures and pressures also decrease capital investment, improve operational
safety and minimize fugitive emissions.
in the mixed-phase CD reaction system, propylene concentration in the liquid
phase is kept extremely low (<0.1 wt%) due to the higher volatility of propylene to
benzene. This minimizes propylene oligomerization, the primary cause of catalyst

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deactivation and results in catalyst run lengths of 3 to 6 years. The vapor-liquid
equilibrium effect provides propylene dilution unachievable in xed-bed systems, even
with expensive reactor pumparound and/or benzene recycle arrangements.
Overhead vapor from the CD column (1) is condensed and returned as reux
after removing propane and lights (p). The CD column bottom section strips benzene
from cumene and heavies. The distillation train separates cumene product and
recovers polyisopropylbenzenes (PIPB) and some heavy aromatics (h) from the net
bottoms. PIPB reacts with benzene in the transalkylator (2) for maximum cumene
yield. Operating conditions are mild and noncorrosive; standard carbon steel can be
used for all equipment.

Figure 3.8: PFD of CDTECH & ABB LUMMUS GLOBAL
Cumene is formed by the catalytic alkylation of benzene with propylene.
CDTECHs patented CDCumene process uses a proprietary zeolite catalyst in its
patented catalytic distillation structures.

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The catalyst is non-corrosive and environmentally sound. This modern process
features higher product yields, with a much lower capital investment, than the
environmentally outdated acid-based processes.
The exceptional quality of the cumene product from the CDCumene process
easily surpasses current requirements of phenol producers, and may well define
tomorrows more stringent quality standards.
The unique catalytic distillation column combines reaction and fractionation in
a single unit operation. The alkylation reaction takes place isothermally and at low
temperature. Reaction products are continuously removed from the reaction zones by
distillation. These factors limit the formation of by-product impurities, enhance product
purity and yields, and result in expected reactor run lengths in excess of two years.
Low operating temperatures result in lower equipment design and operating pressures,
which help to decrease capital investment, improve safety of operations, and minimize
fugitive emissions. All waste heat, including the heat of reaction, is recovered for
improved energy efficiency. The CDCumene technology can process chemical or
refinery grade propylene. It can also use dilute propylene streams with purity as low
as 10 mol%, provided the content of other olefins and related impurities are within
specification.


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3.4.4.4 Advantages

Figure 3.9: Advantages of CDTECH & ABB LUMMUS GLOBAL
3.4.4.5 Performance Characteristics

Figure 3.10: Typical Overall Mass Balance

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Figure 3.11: Cumene Product Quality

3.4.4.6 Process Chemistry

Figure 3.12: Process Chemistry of the Process

3.4.4.7 Yields
100,000 metric tons (mt) of cumene are produced from 65,000 mt of benzene and
35,300 mt of propylene giving a product yield of over 99.7%. Cumene product is at
least 99.95% pure and has a bromine index of less than 2, without clay treatment.

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3.4.4.8 Economics
Based on a 300,000-MTPY cumene plant located in the US Gulf Coast, the ISBL
investment is about US$15 million.

Figure 3.13: Typical Operating Requirements

FORMOSA CHEMICALS & FIBRE CORPORATION, TAIWAN540,000 MTPY.

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3.4.5 Q-MAX Process
The Q-Max process converts benzene and propylene to high-quality cumene by using
a regenerable zeolitic catalyst.
The Q-Max process represents a substantial improvement over older cumene
technologies and is characterized by its exceptionally high yield, superior product
quality, low investment and operating costs, reduction in solid waste, and corrosion-
free environment.
Cumene is produced commercially through the alkylation of benzene with
propylene over an acid catalyst.
Over the years, many different catalysts have been proposed for this alkylation
reaction, including boron trifluoride, hydrogen fluoride, aluminum chloride, and
phosphoric acid.
In the 1930s, UOP introduced the UOP catalytic condensation process, which
used a solid phosphoric acid (SPA) catalyst to oligomerize light olefin by-products from
petroleum thermal cracking into heavier paraffins that could be blended into gasoline.
During World War II, this process was adapted to produce cumene from
benzene and propylene to make a high-octane blending component for military
aviation gasoline. Today, cumene is no longer used as a fuel, but it has grown in
importance as a feedstock for the production of phenol.


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Although SPA is a highly efficient and economical catalyst for cumene synthesis,
it has two important limitations:
1. Cumene yield is limited to about 95 percent, because of the oligomerization of
propylene and the formation of heavy alkylate by-products
2. The catalyst is not regenerable and must be disposed of at the end of each
catalyst cycle.
In recent years, producers have been under increasing pressure to improve cumene
product quality so that the quality of the phenol produced downstream (as well as
acetone and alpha-methylstyrene, which are coproduced with phenol) could be
improved. Twenty-five years ago, most phenol was used to produce phenolic resins,
and acetone was used primarily as a solvent.
Today, both phenol and acetone are used increasingly in the production of
polymers such as polycarbonates and nylon. Over the years, improvements to the SPA
producers still sought an improved cumene process that would produce a better-
quality product at higher yield.
Because zeolites are known to selectively perform many acid-catalyzed
reactions, UOP began searching for a new cumene catalyst that would overcome the
limitations of SPA.
UOPs objective was to develop a regenerable catalyst that would increase the
yield of cumene and lower the cost of production. More than 100 different catalyst
materials were screened, including mordenites, MFIs, Y-zeolites, amorphous silica-
aluminas, and betazeolite.

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The most promising materials were modified to improve their selectivity and
then subjected to more-rigorous testing. By 1992, UOP had selected the most
promising catalyst based on beta-zeolite for cumene production and then began to
optimize the process design around this new catalyst. The result of this work is the Q-
Max process and the QZ- 2000 catalyst system.


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3.5 Description On Q-Max Process
1. Raw material propylene and benzene are used for the production of cumene.
2. These are stored in the respective storage tanks of 500MT capacity in the
storage yard pumped to the unit by the centrifugal pumps.
3. Benzene pumped to the feed vessel which mixes with the recycled benzene.
Benzenestream is pumped through the vaporizer with 25 atm pressure and
vaporized to the temperature of 243degC, mixed with the propylene which
is of same and temperature and pressure of benzene stream.
4. This reactant mixture passed through a fired super heater where reaction
temperature 350degC is obtained.
5. The vapor mixture is sent to the reactor tube side which is packed with the
solid phosphoric acid catalyst supported on the kieselguhr the exothermal
heat is removed by the pressurized water which is used for steam
production and the effluent from the reactor i.e., cumene, p-DIPB,
unreacted benzene, propylene and propane with temperature 350oC is used
as the heating media in the vaporizer which used for the benzene vaporizing
and cooled to 40oC in a water cooler, propylene and propane are separated
from the liquid mixture of cumene, p-DIPB, benzene in a separator
operating slightly above atm and the pressure is controlled by the vapor
control value of the separator, the fuel gas is used as fuel for the furnace
also.
6. The liquid mixture is sent to the benzene distillation column which operates
at 1 atm pressure, 98.1% of benzene is obtained as the distillate and used

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as recycle and the bottom liquid mixture is pumped at bubble point to the
cumene distillation column where distillate 99.9% cumene and bottom pure
p-DIPB is obtained.
7. The heat of bottom product p-DIPB is used for preheating the benzene
column feed, All the utility as cooling water, electricity, steam from the boiler,
pneumatic air are supplied from the utility section
8. The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %
of diiso propylbenzene. The remaining 2.1 % is primarily heavy aromatics.
9. This high yield of cumene is achieved without transalkylation of diiso
propylbenzene and is unique to the solid phosphoric acid catalyst process.
10. The cumene product is 99.9 Wt. % pure and the heavy aromatics, which
have an octane number of 109, can either be used as high octane gasoline
blending components or combined with additional benzene and sent to a
transalkylation section of the plant where diiso propylbenzene is converted
to cumene.
11. The overall yields of cumene for this process are typically 97-98 Wt. % with


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3.6 Description On Process Flow
A representative Q-Max flow diagram is shown. The alkylation reactor is typically
divided into four catalyst beds contained in a single reactor shell.
The fresh benzene is routed through the upper midsection of the depropanizer
column to remove excess water and then sent to the alkylation reactor via a sidedraw.
The recycle benzene to both the alkylation and transalkylation reactors comes from
the overhead of the benzene column.
A mixture of fresh and recycle benzene is charged downflow through the
alkylation reactor. The fresh propylene feed is split between the four catalyst beds. An
excess of benzene is used to avoid polyalkylation and to help minimize olefin
oligomerization.
Because the reaction is exothermic, the temperature rise in the reactor is
controlled by recycling a portion of the reactor effluent to the reactor inlet, which acts
as a heat sink. In addition, the inlet temperature of each downstream bed is reduced
to the same temperature as that of the first bed inlet by injecting a portion of cooled
reactor effluent between the beds.
Effluent from the alkylation reactor is sent to the depropanizer column, which
removes any propane and water that may have entered with the propylene feed.
The bottoms from the depropanizer column are sent to the benzene column,
where excess benzene is collected overhead and recycled. Benzene column bottoms
are sent to the cumene column, where the cumene product is recovered overhead.
The cumene column bottoms, which contain mostly di-isopropylbenzene, are sent to

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the DIPB column. The DIPB stream leaves the column by way of a sidecut and is
recycled to the transalkylation reactor. The DIPB column bottoms consist of heavy
aromatic by-products, which are normally blended into fuel oil. Steam or hot oil
provides the heat for the product fractionation section.
A portion of the recycle benzene from the top of the benzene column is
combined with the recycle DIPB from the sidecut of the DIPB column and sent to the
transalkylation reactor.
In the transalkylation reactor, DIPB and benzene are converted to additional
cumene. The effluent from the transalkylation reactor is then sent to the benzene
column. The QZ-2000 catalyst utilized in both the alkylation and transalkylation
reactors is regenerable.
At the end of each cycle, the catalyst is typically regenerated ex-situ via a simple
carbon burn by a certified regeneration contractor. However, the unit can also be
designed for in-situ catalyst regeneration.
Mild operating conditions and a corrosion-free process environment permit the
use of carbon-steel construction and conventional process equipment.


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3.7 Process Chemistry Chemical Reactions
The synthesis of cumene from benzene and propylene is a modified Friedel-Crafts
alkylation, which can be accomplished by many different acid catalysts. The basic
alkylation chemistry and reaction mechanism are shown in Figure 3.14
The olefin forms a carbonium ion intermediate, which attacks the benzene ring
in an electrophilic substitution. The addition to the olefin double bond is at the middle
carbon of propylene, in accordance with Markovnikovs rule.
The addition of the isopropyl group to the benzene ring weakly activates the
ring toward further alkylation, producing di-isopropyl-benzene (DIPB) and heavier
alkylate by-products.
The QZ-2000 catalyst functions as strong acid. In the QZ-2000 catalyst, the
active surface sites of the silica-alumina structure act to donate the proton to the
adsorbed olefin.
Because the QZ-2000 catalyst is a strong acid, it can be used at a very low
temperature. Low reaction temperature reduces the rate of competing olefin
oligomerization reactions, resulting in higher selectivity to cumene and lower
production of heavy by-products.


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Figure 3.14: Alkylation Chemistry


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3.7.1 Transalkylation Of DIPB
Transalkylation is the acid-catalyzed transfer of one isopropyl group from DIPB to a
benzene molecule to form two molecules of cumene (Figure 3.15). The Q-Max process
is designed with an alkylation reactor section, which produces about 85 to 95 wt %
cumene and 5 to 15 wt % DIPB. After recovery of the cumene product by fractionation,
the DIPB is reacted with recycle benzene at optimal conditions for transalkylation to
produce additional cumene. With the alkylation and transalkylation reactors working
together to take full advantage of the QZ-2000 catalyst, the overall yield of cumene is
increased to 99.7 wt %.

Figure 3.15: Transalkylation Chemistry


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3.7.2 Side Reactions
In addition to the principal alkylation reaction of benzene with propylene, all acid
catalysts promote the following undesirable side reactions to some degree (Figure
3.16):
1. Oligomerization of olefins. The model for acid-catalyzed alkylation is
diffusion of the olefin to an active site saturated with benzene followed by
adsorption and reaction. One possible side reaction is the combination of
the propyl carbonium ion with propylene to form a C6 olefin or even further
reaction to form C9, C12, or heavier olefins.
2. Alkylation of benzene with heavy olefins. Once heavy olefins have been
formed through oligomerization, they may react with benzene to form
hexylbenzene and heavier alkylated benzene by-products.
3. Polyalkylation. The addition of an isopropyl group to the benzene ring to
produce cumene weakly activates the ring toward further substitution,
primarily at the meta and para positions, to make DIPB and heavier alkylates.
4. Hydride-transfer reactions. Transfer of a hydrogen to an olefin by the
tertiary carbon on cumene can form a cumyl carbonium ion that may react
with a second benzene molecule to form diphenylpropane
5. In the Q-Max process, the reaction mechanism of the QZ-2000 catalyst and
the operating conditions of the unit work together to minimize the impact
of these side reactions. The result is an exceptionally high yield of cumene
product.

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Figure 3.16: Possible alkylation side reactions


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3.8 Process Flow Diagram (PFD)

Figure 3.17: Process Flow Diagram For The Production of Cumene Process

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Figure 3.18: Process Flow Diagram For The Production of Cumene Process

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Figure 3.19: Simple Process Flow Diagram For The Production of Cumene Process

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3.9 Description
Basically, cumene is produced in large scale plants as intermediate for the phenol
manufacturing; it is used as raw material for obtaining phenol and acetone. By reacting
benzene and propylene, cumene can be produced.
Actually, this reaction can be occurred in liquid and gas phases, but high
conversion are obtained at gas phase reactions, catalyst like solid phosphoric acid are
replaced by zeolites and the catalytic conversion reaction are held in shell and tube
reactors rather than packed fixed bed reactors. Cumene process reaction is exothermic
in nature so a complex shell and tube reactor designs are not sufficient for energy
conversion, tremendous research work is involved in design a rector of Cumene
production from benzene and propane.


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3.10 Cumene Plant Section
Cumene plant consist of the following sections:
1. Storage and pumping sectio
2. Preheating and vaporization section
3. Reactor section
4. Separation and purification section

3.10.1 Storage and pumping section
Benzene (99.9%) and propane (95%) are stored in liquid state in storage tanks
and propane is stored in sphere.
Benzene excess reactant is mixed in the circulation tank where propane is
added to the stream line of the feed inlet to the cascade of heat exchangers.

3.10.2 Preheating and vaporization section
Benzene and propane are mixed with the 2:1 ratio and fed to preheating section
where a continuous series of heat exchanger are used to heat up the feed
mixture with the effluents form the Cumene reactor.
Finally after the heat exchanger a fired heater is used to vaporize and raise the
temperature of the mixture to the reaction condition temperature.
Pressure is maintained by the compressors from pumping section


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3.10.3 Reactor section
A shell and tube reactor is designed as such to with stand the pressure up to
25 atm and 350 degree centigrade the reactor tube are filled with catalyst and
the feed is charged from the top and gas reacts and pass over the catalyst bed
with 99% conversion of propylene and outlet stream is sent to the recycle and
purification section, where side reaction will generate compounds like diiso
propylbenzene (DIPB).

3.10.4 Separation and purification section
Unreacted benzene is separated in a distillation column from the effluent
obtained from the reactor and the recovered benzene is recycled to the feed
stream, diisopropylbenzene which formed as by product is separated a sieve
tray distillation column which is of 99 percent pure.


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3.11 Current Industrial Cumene Production Process: UOP Process
Cumene is an important chemical in the present industrial world and its uses are
steadily increasing. The process followed for the production of cumene is the catalytic
alkylation of benzene with propylene and now a days zeolite based catalysts are used
in place of the normal acid based catalysts due to added advantages.
Cumene production process has been greatly studied and the reaction
mechanism and the reaction kinetics have been specified by many researchers. Both
experimental as well as computer based simulation and optimization studies have been
carried out by various researchers.
The UOP process converts a mixture of benzene and propylene to high quality
cumene using a regenerable zeolite catalyst. The UOP process is characterized by a
exceptionally high yield, better product quality, less solid waste, decrease in
investment and operating costs and a corrosion free environment. The UOP process
uses QZ-2000/ QZ-2001 catalyst which is a variant of - zeolite.


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3.12 UOP Process Description For Cumene Production
The UOP process provides a very good cumene yield and quality. The QZ-2000 zeolite
based catalyst utilized for the UOP process which operates with a low flow rate of
benzene and hence investment and utility costs are reduced greatly.
QZ-2000 is non-corrosive and regenerate-able. Compared to other zeolite
based cumene technologies, the UOP process provides the highest product quality and
great stability. Impurities in the fee have less effect
The alkylation reactor is divided into four catalytic beds present in a single
reactor shell. The fresh benzene feed is passed through the upper-mid section of the
depropanizer column to remove excess water and then sent to the alkylation reactor.
The recycle benzene to the alkylation and transalkylation reactors is drawn from
the benzene column. This mixture of fresh and recycle benzene is charged through
the alkylation reactor. The fresh propylene feed is split between the catalyst beds and
is fully consumed in each bed.
An excess of benzene helps in avoiding formation of poly alkylation and reduce
the effect of olefin oligomerization.
As the chemical reaction occurs at exothermic condition, the temperature
increase during the alkylation reaction is controlled by the reactor effluent. The
temperature of inlet stream from the catalyst beds is further maintained to the
designed temperature by the circuit reactor effluent passing tubes which are cooled
by the side stream heat exchangers between the beds.

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Reacted effluent from the chemical reactor is fed to depropanizer column which
separates the propane and excess water. The bottoms stream of the depropanizer
column is fed to the benzene distillation column where excess benzene is collected at
top of the column and recycled to the process fed stream.
The benzene distillation column bottom stream fed to the cumene rectifying
column where cumene is recovered overhead. The cumene rectifying column bottom
product is diisopropylbenzene (DIPB), and fed to the DIPB rectifying column. The
DIPB stream is recycled to increase the conversion to the transalkylation reactor.
The DIPB column bottom products contains of heavy aromatic by-products,
which are blended into fuel oil. High pressure steam is used as heating medium to
the fractionation columns. The recycle DIPB from the overhead of the DIPB column
combines with a portion of the recycle benzene and is charged downflow through the
transalkylation reactor. In the transalkylation reactor, DIPB and benzene are converted
to more cumene. The effluent from the transalkylation reactor is then sent to the
benzene column.
The new QZ-2001 catalyst is utilized in the alkylation reactor while the original
QZ-2000 catalyst used for the transalkylation reactor. Catalyst life time is about 24
years.
The UOP process typically produces near equilibrium levels of cumene (between
85 and 95 mol %) and DIPB (between 5 and 15 mol %). The DIPB is separated from
the cumene and is reacted with recycle benzene at optimal conditions for
transalkylation to produce additional cumene.

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3.13 Description Of Process Units
With the aid of the preliminary aid diagram,

Figure 3.20: Simple Process Flow Diagram For The Production of Cumene Process

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3.13.1 V-201 Vaporizer
Liquid feeds are vaporized and heated for reactor

3.13.2 R-201 Reactor
Vapors are reacted over catalyst; temperature 350C; pressure 25 atm.; 99%
propylene conversion per pass; 31/1 cumene/DIPB molar selectivity

3.13.3 S-201 Separator
Vapor is cooled to 40C at 25 atm. pressure, separating essentially all of the benzene,
cumene and DIPB as a liquid from propylene and propane gases

3.13.4 T-201 Distillation Tower No. 1
Overhead stream contains 98.1 mole% benzene, balance cumene; bottoms stream
contains cumene and DIPB

3.13.5 T-202 Distillation Tower No. 2
Overhead stream contains 99.9 mole% cumene; bottoms stream contains pure DIPB


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3.14 Description Of Process Streams
3.14.1 Stream 1
Benzene>99.9 mole% pure; liquid feed

3.14.2 Stream 2
95 mole% propylene; 5 mole% propane; liquid feed

3.14.3 Stream 3
2/1 benzene/propylene molar feed ratio

3.14.4 Stream 4
99% propylene conversion; 31/1 cumene/DIPB molar selectivity

3.14.5 Stream 5
Propylene + propane only

3.14.6 Stream 6
0 mole% propylene + propane

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3.14.7 Stream 7
98.1 mole% benzene purity, balance cumene, sold as gasoline

3.14.8 Stream 8
0 mole% benzene

3.14.9 Stream 9
99.9 mole% cumene, balance DIPB; 100,000 tons/year production

3.14.10 Stream 10
100 mole% DIPB; sold as fuel oil


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3.15 Reaction Mechanism And Kinetics Of Cumene Production
The following reaction mechanism are proposed for the alkylation of benzene for
production of cumene.
The major reactions taking place are alkylation and trans-alkylation. Side
reactions which take place are isomerisation and dis-proportionation.
The reaction mechanism and kinetics may vary depending on the catalyst used.
The reaction can occur in presence or absence of carbonium ion intermidate.


108 | P a g e

4.0 CAPACITY CALCULATION
4.1 Mass Balance
4.1.1 Introduction to Mass Balance
Basically, mass balance or material balance is an application of conservation of
mass to the analysis of physical systems. Mass flows can be identified which might
have been unknown, or difficult to measure without this technique by accounting for
material entering and leaving a system. The exact conservation law used in the
analysis of the system depends on the context of the problem but all revolve around
mass conservation, i.e. that matter cannot disappear or be created spontaneously
(Himmelblau, 1967).
So, in engineering and environmental analyses, mass balances are used widely.
Mass balance theory can be used to design chemical reactors, analyses alternative
processes to produce chemicals as well as in pollution dispersion models and other
models of physical systems. Closely related and complementary analysis techniques
include the population balance, energy balance and the somewhat more
complex entropy balance. These techniques are required for thorough design and
analysis of systems such as the refrigeration cycle.
Therefore, the general form quoted for a mass balance is The mass that enters
a system must, by conservation of mass, either leave the system or accumulate within
the system.


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Mathematically the mass balance for a system without a chemical reaction is as
follows:
Input = Output + Accumulation
above equation holds also for systems with chemical reactions if the terms in
the balance equation are taken to refer to total mass i.e. the sum of all the chemical
species of the system. In the absence of a chemical reaction the amount of any
chemical species flowing in and out will be the same. This gives rise to an equation for
each species in the system. However if this is not the case then the mass balance
equation must be amended to allow for the generation or depletion (consumption) of
each chemical species.
Some use one term in this equation to account for chemical reactions, which
will be negative for depletion and positive for generation. However, the conventional
form of this equation is written to account for both a positive generation term (i.e.
product of reaction) and a negative consumption term (the reactants used to produce
the products). Although overall one term will account for the total balance on the
system, if this balance equation is to be applied to an individual species and then the
entire process, both terms are necessary.
Input + Generation = Output + Accumulation + Consumption
This modified equation can be used not only for reactive systems, but for
population balances such as occur in particle mechanics problems. The equation is
given below. Note that it simplifies to the earlier equation in the case that the
generation term is zero.

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In the absence of a nuclear reaction the number of atoms flowing in and out
are the same, even in the presence of a chemical reaction
To perform a balance the boundaries of the system must be well defined
Mass balances can be taken over physical systems at multiple scales.
Mass balances can be simplified with the assumption of steady state, where the
accumulation term is zero


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4.1.2 Material Balance of Major Equipment - Reactor

The reactions for cumene production from benzene and propylene are as follows:

MAIN REACTION: C3H6 + C6H6 C6H5-C3H7
Propylene Benzene Cumene
SIDE REACTION: C3H6 + C6H5-C3H7 C3H7-C6H4-C3H7
Propylene Cumene Diisopropylbenzene (DIPB)

Major
Equipment
Reactor
Propylene
Benzene
Cumene
DIPB
Unreacted
Benzene

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4.1.2.1 Assume 330 working days per year and 24 hours per day
Basis: Per hour of operation
(a) Assumption
330 working days per year and 24 hours per day
Amount of cumene to be obtained
= 1 M ton of cumene per annum.
=10
6
/330 tons per day of cumene.
= 10
6
/(330 x 24) tons of cumene per hr.
= 126.26 x 10
3
kg of cumene per hr.
(b) Justification
Mass flow rate was converted to molar flow rate to ease the calculation of the mass
balance. The molecular weight for the cumene was 120.19 kg/kmoles.
Amount of cumene to be obtained
= (126.26 x 10
3
)/120.19 kmoles of cumene per hr.
= 1050.50 Kgmole/hr


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4.1.2.2 Assume 97% conversion and 2% loss in the reactor.
(a) Assumption
97% conversion and 2% loss in the reactor.
(b) Justification
The complete conversion of the reactants to the cumene is very hard to achieve since
it require a very high operating temperature. However, it is very expensive to operate
the reactor at elevated temperature. Besides, it is very dangerous to the worker too.
The loss of the product In the reactor is normally due to the fouling of the
product on the wall of the reactor or in the pipeline. Besides, it might due to leaking.
For example, the flange which connect the inlet pipeline to the reactor is not screwed
tightly. Thus, some of the product leak through the flangle.
Hence:
Cumene required
= 1050.50/ 0.98
= 1071.94 Kgmoles/hr
= 128836.32 Kg/hr
Hence 128836.32 kg of cumene is required to be produced per hr.
Propylene required
=1071.94/0.97 = 1105.09 Kgmole
= 1105.09 x 42 Kg/hr of propylene
= 46413.78 Kg/hr of propylene

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4.1.2.3 Assume Benzene required is 25% extra
(a) Assumption
benzene required is 25% extra
Benzene required
= 1105.09 x 1.25 Kmoles of benzene
= 1381.3625 Kgmole/hr
= 107746.27 Kg/hr
(b) Justification
Propane acts as an inert in the whole process. It is used for quenching purpose in the
reactor. It does not take part in the chemical reaction . Also It is inevitably
associated with the propylene as an impurity as their molecular weight is very close.
We assume propylene to propane ratio as 3:1. Being an inert we are
neglecting propane balance in the material balance to avoid complexity.


115 | P a g e

The unreacted propylene will be react to give DIPB (side reaction)
Unreacted propylene available for side reaction
= 1105.09-1071.94
= 33.15 Kmoles/hr is reacted to give DIPB
Benzene required to give DIPB
= 33.15/2 kmoles/hr
= 16.575 kmoles/hr
DIPB produced
= 16.575 x 162 = 2685.15 Kg/hr
Benzene in product
= 1381.3625 1071.94 -16.575
= 292.85 kmoles/hr
= 22820.85 kg/hr
Checking:
Total Input = 46413.78 + 107746.27 = 154160.05 Kg/hr
Total Output = 128836.32 + 2685.15 + 22820.85= 154342 Kg/hr
Input = output


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4.1.2.4 Conclusion Of Mass Balance For Reactor

Major
Equipment
Reactor
Propylene
=46414.78kg/hr
Benzene
=107746.27kg/hr
Cumene=128836.32 kg/hr
DIPB=2685.15kg/hr
Unreacted
Benzene=22820.85kg/hr

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4.1.3 Material Balance of Propane Column
Propane Column is a Depropanasing column. Assuming almost all the propane is
removed in depropanising column and sent to reactor for quenching. Hence material
balance for depropanasing column is not considered.


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4.1.4 Material Balance of Minor Equipment - Benzene Column
The function of the benzene distillation column is to remove the benzene from the
product. The removed benzene is recycled back to the benzene feed tank to minimize
the waste of the raw material.

F = D + W
154160 = D +W

F XF = DXD +WXw
XF = 22820.85/154160 = 0.1480
Taking,
XD = 0.9999
Xw = 0.05

Minor
Equipment
Benzene
Column
Feed, F
= Cumene+Benzene+DIPB
=154160 kg/hr
W
= Cumene +DIPB

D
= Benzene


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154160 x 0. 1480 = D x 0.9999 +W x 0.05
3023.5 = .9999 D + (20374 D) x 0.05

D = 15969.41 Kg/hr
= Benzene

W = 154160 15969.41
= 138190.5 Kg/hr
= cumene + DIPB

Checking:
Total Input = 154160 kg/hr
Total Output = 15969.41 + 138190.5
= 154160 kg/hr
Input = Output


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4.1.4.1 Assumption
Assuming all the Benzene present in benzene column is recycled to the feed.
4.1.4.2 Justification
Hence, considering negligible amount of benzene to be part of residue. This will avoid
the complexity of multi component distillation in Cumene column.

Therefore amount of benzene recycled = 15969.5 Kg/hr.
Therefore feed actually given to the system
= 154160 + 15969.5
= 170129.5 Kg/hr
4.1.4.3 Conclusion of Mass Balance for Benzene Distillation Column

Minor
Equipment
Benzene
Column

Feed, F
= Cumene+Benzene+DIPB
=154160 kg/hr
W
= Cumene +DIPB
=138190kg/hr

D
= Benzene
=15969.41kg/hr


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4.1.5 Material Balance of Minor Equipment Cumene Column
The function of cumene distillation column is to separate the cumene from DIPB.

F = D +W
138190.6 = D +W

FXF = DXD + WXW
XF =128836.3/138190.5 = 0.932
Taking
XD = 0.995
XW = 0.01

Minor
Equipment
Cumene
Column

Feed, F
= Cumene +DIPB
=138190.5 kg/hr
W
= DIPB

D
= Cumene


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138190.5 x 0.932 = D x 0 .995 + W x 0.01
128793.54 = 0.995D + (138190.5 D) 0.01

D = 129051 kg/hr

W = 138190.5 129051
= 9139.5 Kg/hr

Checking:
Input = 138190.5 Kg/hr
Output = 129051 + 9139.5
= 138190.5 Kg/hr.
Input = output


123 | P a g e

4.1.5.1 Conclusion if Mass Balance for Cumene Column

Minor
Equipment
Cumene
Column
Feed, F
= Cumene +DIPB
=138190.5 kg/hr
W
= DIPB
=9139.5 kg/hr

D
= Cumene
=129051kg/hr


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4.2 Heat Balance
4.2.1 Introduction to Heat Balance
Energy also conserved besides mass is conserved. The energy coming into a unit
operation can be balanced with the energy coming out and the energy stored.
Energy In = Energy Out + Energy Stored
ER = EP + EW + EL + ES
Where,
ER = ER1 + ER2 + ER3 + . = Total Energy Entering
Ep= EP1 + EP2 + EP3 + . = Total Energy Leaving with Products
EW = EW1 + EW2 + EW3 + = Total Energy Leaving with Waste Materials
EL = EL1 + EL2 + EL3 + . = Total Energy Lost to Surroundings
ES = ES1 + ES2 + ES3 + . = Total Energy Stored
Since forms of energy can be interconverted, energy balances are often
complicated. For example mechanical energy to heat energy, but overall the quantities
must balance.
Besides that, energy also takes many forms, such as heat, kinetic energy,
chemical energy, potential energy but because of interconversions it is not always
easy to isolate separate constituents of energy balances. However, under some
circumstances certain aspects predominate. In many heat balances in which other
forms of energy are insignificant; in some chemical situations mechanical energy is

125 | P a g e

insignificant and in some mechanical energy situations, as in the flow of fluids in
pipes, the frictional losses appear as heat but the details of the heating need not be
considered. We are seldom concerned with internal energies.
Therefore practical applications of energy balances tend to focus on particular
dominant aspects and so a heat balance, for example, can be a useful description of
important cost and quality aspects of process situation. When unfamiliar with the
relative magnitudes of the various forms of energy entering into a particular
processing situation, it is wise to put them all down. Then after some preliminary
calculations, the important ones emerge and other minor ones can be lumped
together or even ignored without introducing substantial errors. With experience, the
obviously minor ones can perhaps be left out completely though this always raises the
possibility of error.
Energy balances can be calculated on the basis of external energy used per
kilogram of product, or raw material processed, or on dry solids or some key
component. The energy consumed in food production includes direct energy which is
fuel and electricity used on the farm, and in transport and in factories, and in storage,
selling, etc.; and indirect energy which is used to actually build the machines, to make
the packaging, to produce the electricity and the oil and so on. Food itself is a major
energy source, and energy balances can be determined for animal or human feeding;
food energy input can be balanced against outputs in heat and mechanical energy and
chemical synthesis.

126 | P a g e

In the SI system there is only one energy unit, the joule. However, kilocalories are still
used by some nutritionists and British thermal units (Btu) in some heat-balance work.
Heat Balances
The most common important energy form is heat energy and the conservation
of this can be illustrated by considering operations such as heating and drying. In
these, enthalpy (total heat) is conserved and as with the mass balances so enthalpy
balances can be written round the various items of equipment. or process stages, or
round the whole plant, and it is assumed that no appreciable heat is converted to
other forms of energy such as work.
Enthalpy (H) is always referred to some reference level or datum, so that the
quantities are relative to this datum. Working out energy balances is then just a
matter of considering the various quantities of materials involved, their specific heats,
and their changes in temperature or state (as quite frequently latent heats arising
from phase changes are encountered). Figure 1.2 illustrates the heat balance.


127 | P a g e

Heat is absorbed or evolved by some reactions in processing but usually the
quantities are small when compared with the other forms of energy entering into food
processing such as sensible heat and latent heat. Latent heat is the heat required to
change, at constant temperature, the physical state of materials from solid to liquid,
liquid to gas, or solid to gas. Sensible heat is that heat which when added or
subtracted from materials changes their temperature and thus can be sensed. The
units of specific heat are J/kg K and sensible heat change is calculated by multiplying
the mass by the specific heat by the change in temperature, (m x c x T). The units
of latent heat are J/kg and total latent heat change is calculated by multiplying the
mass of the material, which changes its phase by the latent heat. Having determined
those factors that are significant in the overall energy balance, the simplified heat
balance can then be used with confidence in industrial energy studies. Such
calculations can be quite simple and straightforward but they give a quantitative
feeling for the situation and can be of great use in design of equipment and process.


128 | P a g e

4.2.2 Heat Balance for Major Equipment - Reactor
Basis: Per hour of operation
The gases viz. Propylene, propane, benzene enter at 25 C and benzene enters at
80C.
To calculate the temperature of the mixture of gases after compression to 25 atm :
Component Cp values (J/mole K) at avg temperature of 53 C
A Propylene 64.18
B Benzene 82.22
C Propane 73.89

Propylene in feed = 1105.09 kmoles/hr.
Benzene in feed
= Benzene fed + recycled Benzene
= 1381.36 + 204.73
= 1586.09 kmoles/hr.


129 | P a g e

4.2.2.1 Assumption
(a) Assume Ratio of Propylene to Propane is 3:1
Assuming that propylene is accompanied with propane as impurity in the ratio of 3:1.
Therefore propane in feed = 368.36 kmoles/hr.
Hence,
XA =0.3612 ,
XB = 0.5184 ,
XC = 0.1204

Cp avg =XACpA + XBCpB + XcCpc
Cp avg = 0.3612x 64.18 + 0.5184 x 82.22 + 0.1204 x 73.89
= 71.38 J/mole K
Temperature of the stream after mixing :
Component Cp value J/kmole k at 30
0
C
A Propylene 64.52
B Propane 70.17
C Benzene 98.20

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(1105.09 x 64.52 + 1381.36 x 98.20 + 368.36 x 70.17) x 103 x (T-25)
= 204.73 x 86.22 x 103 x (80-T)
or, 80 T = 13.18 ( T-25 )
or, 14.18 T = 409.5
or, T = 29
0
C

P1 =1 atm, T 1= 290C
P2 = 25 atm, To find T 2

Considering isentropic process, we have
T 2 = T1 (P2 /P1 )
( R / Cp avg )

= 29( 25 /1 )
( 8.314 / 71.38)

= 42.19 C
Cp avg at 42.19 C Cp avg at 53 C =71.38 J/ mole K


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(b) Assume Exit Stream from Pre-Heater Leaves at 100 C
Assuming that the exit stream from pre-heater leaves at 100 C

For the products from the reactor,
m = cumene+DIPB+Benzene+propane
=1071.94+16.575+292.85+368.36
= 1749.72 kmoles/hr

To find Cp avg at ( 250+100) /2 =175C ,Cp J /mole K

Cp avg = 0.6126 x 205.24 + 0.0095 x 302.97 + 0.1673 x121.19 + 0.2105x107.76
= 168.22 J/mole K

Propane 107.76
Cumene 205.24
Di-isopropyl Benzene 302.97
Propylene 97.60
Benzene 121.19


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For the reactants leaving the pre-heater :

m= propylene+benzene+propane
= 1105.09+1586.09+368.36
= 3059.54 k moles/hr

4.2.2.2 Heat Balance Around The Pre-Heater
11749.72 x 168.22 (250-100)x10
3

= 3059.54 x 91.38 x (T 42.19)x10
3

T 200 C
The reactants have to be further heated to the reaction temperature of 250 C before
being fed to the reactor.


133 | P a g e

4.2.2.3 To Find Saturated Steam Required
Cp avg of reactants has to be determined at (200 + 250 )/2=225 C
Cp value at average temperature of 225
0
C , J/kmole K

Cp avg= 0.3612 x 97.60 + 0.5184 x 141.19 + 0.1204 x 117.76
= 122.62 J/mole K

m Cp avg(250-100)=msteam
3059.4 x 122.62x103 x 150 = msteam x 2676
msteam = 21.028 x 106 kg /hr

Propane 117.76
Propylene 97.60
Benzene 141.19


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4.3.3.4 Energy Balance Around The Reactor

Enthalpy of reactants + heat evolved = Q + Enthalpy of products
m Cp dT reactants + heat evolved = Q + m Cp dT products

Heat evolved = 23.7683 K cal / g mole
=99.3964 KJ/g mole

Moles of cumene produced = 1072 k moles /hr

Heat evolved =99.3964 x 1072 x 10
3

=106.63 x 10
6
KJ/hr

m Cp dT reactants = 1105.09 x 87.37x10
3
(250 25) +1586.09 x 93.97x10
3

(250-25)+368.36 x 97.34 x 10
3
x (250-25)
= 6.3326 x 10
10
KJ/hr


135 | P a g e

m Cp dT products = 368.36 x10
3
x (250 25) + 292.85 x 93.97 x10
3
(250
25)+1071.94 x 10
3
x 177.07(250 25) +16.575 x 10
3
x 267.19 x (250 25)
= 5.796 x 10
10
KJ/hr
Hence,
6.3326 x 10
10
+ 106.63 x 10
6
= Q+ 5.796 x 10
10

Q=54.698 x 10
8
KJ/hr

4.2.2.4 Total Propane Requirement for Quench
Latent heat of vaporisation of propane liquid at 25 atm
(B .P =68.4 C)=0.25104 KJ/gm =251.04 KJ/kg
Heat removal by propane heat quench:
Assuming that propane is removed completely in the depropanasing column and is
sent for quenching .
Propane i.e recycled
= 368.36 kmoles/hr
= 368.36 x 44 kg/hr
= 16207.84 kg/hr


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Cp of propane at T avg = (250 + 68.4) /2 = 159.2 C is 2.56 KJ/kgC
Q = m + m Cp (250 68.4)
= 16207.84 x (251.04 + 2.56 x 181.6)
= 11.603 x 10
6
KJ/hr

Additional heat to be removed
= 54.698 x 10
8
11.603 x 10
6

= 54.58 x 10
8
KJ/hr
= Q
l


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4.2.2.5 Water Is Used For Additional Heat Removal

To find flow rate of water:
B.P. of water at 25 atm = 223.85C
Latent heat of vaporisation = 2437 KJ/kg
Assuming that water at 25 C is used for quenching
Cp of water at T avg = (25+223.8)/2=124.43 C is 3.7656 KJ/kg C
Q
l
= m Cp (223.85 25) + m
54.58 x 10
8
=m (3.7656 x 198.85 +2437)
m = 1.713233 x 10
6
kg/hr


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4.2.3 Heat Balance for Propane Column

To find the temperature at which the product stream is fed to propane distillation
column:
At P1 = 25 atm, T1 = 200 C
At P
2
=1 atm T
2
= ?

Cp avg at 100 C
= 0.6126 x 163.42 +0.0095 x 243.76 + 0.1673 x 107.01 +0.2105 x 79.47
= 137.05 J/gm mole

T 2 = T1 (P2 /P1)
R/Cp avg

=100(1/25)
8.314 / 137.05

=82.26
0
C

This is further cooled to 25 C and fed to the distillation column.
F=1749.72 kmoles/hr
D=368 kmoles/hr
W=1381.72 kmoles/hr

139 | P a g e

Enthalpy of vapor that goes as overhead:
Hv= Latent heat of vaporisation + sensible heat
As propane is the major constituent that goes with the overhead, taking and Cp
values of Propane,
Hv =V [ + Cp (Tb To )]
Assuming a reflux ratio of 0.5, we have R=L/D =0.5
L=0.5 D =0.5 x 368 x 44 =8096 kg/hr
V=L+D=8096+16192 =24288 kg/hr

Taking reference temperature as the temperature at which feed enters,
T0=25 C ;
Tb= 42.1 C ,
Cp =2.41 KJ/kg C
= 0.4251 KJ/gm =425.1 KJ/kg
Therefore
Hv =24288 [425.1 + 2.41 ( 42.1 25 )]
=11.3257 x 10
6
KJ/hr


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HD =DCp(TbT0)
=16192 x 2.41 ( 42.1 25 )
=6.673 x 10
5
KJ/hr
HL=L Cp (TbT 0)
=8096 x 2.41 (42.1 25)
=3.336 x 10
5
KJ/hr

Taking enthalpy balance around the condenser,
Hv= Qc+HD +HL
11.3257 x 10
6
= Qc+6.675 x10
5
+3.336x 10
5

Qc = 10.325 x 10
6
KJ/hr


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4.2.3.1 Cooling Water Requirement

Let us assume inlet and exit water temperature as 25 C and 45 C
Cp=4.18 KJ/kg C
Therefore
Qc= msteam CpdT
10.325 x 10
6
= msteamx 4.18x 20
m=123.5 x 10
3
kg/hr

4.2.3.2 Total Enthalpy Balance

HF + QB = HD + QC + HW
To find HW:
HW=WCp avg (TbT0)
By using
pi = XiPi and checking
Pt= 760 mm Hg we found
Tb = 137
0
C

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Cp avg = 0.776 x 176.32 + 0.01199 x 257.11 + 0.2120 x 110.73
= 174 J/mole K
= 174 kJ/kmole K

Mavg = 111.72 kg/kmole

Therefore Cp avg = 174 / 111.72
=1.5575 KJ/kg K

Hw = 1381.72 x 1.5575(137-25) x 111.72
= 26.927 x 10
6
KJ/hr

HF = 0 [ because TF = T0 ]
QB =HD + QC + H W - HF
= 6.673 x 10
5
+ 10.325 x 10
6
+26.927 x 10
6
-0
=37.92 x 10
6
KJ/hr


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4.2.3.4 Saturated Steam Required

QB = msteam
37.92 x 10
6
= msteamx 2256.9
msteam = 16801.5 kg/hr


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4.2.4 Heat Balance for Minor Equipment - Benzene Column

Benzene Distillation Column:
F = 154160 kg/hr enters at 137 C
D = 15969.4 kg/hr
W = 138190 kg/hr

Benzene vapor from the top is recycled. Assuming very small propane content to be a
part of Benzene stream.
Again assuming R = 0.5 = L/D
Hence,
L = 0.5 x 15969.4 =7984.7 kg/hr.
V = L+D = 167954.1 kg/hr
Enthalpy of vapor Hv=V[ Cp(Tb T0) ]
Taking referenced temperature
T0 = TF = 137 C
B.P. of Benzene at 1 atm = 80.1 C = Tb


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of benzene
=94.14cal/gm mole
= 393.8818 KJ/gm
=393.88 x 10
3
KJ/kg

Cp of Benzene vapor at 80.1C
= 22.83 cal/gm mole
= 95.52 J/gm mole K
= 1.2246 KJ/kg K

Hv= 167954.1 [ 393.8818 + 1.2246 ( 80.1 137 )]
= 64.94 x 10
6
KJ/hr

HD= 15969.4 x 1.2246 (80.1 137 )
= -1.1127 x 10
6
KJ/hr.


146 | P a g e

HL = L Cp (TbT0)
= 7984.7 x 1.2246 (80.1 137 )
= -0.55637 x 10
6
KJ/hr

Hv = QC + HL +HD
54.45 x 106= QC 0.55637 x 106 1.1127 x 106
QC = 56.12 x 106 KJ/hr

4.2.4.1 Cooling Water Requirement For Benzene Distillaton Column

Cp=4.18 KJ/kg C

Therefore,
Qc= msteam CpdT
54.45 x 10
6
= msteam x 4.18 x 20
msteam = 67.128 x 10
4
kg/hr


147 | P a g e


HF + QB = HV + QC +Hw
To find HW :
w = 138190 Kg/hr
T b = TF for cumene distillation column
= 153.4 C

Cp avg =Cp of cumene
= 1.91 KJ/kg C
Hw= 138190 x 1.91(153.4 137)
= 3.0774 x 10
6
KJ/hr
HF = 0 [ because TF= TD]

QB= 54.94 x 10
6
+ 65.11 x 10
6
+4.06 x 10
6
-12.245 x 10
6

= 11.46 x 10
7
KJ/hr


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QB = msteam
11.46 x 107 = msteam x 2256.9
msteam = 50.81 x 103kg/hr


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4.2.5 Heat Balance for Minor Equipment - Cumene Column

Cumene Distillation column:
F = 138190 kg/hr
D = 129051 kg/hr
w = 9139 kg/hr

Enthalpy of vapor that goes at the top:
As the cumene is the major constituent that goes with the overhead, taking and Cp
values of Cumene,
Hv=V[ Cp(T0 Tb) ]
Taking reference temperature T0 =TF = 153.4 C
B.P. of Cumene at 1 atm = 152.4 C

of cumene
=74.6 cal/gm
= 312.1264 KJ/kg


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Cp of Cumene vapor at 152.4 C
= 0.4047 cal/gm K
= 1.6931 KJ/kg K

V = D + L
= 129051 + 68655.1
=197706.1 kg/hr

Hv = 197706.1[ 312.1264 + 1.6931 ( 152.4 153.4)]
= 61.3745 x 10
6
KJ/hr

HD = D Cp (TbT0)
= 129051 x 1.6931(152.4 153.4)
= -0.218496 x 10
6
KJ/hr

HL = L Cp(Tb T0 )
= 68655.1 x 1.6931(152.4 153.4)
= -0.116239 x 10
6
KJ/hr

151 | P a g e

Hv = QC + HD +HL
61.3745 x 10
6
= QC 0.218496 x 10
6
-0.116239 x 10
6

QC = 61.71 x 10
6
KJ/hr

4.2.5.1 Cooling Water Requirement

Cp=4.18 KJ/kg C
Therefore Qc= msteamCpdT
61.71 x 106 = msteam x 4.18 x 20
msteam = 73.8148 x 10
3
kg/hr


152 | P a g e


HF + QB = HV + QC +Hw
To find HW :
W = 9139 kg/hr
Hw = W Cp avg (TbT 0 )
T b at xw
= 0.2934 =184.5 C

Cp avg at 184.5 C = 0.013x 214.1952 + (1 0.013) x 288.93
= 287.9584 J/mole K
= 2.88795 KJ/kg K

Hw = 9139 x 2.8795(184.5 153.4)
= 81.84 x 10
4
KJ/hr


153 | P a g e

HF = 0 [ because TF = T0 ]
QB = HV + QC + HW - HF
= 61.3745 x 10
6
+ 73.8143 x 10
3
+ 81.84 x 10
4

=62.2667 x 10
6
KJ/hr


QB = msteam
62.2667 x 106 = msteam x 2256.9
msteam= 27589.5 kg/hr


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4.2.6 Product Yield
4.2.6.1 Overall Plant Material Balance

Chemical Input Output
molwt kmol/h kg/h kmol/h kg/h
BENZENE 78 1382.4 107,746.27 204.74 15,969.42
PROPYLENE 42 1105.09 46413.78 0 0
PROPANE 44 5.9 259.3844 5.9 259.3844
CUMENE 120 0 0 1075.43 129,051
DIPB 162 0 0 56.42 9139.5
TOTAL - - 154,160.05 - 145,371.2


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4.2.6.2 Yield (In Percent, Kg, SCFD)

As 1 mole of cumene is produced from 1 mole of propylene the stoichiometry
factor is 1

Moles of Cumene produced = 1075.43
Stiochiometry factor = 1 (from the equation)
Moles of reactant fed = 1105.09Kmole

Yield of cumene based on propylene:

1. Yield (percent form)
= (moles of product produced) (Stiochiometry Factor) / (Moles of reactant fed
to process)
= 1075.43X1/1105.09
= 97.31%

2. Yield (kg form)
= 129,051kg/hr (from mass balance)


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3. Yield (scfd form)
Density of cumene = 862kg/m
3

scfd = 129,051
kg
hr
24hr
day
m
3
862kg
[
3.28ft
1m
]
3

scfd = 126,790.5 standard cubic feet per day


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4.3 Flow Summary for Cumene Production at Design Conditions

Figure 4.1: P&ID for Cumene Production Process

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Table 4.1: Flow Summary Table for Cumene Production at Design Conditions (Based on Figure 4.1)
Stream No. 1 2 3 4 5 6 6a 7
Temperature (C) 25 25 41 28 44 41 214.0 350
Pressure (bar) 1.00 11.66 1.01 31.50 31.50 31.25 30.95 30.75
Vapor mole fraction 0 0 0 0 0.0 0.0 1.0 1.0
Flowrate (tonne/h) 8.19 4.64 16.37 4.64 16.37 21.01 21.01 21.01
Benzene 105.00 - 205.27 - 205.27 205.27 205.27 205.27
Propylene - 105.00 2.89 105.00 2.89 107.89 107.89 107.89
Propane - 5.27 2.79 5.27 2.79 8.06 8.06 8.06
Cumene - - 0.94 - 0.94 0.94 0.94 0.94
P-Diisopropyl Benzene - - - - - - - -
Total (kmol/h) 105.00 110.27 211.89 110.27 211.89 322.16 322.16 322.16

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Table 4.1: Flow Summary Table for Cumene Production at Design Conditions (Based on Figure 4.1) (Cont.)
Stream No.
8 9 10 11 12 13 14
Temperature (C)
350 90 90 57 179 178 222
Pressure (bar)
30.25 1.75 1.75 1.75 1.90 1.90 2.10
Vapor mole fraction
1.0 1.0 0.0 0.0 0.0 0.0 0.0
Flowrate (tonne/h)
21.01 1.19 19.82 8.18 11.64 11.08 0.56
Benzene
108.96 7.88 101.08 100.27 0.81 0.81 -
Propylene
8.86 5.97 2.89 2.89 - - -
Propane
8.06 5.27 2.79 2.79 - - -
Cumene
94.39 0.77 93.62 0.94 92.68 91.76 0.92
P-Diisopropyl Benzene
2.79 - 2.79 - 2.79 0.03 2.76
Total (kmol/h)
223.06 19.89 203.17 106.89 96.28 92.60 3.68


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4.4 Flow Summary for Utility Streams

Table 4.2: Flow Summary Table for Utility Streams (Based on Figure 4.1)

Stream Name
hps to
E-801
condensate
from E-801
mps to
E-804
condensate
from E-804
hps to
E-806
condensate
from E-806
Temperature (C) 254 254 185.5 185.5 254 254
Pressure (bar) 42.37 42.37 11.35 11.35 42.37 42.37
Flowrate (tonne/h) 7.60 7.60 3.56 3.56 3.25 3.25

Stream Name
cw to
E-802
cw from
E-802
cw to
E-803
cw from
E-803
cw to
E-805
cw from
E-805
Temperature (C) 30 45 30 45 30 45
Pressure (bar) 5.16 4.96 5.16 4.96 5.16 4.96
Flowrate (tonne/h) 261.30 261.30 85.88 85.88 87.50 87.50


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4.4 Equipment Summary with Capacity for Cumene Producition Process


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163 | P a g e


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5.0 BEHAVIOUR OF CATALYSTS/SOLVENTS
5.1 Feedstock Considerations
5.1.1 Impact Of Feedstock Contaminants On Cumene Purity
The impact of undesirable side reactions is minimal in the Q-Max process. Impurities
in the cumene product are governed primarily by trace contaminants in the feeds.
Cumene can be operated at very low temperature due to the high activity of the QZ-
2000 catalyst. This will dramatically reduces the rate of competing olefin
oligomerization reactions and decreases the formation of heavy by-products.
As a result, cumene product impurities are primarily from impurities in the
feedstocks in the Q-Max process. Cumene is formed by the alkylation of toluene with
propylene. Table 1.6.1 lists the common cumene impurities of concern to phenol
producers, and Fig. 1.6.5 graphically shows the reactions of some common
feedstock contaminants that produce these impurities n cumene and ethylbenzene.
Ethylbenzene is primarily formed from ethylene impurities in the propylene
feed. The toluene may already be present as an impurity in the benzene feed, or it
may be formed in the alkylation reactor from methanol and benzene. However, as
with cumene, ethylbenzene can also be formed from ethanol.
To protect against hydrate freezing, small quantities of methanol and ethanol
are sometimes added to the pipeline. Although the Q-Max catalyst is tolerant of
these alcohols, removing them from the feed by a water wash may be desirable.
This is done to achieve the lowest possible levels of ethylbenzene or cumene in the
cumene product n Butylbenzene.

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While butylbenzene is produced primarily from traces of butylene in the
propylene feed, it may also be created through the oligomerization of olefins.
However, oligomerization is reduced as a result of the very low reaction temperature
of the Q-Max process. This will caused minimal overall butylbenzene formation.
The n-propylbenzene (NPB) is produced from trace levels of cyclopropane in
the propylene feed. The chemical behavior of cyclopropane is similar to that of an
olefin. It reacts with benzene to form either cumene or NPB. As the reaction
temperature is lowered, the tendency to form NPB rather than cumene decreases.
However, the catalyst deactivation rate increases with lower reaction temperature
(Fig. 1.6.6). A Q-Max unit can be operated for extended cycle lengths and still
maintain an acceptable level of NPB in the cumene product because of the
exceptional stability of the QZ-2000 catalyst system.
For example, with a typical FCC-grade propylene feed containing normal
amounts of cyclopropane, the Q-Max process can produce a cumene product
containing less than 250 wt ppm NPB and maintaining an acceptable catalyst cycle
length.


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Table 5.1: Common Cumene Impurities

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Figure 5.1: Reactions of feed impurities


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5.1.2 Impact of Catalyst Poisons On Catalyst Performance
Table 5.1 showed a list of potential Q-Max catalyst poisons. All the listed compounds
are known to neutralize the acid sites of zeolites. Good feedstock treating practice or
proven guard-bed technology easily handles these potential poisons.
To neutralize some of the stronger zeolite acid sites first, water in an
alkylation environment can act as a Brnsted base. Unfortunately, water does not
have a detrimental effect at the typical feedstock moisture levels and normal
alkylation and transalkylation conditions as a result of the inherently high activity of
the Q-Max catalyst.
Sulfur does not affect Q-Max catalyst stability or activity at the levels normally
present in the propylene and benzene feeds processed for cumene production. The
Q-Max catalyst can process feedstocks up to the normal water saturation conditions,
typically 500 to 1000 ppm, without any loss of catalyst stability or activity.
Within the Q-Max unit, the majority of sulfur compounds associated with
propylene (mercaptans) and those associated with benzene (thiophenes) are
converted to products outside the boiling range of cumene. Thus, trace sulfur in the
cumene product, for example, might be a concern in the downstream production of
certain monomers (e.g., phenol hydrogenation for caprolactam).
Sulfur at the levels normally present in propylene and benzene feeds
considered for cumene production will normally result in cumene product sulfur
content that is within specifications (for example, 1 wt ppm). Thus, the sulfur

169 | P a g e

content of the cumene product does depend on the sulfur content of the propylene
and especially benzene feeds. Chemical-grade, FCCgrade, and polymer-grade
propylene feedstocks can all be used to make high-quality cumene
product.Successful operation with a wide variety of propylene feedstocks from
different sources has demonstrated the flexibility of the Q-Max process.

Figure 5.2: Effect of reactor temperature


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5.2 Process Performance

Based on typical propylene and benzene feedstock, the Q-Max unit has high raw
material utilization and an overall cumene yield of at least 99.7 wt %. The remaining
0.3 wt % or less of the overall yield is in the form of a heavy aromatic by-product.
The cumene product quality summarized in Table 1.6.3 is representative of a
Q-Max unit processing commercially available, high-quality feedstocks.
The specific contaminants present in the feedstocks strongly influenced the
quality of the cumene product from any specific Q-Max unit,
Propane entering the unit with the propylene feedstock is unreactive in the
process. It is then is separated in the fractionation section as a propane product.


171 | P a g e

Table 5.2: Representative Cumene Product Quality

Table 5.3: Handling Potential Catalyst Poisions


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5.3 Production Of Cumene Using Zeolite Catalysts
In the late 1980s, two new processes using zeolite based catalyst systems were
developed.
5.3.1 Unocals technology is based on a conventional fixed-bed system
Based on a Y-type zeolite catalyst, Unocal has introduced a fixed bed liquid phase
reactor system. The distillation requirements involve the separation of propane for
LPG use, the recycle of excess benzene to polypropyl benzene for transalkylation to
cumene and the production of purified cumene product. The selectivity to cumene is
generally between 70 and 90 Wt.%. The remaining components are primarily
polypropyl benzenes, which are transalkylated to cumene in a separate reaction
zone. This give an overall yield to cumene of about 99 Wt. %.
5.3.2 The second zeolite process, which was developed by CR&L
It is based on the concept of catalytic distillation, which is a combination of catalytic
reaction, and distillation in a single column. The basic principle is to use the heat of
reaction directly to supply heat for fractionation. This concept has been applied
commercially for the production of MTBE but has not yet been applied commercially
to cumene.


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5.4 Disadvantages Of Using Solid Phosphoric Acid (SPA) Process

1. Relative high selectivity to hexyl benzene
2. Significant yield of DIPB
3. Unloading of spent catalyst from reactor difficult
4. Lower activity
5. Catalyst non-regenerability

5.5 Disadvantages of Using Aluminum Chloride As Catalyst

1. Environmental hazard
2. Washing step for catalyst removal
3. High corrosion


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5.6 Catalysts in Cumene Production Process
In the present industrial world, cumene is an important chemical thus its uses are
steadily increasing. The process followed for the production of cumene is the
catalytic alkylation of benzene with propylene. Recently, zeolite based catalysts are
used to replace the normal acid based catalysts due to added advantages.
Many researchers have greatly studied and specified on the cumene
production process and the reaction mechanism and the reaction kinetics. They have
carried out both experimental as well as computer based simulation and optimization
studies.
With the Q-MAX
TM
process, mixture of benzene and propylene is converted to
high quality cumene using a regenerable zeolite catalyst. The Q-MAX
TM
process is
characterized by an exceptionally high yield, better product quality, less solid waste,
decrease in investment and operating costs and a corrosion free environment. The
UOP process uses QZ-2000/ QZ-2001 catalyst which is a variant of - zeolite.
A very good cumene yield and quality has been produced by the Q-MAX
TM

process. This is because the QZ-2000 zeolite based catalyst utilized for the UOP
process operates with a low flow rate of benzene. Because of that, the investment
and utility costs are reduced greatly.
Compared to other zeolite based cumene technologies, the UOP process
provides the highest product quality and great stability. QZ-2000 is non-corrosive
and regenerate-able. Impurities in the fee have less effect.

175 | P a g e

In a single reactor shell, the alkylation reactor is divided into four catalytic
beds. The fresh benzene feed is passed through the upper-mid section of the
depropanizer column to remove excess water and then sent to the alkylation reactor.


176 | P a g e

5.7 Catalysts And Reactions
By alkylating benzene with monoolefins, most of the industrially important alkyl
aromatics used for petrochemical intermediates are produced. For the production of
ethylbenzene, cumene, and detergent alkylate, the most important monoolefins are
ethylene, propylene, and olefins with 10-18 carbons, respectively. This section
focuses primarily on these alkylation technologies.
The rearrangement of carbonium ions that readily occurs according to the
thermodynamic stability of cations sometimes limits synthetic utility of aromatic
alkylation. For example, the alkylation of benzene with n-propyl bromide gives
mostly isopropylbenzene (cumene) C9H12 and much less n-propylbenzene.
However, the selectivity to n-propylbenzene versus isopropylbenzene changes
depending on alkylating reagents, conditions, and catalysts; eg, the alkylation of
benzene with n-propyl chloride at room temperature gives mostly n-propylbenzene.
Today, the alkylation of aromatics is dominated by liquid - phase processes
based on zeolites. The term zeolitic refers to molecular sieves whose
framework consists essentially of silica and alumina tetrahedra. The complexity of
tetrahedral groups may be linked in polynuclear structures. Five types of zeolites are
the most applied: beta, Y, ZSM - 12, MCM - 22 and mordenite. These catalysts are
characterized by large pore opening necessary for achieving high selectivity.
Since industrial catalysts are employed as pellets, the mass - and heat
transfer effects can play an important role. The internal diffusion is often the critical

177 | P a g e

step controlling the overall process rate. The use of an efficient catalyst is the
decisive element in designing a competitive process.
Beta-zeolite is quickly becoming the catalyst of choice for commercial
production of ethylbenzene and cumene. Mobil invented the basic beta-zeolite
composition of matter in 1967 (63). Since that time, catalysts utilizing beta-zeolite
have undergone a series of evolutionary steps leading to the development of state-
of-the-art catalysts such as the UOP EBZ-500 and QZ-2000 for ethylbenzene and
cumene alkylation service, respectively.
At the same time that the structure of beta was being investigated, extensive
research was being conducted to identify new uses for this zeolite.
A major breakthrough came in late 1988 with the invention by workers at
Chevron of a liquid phase alkylation process using beta-zeolite catalyst.
While Chevron had significant commercial experience with the use of Y (FAU)
zeolite in liquid phase aromatic alkylation service, they were quick to recognize the
benefits of BEA over Y as well as the other acidic zeolites used at the time, such as
mordenite (MOR) or ZSM-5 (MFI).
Chevron discovered that the open 12-membered ring structure characteristic
of beta coupled with the high acidity of the material made it an ideal catalyst for
aromatic alkylation.

178 | P a g e

These properties were shown to be key in the production of aromatic
derivative products such as ethylbenzene and cumene with extremely high yields
and product purities approaching 100%.
Moreover, the combination of high activity and porous structure imparted a
high degree of tolerance to many of the contaminants ordinarily found in the
feedstocks to these processes.
A liquid-phase process was developed by Chevron in 1990 and the rights were
acquired by UOP in 1995 as a basis for the Lummus/ UOP EBOne process for
ethylbenzene and Q-Max process for cumene production


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5.8 Cumene Process And Catalysts

To meet the demand for high octane aviation gasoline during World War II, cumene
processes were originally developed between 1939 and 1945. 95% of cumene
demand was as an intermediate for the production of phenol and acetone in 1989. A
small percentage is used for the production of a-methylstyrene. Since 1970, the
demand for cumene has risen at an average rate of 2-3% per year and this trend
continued throughout the 1990s.
Currently, almost all cumene is produced commercially by two processes:
1) A homogeneous AlCl3 and hydrogen chloride catalyst system developed by
Monsanto and
2) A fixed-bed, kieselguhr-supported phosphoric acid catalyst system developed
by UOP
In the late 1980, two new processes using zeolite-based catalyst systems
were developed. CR&L has developed a catalytic distillation system based on an
extension of the CR&L MTBE technology. Unocals technology is based on a
conventional fixed-bed system.


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5.8.1 SPA Catalyst
Since the 1930s, the solid phosphoric acid (SPA) catalyst process has been the
dominant source of cumene. This process accounts for >90% of cumene operating
capacity (72). Propylene feed, fresh benzene feed, and recycle benzene are charged
to the upflow reactor, which operates at 3-4 MPa and at 200-260
o
C.
A typical reactor effluent yield contains 94.8 wt% cumene and 3.1 wt%
diisopropylbenzene (DIPB). The SPA catalyst provides an essentially complete
conversion of propylene on a one-pass basis.
The remaining 2.1% is primarily heavy aromatics. This high yield of cumene is
achieved without transalkylation of DIPB and is unique to the SPA catalyst process.
The cumene product is 99.9 wt% pure while the heavy aromatics which have
a research octane number (RON) of 109. It can either be used as high octane
gasoline-blending components or combined with additional benzene and sent to a
transalkylation section of the plant where DIPB is converted to cumene.
With transalkylation and 9496 wt% without transalkylation, the overall yields
of cumene for this process are typically 9798 wt%.


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5.8.2 AlCl3 and Hydrogen Chloride Catalyst
Generally, AlCl3 processes have been used more extensively for the production of
ethylbenzene than for the production of cumene.
In 1976, Monsanto developed an improved cumene process that uses an AlCl3
catalyst. By the mid-1980s, the technology had been successfully commercialized.
The overall yields of cumene for this process can be as high as 99 wt% based
on benzene and 98 wt% based on propylene.
At a temperature of <135
o
C and a pressure of <0.4 MPa, dry benzene, fresh
and recycle, and propylene are mixed in the alkylation reaction zone with the AlCl3
and hydrogen chloride catalyst .
Polyisopropylbenzenes are transalkylated to cumene as the effluent from the
alkylation zone is combined with recycle polyisopropylbenzene and fed to the
transalkylation zone.
The strongly acidic catalyst is separated from the organic phase by washing
the reactor effluent with water and caustic.
The distillation system is designed to recover a high-purity cumene product.
The unconverted benzene and polyisopropylbenzenes are separated and recycled to
the reaction system.
Propane in the propylene feed is recovered as liquid petroleum gas (LPG).


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5.8.3 Zeolite Catalysts
In the early 1980s, Unocal introduced a fixed-bed liquid-phase reactor system based
on a Y-type zeolite catalyst. The selectivity to cumene is generally between 70 and
90 wt%.
The remaining components are primarily polyisopropylbenzenes. This is then
transalkylated to cumene in a separate reaction zone to give an overall yield of
cumene of 99 wt%.
The distillation requirements involve the separation of propane for LPG use,
the recycle of excess benzene to the reaction zones, the separation of
polyisopropylbenzene for transalkylation to cumene, and the production of a purified
cumene product.
Based on the concept of catalytic distillation, the second zeolite process was
developed by CR&L. This is a combination of catalytic reaction and distillation in a
single column.
The basic principle is to use the heat of reaction directly to supply heat for
fractionation. This concept has been applied commercially for the production of
MTBE and cumene.
Over the past decade, great progress has been made in improving and
optimizing catalyst formulations for use in both the EB and cumene alkylation
applications. For example, the ability to synthesize beta-zeolite in a wide range of
Si/Al2 ratios has given catalyst designers the ability to tailor the zeolite into a form
that optimizes activity and selectivity. Current state-of-the-art processes for cumene

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are similar to ethylbenzene and consist of liquid-phase technologies offered by UOP
and ExxonMobil based on beta-zeolite and MCM-22 catalysts, respectively.
A parametric study on the effects of Si/Al2 ratio on activity and selectivity was
published by Bellusi. In this work, it was found that as the silica to alumina ratio was
increased from 28 to 70, there was a decrease in both activity and selectivity toward
IPBs. Additionally, the less active catalysts had a greater tendency toward
oligomerization and were more prone toward coking. An analogous trend was
observed for ethylene, as well. This study parallels work performed at UOP, where,
through the use of nonconventional synthesis techniques, samples have also been
prepared with Si/Al2 ratios down to 10.
Through this work it has been found that with a Si/Al2 ratio of 25, the catalyst
maintains sufficient activity to achieve polyalkylate equilibrium (eg,
diisopropylbenzene equilibrium) and, at the same time, minimizes formation of
heavier diphenyl compounds (and hence maximizes yield) in cumene service.
Perhaps the most critical understanding was developed with regard to the
need to minimize the Lewis acidity of the catalyst and at the same time maintain
high Brnsted acidity.
Studies at UOP demonstrated that olefin oligomerization was directly related
to the Lewis acid function of the catalyst. Olefin oligomerization reactions can lead to
the formation of heavy compounds (coke-type precursors), which have a negative
effect on catalyst stability.

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Thus, minimization of the Lewis character of the beta leads to a catalyst with
high stability. Generally, Lewis acidity in beta-zeolite has been attributed to the
existence of nonframework aluminum atoms.
The most common mechanism for the formation of non framework alumina is
through steam dealumination during the catalyst calcination step of the
manufacturing process. By careful control of the temperature, time, and steam levels
during the manufacturing process, it is possible to produce a catalyst that is
extremely stable at typical alkylation conditions.
The feature of complete regenerability is another attribute that distinguishes
beta-zeolite catalysts from other commercially practiced technology, where
selectivity can be lost upon regeneration (77).The ability to regenerate catalyst is
essential in a commercial environment to provide additional flexibility to cope with a
wide range of feedstock sources, feedstock contaminants, and potential operational
upsets.
The historical development of beta-zeolite showed that early versions of beta
catalyst demonstrated less than optimal performance when compared to todays
state-of-the-art formulation.
Figure 5.3 is a plot of the relative stability of beta-zeolite as a function of the
Si/Al2 ratio of the beta-zeolite structure in which the dominating influence of this
parameter is evident.

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Figure 5.3: Relative Stability of beta-zeolite as a function the Si/Al ratio
Stabilizing the zeolitic structure through careful process and chemical means
results in a catalyst system that is extremely robust, highly regenerable, and tolerant
of most common feedstock impurities. Additional studies of beta-zeolite have come
to similar conclusions.
For example, Enichem finds that beta-zeolite is the most effective catalyst for
cumene alkylation among others tested including Y, mordenite and an isostructural
synthesis of MCM-22.

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Figure 5.4: Comparison of QZ-2000 and QZ-2001 Catalyst Stability
The principles described above also led to the development of a new
generation cumene alkylation catalyst, QZ-2001.
In Figure 5.4, results from accelerated stability testing of QZ-2000 and QZ-
2001 catalyst demonstrates the superior stability of the latest catalyst version.
Since new high activity beta-zeolite catalysts such as QZ-2000 are such strong
acids, they can be used at lower temperatures than SPA catalyst or competing lower
activity zeolites such as MCM-22 (43,78).

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The lower reaction temperature reduces the rate of competing olefin
oligomerization reactions that is particularly high in SPA based processes.
The result is higher selectivity to cumene and lower production of non-
aromatics that distill with cumene (including olefins, which are analyzed as Bromine
Index, and saturates) as well as lower heavy by-products production.
For example, although butylbenzene is typically produced from traces of
butylene in the propylene feed, there is always the potential for butylbenzene
formation through the oligomerization of propylene to nonene, followed by cracking
and alkylation to produce butylbenzenes and amylbenzenes.
As a result of the high-activity and low-operating temperature of the beta-
zeolite catalyst system, the Q-Max process essentially eliminates oligomerization.
This results in almost no butylbenzene formation beyond that from butylenes
in the feed.
The cumene product from a Q-Max unit processing a butylene-free propylene
feedstock typically contains <15 wt-ppm butylbenzenes. The Q-Max process typically
produces equilibrium levels of cumene (between 85 and 95 mol.%) and DIPB
(between 5 and 15 mol%).
The DIPB is fractionated from the cumene and reacted with recycle benzene
at optimal conditions for transalkylation to produce additional cumene.
Beta-zeolite catalyst is also an extremely effective catalyst for the
transalkylation of DIPB to produce cumene.

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Due to the high activity of beta-zeolite, transalkylation in the Q-Max process
can be accomplished at very low temperatures to achieve high conversion and
minimum side products such as heavy aromatics and additional n-propylbenzene.
As a result of the high activity and selectivity properties of beta-zeolite, the
same catalyst (eg, QZ-2000) is specified for both the alkylation and transalkylation
sections of the process.
With both of these reactors working together to take full advantage of the
QZ-2000 catalyst, the overall yield of cumene is increased to at least 99.7 wt%.
The improvement in beta-zeolite catalyst quality has progressed to the point
that any significant impurities in the cumene product are governed largely by trace
impurities in the feeds.
The selectivity of the catalyst typically reduces by-products to a level resulting
in production of ultra-high cumene product purities of up to 99.97 wt%.
At this level, the only significant by-product is n-propylbenzene with the
catalyst producing essentially no ethylbenzene, butylbenzene, or cymene beyond
precursors in the feed.
Cumene processes based on zeolites are environmentally friendly, offering
high productivity and selectivity. The most important are listed in Table 5.4. The
catalyst performance determines the type and operational parameters of the reactor
and, accordingly the flowsheet configuration. The technology should find an efficient

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Table 5.4: Technologies for cumene manufacturing based on zeolites

Figure 5.5 illustrates a typical conceptual flowsheet. Propylene is dissolved in
a large excess of benzene (more than 5 : 1 molar ratio) at sufficiently high pressure
that ensures only one liquid phase at the reaction temperature, usually between 160
and 240
0
C.

Figure 5.5: Typical Conceptual Flowsheet

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The alkylation reactor is a column filled with fixed - bedcatalyst, designed to
ensure complete conversion of propylene. The reactor effluent is sent to the
separation section, in this case a series of four distillation columns: propane (LPG)
recovery, recycled benzene, cumene product and separation of
polyisopropylbenzenes.
The flowsheet involves two recycles: nonreacted benzene to alkylation and
polyalkylbenzenes to transalkylation. The minimization of recycle flows and of energy
consumption in distillation are the key objectives of the design.
These can be achieved by employing a highly active and selective catalyst, as
well as by implementing advanced heat integration.
In general, the alkylation of aromatics is dominated today by liquid - phase
processes based on zeolites. The term zeolitic refers to molecular sieves whose
framework consists essentially of silica and alumina tetrahedra. The complexity of
tetrahedral groups may be linked in polynuclear structures. Five types of zeolites are
the most applied: beta, Y, ZSM - 12, MCM - 22 and mordenite. These catalysts are
characterized by large pore opening necessary for achieving high selectivity.


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Figure 5.6: Spatial structure of beta-zeolite
As an illustration, Figure 5.6 shows the spatial structure of a beta - zeolite.
Both the specific three - dimensional structure and the chemical composition,
including the presence of doping elements, lead to substantial differences in activity
and selectivity. The catalytic properties depend strongly on the surface treatment
and on the activation procedure. Since industrial catalysts are employed as pellets,
the mass - and heat transfer effects can play an important role. The internal
diffusion is often the critical step controlling the overall process rate. The use of an
efficient catalyst is the decisive element in designing a competitive process.
Table 5.5: Selectivity obtained with different zeolite catalysts in cumene
synthesis


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Table 5.5 presents some global yield data, including transalkylation. Zeolite
beta is often mentioned among the best suited for fixed - bed operation, with
selectivity Figure 5.6 in cumene around 90%. Other studies prefer MCM - 22
because of better stability against deactivation .
Table 5.6: Selectivity and DIPB distribution at different temperature and
propylene conversions

As Table 5.6 shows, the selectivities of zeolite - beta and MCM - 22 are similar
in the range of temperature of 180
0
C to 220
0
C and benzene/propylene ratios of 3.5
0
C 7.2. Modified Y - type zeolites were found capable of selectivity over 97%
at lower temperature, and are therefore recommended for catalytic distillation.
Recent patents show that the new superactive zeolite catalysts are suitable
for both alkylation and transalkylation reactions.

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At quasi equal selectivity the differences in performance of catalysts can be
justify ed by the amount of trace impurities produced. Because operating at lower
temperature is more favorable, material efficiency seems to be in contradiction with
heat integration.
Table 5.7: Physical Properties of a zeolite catalyst

Table 5.7 displays some physical properties of zeolites. A study issued from
industry demonstrates the significant role of mass - transfer resistances, even for
small particles below 1 mm, reporting that pore diffusion may decrease the
effectiveness from low to very low values (0.4 to 0.06).
The external mass transfer resistance is much less important. In
consequence, in commercial operation only a small part of the catalyst is effectively
used, typically less than 10%. Since the reduction of particle size is restricted in
practice for technological reasons, another alternative is the use of a surface -
coated monolith catalyst.
However, high exothermicity raises problems with respect to temperature
control. In conclusion, the subtle combination of chemical and physical factors leads
to a large variability in the behavior of the commercial catalysts with respect to
reaction rate and selectivity.

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5.9 Future Technology Trends

Over the years, improvements in aromatic alkylation technology have come in the
form of both improved catalysts and improved processes. This trend is expected to
continue into the future.
5.9.1 Catalysts.
Nearly all of the industrially significant aromatic alkylation processes of the past have
been carried out in the liquid phase with unsupported acid catalysts.
For example, AlCl3 and HF have been used commercially for at least one of
the benzene alkylation processes to produce ethylbenzene , cumene , and detergent
alkylates .
Exceptions to this historical trend have been the use of a supported boron
trifluoride for the production of ethylbenzene and of a solid phosphoric acid (SPA)
catalyst for the production of cumene .
Since 1976, these forms of acids have become a significant environmental
concern from both a physical handling and disposal perspective. This concern has
fueled much development work toward solid acid catalysts, including zeolites, silica
Caluminas, and clays.
A liquid-phase ethylbenzene process jointly licensed by ABB Lummus and UOP
initially used a Y-type zeolite catalyst developed by Unocal. During the 1990s,
significant advances took place with numerous new zeoletic and other solid acid

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catalysts that were introduced for the production of ethylbenzene, cumene and
detergent alkylate .
Because of their initial commercial success and the industries growing
awareness of environmental issues, solid acid catalysts are expected to ultimately
replace liquid acid catalysts.


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6.0 PROCESS AND INSTRUMENTATION DIAGRAM
6.1 Introduction To P&ID
A piping and instrumentation diagram/drawing (P&ID) is a diagram in the
process industry diagram with standard symbols which shows the interconnection of
process equipment and the instrumentation used to control the process. The P&ID
also provides important information needed by the constructor and manufacturer to
develop the other construction input documents (the isometric drawings or
orthographic physical layout drawings). A piping and instrumentation diagram/drawing
(P&ID) is defined by the Institute of Instrumentation and Control as follows:
1. A diagram which shows the interconnection of process equipment and the
instrumentation used to control the process. In the process industry, a standard
set of symbols is used to prepare drawings of processes. The instrument
symbols used in these drawings are generally based on International Society of
Automation (ISA) Standard.
2. The primary schematic drawing used for laying out a process
control installation.
P&IDs play a significant role in the maintenance and modification of the
process that it describes. It is critical to demonstrate the physical sequence of
equipment and systems, as well as how these systems connect. During the
design stage, the diagram also provides the basis for the development of
system control schemes, allowing for further safety and operational
investigations, such as the hazard and operability study (HAZOP).


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For processing facilities, it is a pictorial representation of
Key piping and instrument details
Control and shutdown schemes
Safety and regulatory requirements
Basic start up and operational information
6.2 P&ID Diagram
The P and I diagram shows the arrangement of the process equipment, piping,
pumps, instruments, valves and other ttings. It should include:
1. All process equipment identied by an equipment number. The equipment should
be drawn roughly in proportion, and the location of nozzles shown.
2. All pipes, identied by a line number. The pipe size and material of construction
should be shown. The material may be included as part of the line identication
number.
3. All valves, control and block valves, with an identication number. The type and
size should be shown. The type may be shown by the symbol used for the valve or
included in the code used for the valve number.
4. Ancillary ttings that are part of the piping system, such as inline sight-glasses,
strainers and steam traps; with an identication number.
5. Pumps, identied by a suitable code number.
6. All control loops and instruments, with an identication number.

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For simple processes, the utility (service) lines can be shown on the P and I
diagram. For complex processes, separate diagrams should be used to show the
service lines, so the information can be shown clearly, without cluttering up the
diagram. The service connections to each unit should, however, be shown on the P
and I diagram. The P and I diagram will resemble the process ow-sheet, but the
process information is not shown. The same equipment identication numbers should
be used on both diagrams.

6.2.1 Symbols and layout
The symbols used to show the equipment, valves, instruments and control loops will
depend on the practice of the particular design ofce. The equipment symbols are
usually more detailed than those used for the process ow-sheet.
Standard symbols for instruments, controllers and valves are given in the
British Standard BS 1646.
Austin (1979) gives a comprehensive summary of the British Standard symbols,
and also shows the American standard symbols (ANSI) and examples of those used by
some process plant contracting companies.
The German standard symbols are covered by DIN 28004, DIN (1988).
When laying out the diagram, it is only necessary to show the relative elevation
of the process connections to the equipment where these affect the process
operation; for example, the net positive suction head (NPSH) of pumps, barometric
legs, syphons and the operation of thermosyphon reboilers.

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6.2.2 List Of Pid Items
Instrumentation and designations
Mechanical equipment with names and numbers
All valves and their identifications
Process piping, sizes and identification
Miscellanea - vents, drains, special fittings, sampling lines, reducers, increasers
and swagers
Permanent start-up and flush lines
Flow directions
Interconnections references
Control inputs and outputs, interlocks
Interfaces for class changes
Computer control system input
Identification of components and subsystems delivered by others


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6.2.3 Basic symbols
The symbols illustrated below are those given in BS 1646.


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6.2.3.1 Control valve

This symbol is used to represent all types of control valve, and both pneumatic an
electric actuators.
6.2.3.2 Failure mode
The direction of the arrow shows the position of the valve on failure of the power
supply.

6.2.3.3 Instruments and controllers

Locally mounted means that the controller and display is located out on the plant near
to the sensing instrument location. Main panel means that they are located on a panel

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in the control room. Except on small plants, most controllers would be mounted in the
control room.

6.2.3.4 Type of instrument
This is indicated on the circle representing the instrument-controller by a letter code


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The first letter indicates the property measured; for example, F D flow. Subsequent
letters indicate the function; for example,
I = indicating
RC = recorder controller
The suffixes E and A can be added to indicate emergency action and/or alarm
functions. The instrument connecting lines should be drawn in a manner to distinguish
them from the main process lines. Dotted or cross-hatched lines are normally used.


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6.3 Introduction to Valve
By definition, valves are mechanical devices specifically designed to direct, start, stop,
mix, or regulate the flow, pressure, or temperature of a process fluid. Valves can be
designed to handle either liquid or gas applications.
By nature of their design, function, and application, valves come in a wide
variety of styles, sizes, and pressure classes. The smallest industrial valves can weigh
as little as 1 lb (0.45 kg) and fit comfortably in the human hand, while the largest can
weigh up to 10 tons (9070 kg) and extend in height to over 24 ft (6.1 m). Industrial
process valves can be used in pipeline sizes from 0.5 in [nominal diameter (DN) 15] to
beyond 48 in (DN 1200), although over 90 percent of the valves used in process
systems are installed in piping that is 4 in (DN 100) and smaller in size. Valves can be
used in pressures from vacuum to over 13,000 psi (897 bar).
Todays spectrum of available valves extends from simple water faucets to
control valves equipped with microprocessors, which provide single-loop control of the
process. The most common types in use today are gate, plug, ball, butterfly, check,
pressure-relief, and globe valves.
Valves can be manufactured from a number of materials, with most valves
made from steel, iron, plastic, brass, bronze, or a number of special alloys.
A valve is a device that regulates, directs or controls the flow of a fluid (gases,
liquids, fluidized solids, or slurries) by opening, closing, or partially obstructing various
passageways. Valves are technically pipe fittings, but are usually discussed as a
separate category.

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In an open valve, fluid flows in a direction from higher pressure to lower
pressure. The simplest, and very ancient, valve is simply a freely hinged flap which
drops to obstruct fluid (gas or liquid) flow in one direction, but is pushed open by flow
in the opposite direction.
Valves are used in a variety of contexts, including industrial, military,
commercial, residential, and transport. The industries in which the majority of valves
are used are oil and gas, power generation, mining, water
reticulation, sewage and chemical manufacturing.
In daily life, most noticeable are plumbing valves, such as taps for tap water.
Other familiar examples include gas control valves on cookers, small valves fitted
to washing machines and dishwashers, safety devices fitted to hot water systems, and
valves in car engines. In nature, veins acting as valves are controlling the blood
circulation; heart valves control the flow of blood in the chambers of the heart and
maintain the correct pumping action.
Valves play a vital role in industrial applications ranging from transportation of
drinking water to control of ignition in a rocket engine.
Valves may be operated manually, either by a handle, lever or pedal. Valves
may also be automatic, driven by changes in pressure, temperature, or flow. These
changes may act upon a diaphragm or a piston which in turn activates the valve,
examples of this type of valve found commonly are safety valves fitted to hot water
systems or boilers.

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More complex control systems using valves requiring automatic control based
on an external input (i.e., regulating flow through a pipe to a changing set point)
require an actuator. An actuator will stroke the valve depending on its input and set-
up, allowing the valve to be positioned accurately, and allowing control over a variety
of requirements (http://en.wikipedia.org/wiki/Valve).


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6.3.1 Type of Valve
Valves are quite diverse and may be classified into a number of basic types. There are
generally three major type of valve, which are (http://www.valvias.com/types-of-
valves.php):
1. Multi-turn valve
Annular valve
Diaphragm valve
Fixed valve
Gate valve
Needle valve
Pinch valve
2. Quarter-turn valve
Ball valve
Butterfly valve
Plug valve
3. Check valve
Rubber duck-bill check valve
Tilting disc check valve


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6.3.2 Multi-Turn Valve
6.3.2.1 Annular Valves

Annular valves are suitable for regulating flow and pressure. They are prepared
to work against all column water pressure without cavitation.
The closure member has conical shape, and it moves in the axial direction of the tube.
The flow goes around the closure member when the valve is open.


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6.3.2.2 Diaphragm Valves

Diaphragm valves are used on shut-off and throttling service for liquids, slurries and
vacuum/gas. The seal is achieved by a flexible membrane, usually elastomer, and
possibly reinforced with a metal part. The membrane is tensed by the effect of a
stem/compressor with lineal movement until contact is made against the seal of the
body.
The operating parts of the diaphragm valve are isolated from the flow. This
makes this valve suitable for viscous flows and also hazardous, abrasive and corrosive
flows as its sealing system avoids any contamination towards or from the environment.

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Diaphragm valves are available in a wide variety of metals, solid plastics, plastic,
rubber and glass linings. They are well suited to the handling of multiple chemical
applications both clear fluids as well as slurries.
The diaphragm valve has an extended use for applications at low pressures and
slurry fluid where most other kinds of valves corrode or become obstructed.It is a
quick opening valve.
There are two types of diaphragm valves:
Weir: The Weir Diaphragm valve can be used for either off/on and throttling
services
Straightway: named also Straight-Thru is only used for on/off services.


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6.3.2.3 Fixed Cone Valve
Fixed Cone valve is a Free Discharge valve, it is also known as Howell Bunger and
Hollow Jet valves. These valves are used to discharge water at high pressure from
reservoirs or full pipes into atmosphere. Some designed valves can also work
submerged in the water.
The flow towards the exit of the valve is not converging so that the discharge is
in the shape of a hollow jet. A major air area contact with the water spray reduces the
kinetic energy of water.
The hollow jet valve is designed to dissipate huge amount of energy without
cavitation and vibration. A hood can be incorporated at the end of the valve in order
to reduce the risk of erosion from the water jet against the immediate environment.
Submerged valves need a special profile chamber to avoid hydraulic instabilities.


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6.3.2.4 Gate Valves

The gate valve, also known as a sluice valve, is a valve that opens by lifting
around or rectangular gate/wedge out of the path of the fluid. The distinct feature of
a gate valve is the sealing surfaces between the gate and seats are planar, so gate
valves are often used when a straight-line flow of fluid and minimum restriction is
desired. Thgate faces can form a wedge shape or they can be parallel. Gate valves are
primarily used to permit or prevent the flow of liquids, but typical gate valves
shouldn't be used for regulating flow, unless they are specifically designed for that
purpose. Because of their ability to cut through liquids, gate valves are often used in
the petroleum industry. For extremely thick fluids, a specialty valve often known as
a knife valve is used to cut through the liquid.

On opening the gate valve, the flow
path is enlarged in a highly nonlinear manner with respect to percent of opening. This
means that flow rate does not change evenly with stem travel. Also, a partially open
gate disk tends to vibrate from the fluid flow. Most of the flow change occurs near
shutoff with a relatively high fluid velocity causing disk and seat wear and eventual
leakage if used to regulate flow. Typical gate valves are designed to be fully opened

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or closed.

When fully open, the typical gate valve has no obstruction in the flow path,
resulting in very low friction loss.
Gate valves are characterized as having either a rising or a nonrising stem.
Rising stems provide a visual indication of valve position because the stem is attached
to the gate such that the gate and stem rise and lower together as the valve is
operated. Nonrising stem valves may have a pointer threaded onto the upper end of
the stem to indicate valve position, since the gate travels up or down the stem on the
threads without raising or lowering the stem. Nonrising stems are used underground
or where vertical space is limited.
Bonnets provide leakproof closure for the valve body. Gate valves may have a
screw-in, union, or bolted bonnet. Screw-in bonnet is the simplest, offering a durable,
pressure-tight seal. Union bonnet is suitable for applications requiring frequent
inspection and cleaning. It also gives the body added strength. Bolted bonnet is used
for larger valves and higher pressure applications.
Another type of bonnet construction in a gate valve is pressure seal bonnet.
This construction is adopted for valves for high pressure service, typically in excess of
15 MPa (2250 psi). The unique feature about the pressure seal bonnet is that the
body - bonnet joints seals improves as the internal pressure in the valve increases,
compared to other constructions where the increase in internal pressure tends to
create leaks in the body-bonnet joint.
Gate valves may have flanged ends which are drilled according to pipeline
compatible flange dimensional standards. Gate valves are typically constructed

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from cast iron, ductile iron, cast carbon steel, gun metal, stainless steel, alloy steels,
and forged steels.


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6.3.2.5 Needle Valve

A needle valve is a type of valve having a small port and a threaded, needle-shaped
plunger. It allows precise regulation of flow, although it is generally only capable of
relatively low flow rates
It is called needle valve due to the shape of the closure member. It consists on
a threaded stem with a conical end.
A needle valve has a relatively small orifice with a long, tapered seat, and a
needle-shaped plunger, on the end of a screw, which exactly fits this seat.
As the screw is turned and the plunger retracted, flow between the seat and
the plunger is possible; however, until the plunger is completely retracted the fluid
flow is significantly impeded. Since it takes many turns of the fine-threaded screw to
retract the plunger, precise regulation of the flow rate is possible.
The virtue of the needle valve is from the vernier effect of the ratio between
the needle's length and its diameter, or the difference in diameter between needle

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and seat. A long travel axially (the control input) makes for a very small and precise
change radially (affecting the resultant flow).
Needle valves may also be used in vacuum systems, when a precise control of
gas flow is required, at low pressure,
[1]
such as when filling gas-filled vacuum
tubes, gas lasers and similar devices.
Stems with fine threaded have a slow linear movement when they turn,
therefore a great number of turns are needed to have a full flow section. This makes
the needle valve suitable for regulating flow, with a minimal waste and without
cavitation at important differential pressures.
This valve is also placed in the bypass of the turbine inlet valve. That valve is
normally butterfly or spherical type and not prepared to open against all column water
pressure. The slow opening and regulated closure of the needle valve avoid cavitation
and water hammer in the pipeline system.
Needle valves are usually used in flow metering applications, especially when a
constant, calibrated, low flow rate must be maintained for some time, such as the idle
fuel flow in a carburetor. Since flow rates are low and many turns of the valve stem
are required to completely open or close, needle valves are not used for simple
shutoff applications.
Since the orifice is small and the force advantage of the fine-threaded stem is
high, needle valves are usually easy to shut off completely, with merely "finger tight"

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pressure. The spindle and/or seat of a needle valve, especially one made from brass,
are easily damaged by excessive turning force when shutting off the flow.
Small, simple needle valves are often used as bleed valves in hot water heating
applications.
Unlike a ball valve, or valves with a rising stem, it is not easy to tell from
examining the handle position whether the valve is open or closed.


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6.3.2.6 Pinch Valves

Pinch valves used for fluids usually employ a device that directly contacts process
tubing. Forcing the tubing together will create a seal that is equivalent to the
tubing's permeability. Major components of a pinch valve consists of body and a
sleeve. The sleeve will contain the flow media and isolate it from the environment
hence reducing contamination to the environment. Generally used for slurries or
processes with entrained solids, because the flexible rubber sleeve allows the valve to
close droptight around solidssolids that would typically be trapped by the seat or
stuck in crevices in globe, diaphragm, butterfly, gate, or ball valves. The sleeve
material can be selected upon the corrosiveness and abrasiveness of the flow media, a
suitable synthetic polymer can be chosen. A pinch valve may be the best type of valve

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for flow control application if the operation temperature is within the limit of the
polymer.
The sealing in pinch valves is achieved throttling the flexible tube of the valve
named elastic sleeve which is the only part in contact with the medium. Pinch valves
are suitable for handling slurries and solids in suspension, avoiding contact with the
valve mechanism and any contamination towards or from the environment.
Generally, the pinch valve is limited to work at low pressures. Pinch valves can
be mechanically or pressure actuated. In mechanically actuated valves, as shown in
the above picture, especially when they are handing abrasive fluids, it is advised to
close tightly the valve to prevent erosion of the flexible tube by the effect of leakage
flow.
In pressure actuated pinch valves, as in the valve shown in the picture on the
right, the pressure is uniformly distributed over the external side of the flexible tub.
As advantage over the mechanically actuated valves, the pass section is always
circular and then bigger particles can go through. But pressure actuated pinch valves
can not be 100% closed and can not be manually controlled since there is a
dependency on the flow pressure, this can be resolve with a pressure regulator.
The flexible tube is made of elastomer, usually reinforced. Material selection
should be done according to a corrosion-strength commitment since the elastomer
strength properties can be reduced by the attack of the corrosive fluid. Fatigue limit of
the material must fit on-off valve cycling.

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Sleeve Type:
Full port: the sleeve diameter remains constant from inlet to outlet port.
-Double Wall: This wall gives more protection at cost effective and simple
design for highly abrasive applications.
Cone: design for control applications. By reducing the center section of the
valve sleeve, it is possible to achive the required flow coefficient (Cv, Kv) of the
valve.
Reduced Port: as cone sleeve, the flow coefficient of the valve fits control
application.
Variable orifices: These orifices are designed for high-turndown control
application. They also help avoid cavitation

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6.3.3 Quarter-Turn Valve
6.3.3.1 Ball Valve

A ball valve is a valve with a spherical disc, the part of the valve which controls the
flow through it. The sphere has a hole, or port, through the middle so that when the
port is in line with both ends of the valve, flow will occur. When the valve is closed,
the hole is perpendicular to the ends of the valve, and flow is blocked. The handle or
lever will be inline with the port position letting you "see" the valve's position. The ball
valve, along with the butterfly valve and plug valve, are part of the family of quarter
turn valves.
Ball valves are durable and usually work to achieve perfect shutoff even after
years of disuse. They are therefore an excellent choice for shutoff applications (and
are often preferred to globe valves and gate valves for this purpose). They do not
offer the fine control that may be necessary in throttling applications but are
sometimes used for this purpose.
Ball valves are used extensively in industrial applications because they are very
versatile, supporting pressures up to 1000 bar and temperatures up to 482F (250C).

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Sizes typically range from 0.2 to 11.81 inches (0.5 cm to 30 cm). They are easy to
repair and operate.
The body of ball valves may be made of metal, plastic or metal with
a ceramic center. The ball is often chrome plated to make it more durable.
The ball valve has a spherical plug as a closure member. Seal on ball valves is
excellent, the ball contact circumferentially uniform the seat, which is usually made of
soft materials.
Ball valves are mostly used in shutoff applications. They are not recommended
to be used in a partially open position for a long time under conditions of a high
pressure drop across the valve, thus the soft seat could tend to flow through the
orifice and block the valve movement.
Depending on the type of body the ball valve can be more or less easily
maintained. Drop pressure relative its hole size is low. The seat material resistance of
the ball valve limits the working temperature and pressure of the valve. The seat is
plastic or metal made.
They are used in steam, water, oil, gas, air, corrosive fluids, and can also
handle slurries and dusty dry fluids. Abrasive and fibrous materials can damage the
seats and the ball surface.


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Types of ball valve:
Float ball valve: the ball is held on two seat rings.

Trunnion ball valve: the ball is supported on its vertical rotation axis by a
trunnion. The trunnion absorbs the pressure from the flow, therefore the
contact between the ball and the seat is not excessively stressed and the
operating torque can remain low. This design is recommend for big diameters
and high pressure.


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Types of Body:
Welded: Welded ball valves guarantee the absence of leakages along all the
valve's life, with no requirement for maintenance operations. This is a highly
important requisite especially for ball valves installed onto underground and
submarine pipelines. It is also often chosen for hazardous fluids.
Top entry: The ball can be taken out removing the top cover. It can be
repaired on site.
End entry: The body is one piece. The ball is entered from the axial entry.
Split body: there are two or three pieces. It allows easy inspection and
maintenance of all internal parts.


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6.3.3.2 Butterfly Valves

A butterfly valve is a valve which can be used for isolating or regulating flow. The
closing mechanism takes the form of a disk. Operation is similar to that of a ball valve,
which allows for quick shut off. Butterfly valves are generally favored because they
are lower in cost to other valve designs as well as being lighter in weight, meaning
less support is required. The disc is positioned in the center of the pipe, passing
through the disc is a rod connected to an actuator on the outside of the valve.
Rotating the actuator turns the disc either parallel or perpendicular to the flow. Unlike
a ball valve, the disc is always present within the flow, therefore a pressure drop is
always induced in the flow, regardless of valve position.
A butterfly valve is from a family of valves called quarter-turn valves. The
"butterfly" is a metal disc mounted on a rod. When the valve is closed, the disc is
turned so that it completely blocks off the passageway. When the valve is fully open,

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the disc is rotated a quarter turn so that it allows an almost unrestricted passage of
the fluid. The valve may also be opened incrementally to throttle flow.
There are different kinds of butterfly valves, each adapted for different
pressures and different usage. The resilient butterfly valve, which uses the flexibility of
rubber, has the lowest pressure rating. The high performance butterfly valve, used in
slightly higher-pressure systems, features a slight offset in the way the disc is
positioned, which increases the valve's sealing ability and decreases its tendency to
wear. The valve best suited for high-pressure systems is the triple offset butterfly
valve, which makes use of a metal seat, and is therefore able to withstand a greater
amount of pressure.
Butterfly valves are quite versatile ones. They can be used at multiples
industrial applications, fluid, sizes, pressures, temperatures and connections at a
relative low cost.
The development of this type of valve has been more recent than other ones. A
major conviction on saving energy in the installations was an advantage for its
introduction, due its head loss is small. At the beginning they were used in low
pressure installations service, but technologic improvements, specially in the
elastomer field let their extension to higher performances.
As any quarter turn valve, the operative of the butterfly valve is quiet easy. The
closure member is a disc that turns only 90; to be full opened/closed. This is a quick
operation. Few wear of the shaft, little friction and then less torque needed means a

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cheaper actuator. The actuator can be manual, oleo hydraulic or electrical motorized,
with automation available.
Butterfly valves geometry is simple, compact and revolute, therefore it is a
cheap valve to manufacture either saving material and post mechanization.
Its reduced volume makes easy its installation. Gate and globe valves are heavier and
more complex geometry, therefore butterfly valve can result quiet attractive at big
sizes regarding other types of valves.
The head loss is small as the flow goes aerodynamically around the disc when valve is
full open. Although the head loss is slightly higher than in spherical and gate valves,
because their flow sections are totally free from obstacles, it is clearly lower than in
globe valves.
Butterfly valves can work with any kind of fluid, gas, liquid and also with solids
in suspension. As a difference from gate, globe or ball valves, there are not cavities
where solid can be deposit and difficult the valve operative.
Pressure and temperature are determinant and correlated designing factors. At
a constant pressure, rising temperature means a lower performance for the valve,
since some materials have lower capacity. As well gate, globe and ball valves, the
butterfly valve can be manufactured with metallic seats that can perform at high
pressure and extreme temperatures.

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Types of Butterfly Valves
1. Concentric butterfly valves - This type of valves has a resilient rubber seat with
a metal disc.
2. Doubly-eccentric butterfly valves (high-performance butterfly valves or double-
offset butterfly valves) - Different type of materials is used for seat and disc.
3. Triply-eccentric butterfly valves (triple-offset butterfly valves) - The seats are
either laminated or solid metal seat design.
Triply-eccentric (offset) design
Triple eccentric (offset) Design prevents galling and scratches between the
metal seat and the metal disc due to its unique design. The only time where the seal
comes into contact with the seat is at the point of complete closure. Triple offset
valves are generally used in applications which require bi-directional tight shut-off in
oil and gas, LNG/NPG terminal and tanks, chemical factories, and shipbuilding. They
are also used for dirty/heavy oil to prevent extrusion.
Wafer-style butterfly valves

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The wafer style butterfly valve is designed to maintain a seal against bi-
directional pressure differential to prevent backflow in systems designed for
unidirectional flow. It accomplishes this with a tightly fitting seal; i.e., gasket, o-ring,
precision machined, and a flat valve face on the upstream and downstream sides of
the valve.
Lug-style butterfly valve
Lug-style valves have threaded inserts at both sides of the valve body. This
allows them to be installed into a system using two sets of bolts and no nuts. The
valve is installed between two flangesusing a separate set of bolts for each flange.
This setup permits either side of the piping system to be disconnected without
disturbing the other side.
A lug-style butterfly valve used in dead end service generally has a reduced
pressure rating. For example a lug-style butterfly valve mounted between two flanges
has a 150 psi pressure rating. The same valve mounted with one flange, in dead end
service, has a 75 psi rating.


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6.3.3.3 Plug Valves

Plug valves are valves with cylindrical or conically tapered "plugs" which can be
rotated inside the valve body to control flow through the valve. The plugs in plug
valves have one or more hollow passageways going sideways through the plug, so
that fluid can flow through the plug when the valve is open. Plug valves are simple
and often economical.
When the plug is conically tapered, the stem/handle is typically attached to the
larger diameter end of the plug. Plug valves usually do not have bonnets but often
have the end of the plug with the handle exposed or mostly exposed to the outside.
In such cases, there is usually not much of a stem. The stem and handle often come
in one piece, often a simple, approximately L-shaped handle attached to the end of
the plug. The other end of the plug is often exposed to the outside of the valve too,
but with a mechanism that retains the plug in the body.

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The simplest and most common general type of plug valve is a 2-port valve
with two positions: open to allow flow, and shut (closed) to stop flow. Ports are
openings in the valve body through which fluid can enter or leave. The plug in this
kind of valve has one passageway going through it. The ports are typically at opposite
ends of the body; therefore, the plug is rotated a fourth of a full turn to change from
open to shut positions. This makes this kind of plug valve aquarter-turn valve. There is
often a mechanism limiting motion of the handle to a quarter turn, but not in glass
stopcocks.
Slightly conically tapered metal (often brass) plug valves are often used as
simple shut-off valves in household natural gas lines.
It is also possible for a plug valve to have more than two ports. In a 3-way plug
valve, flow from one port could be directed to either the second or third port. A 3-way
plug valve could also be designed to shift flow between ports 1 and 2, 2 and 3, or 1
and 3, and possibly even connect all three ports together. The flow-directing
possibilities in multi-port plug valves are similar to the possibilities in corresponding
multi-port ball valves or corresponding multi-port valves with a rotor. An additional
possibility in plug valves is the have one port on one side of the plug valve and two
ports on the other side, with two diagonal and parallel fluid pathways inside the plug.
In this case the plug can be rotated 180 to connect the port on the one side to either
of the two ports on the other side.
Stopcocks used in laboratory glassware are typically forms of conically tapered
plug valves. When fused with the glassware, the valve bodies are made of glass.

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Otherwise, they can be made of an inert plastic such as Teflon. The plugs can be
made of a similar plastic or glass. When the plug is made of glass, the handle and
plug are fused together in one piece out of glass. When glass is used for both the
stopcock body and the plug, the contacting surfaces between them are special ground
glass surfaces (see Laboratory glassware) often with stopcock grease in between.
Special glass stopcocks are made for vacuum applications, such as in use with
vacuum manifolds. Stopcock grease is always used in high vacuum applications to
make the stopcock air-tight. Also if the plug valve is "locked" from being in the open
or closed position for an extended amount of time lubricant can be added through the
greaser with the valve in service.


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6.3.3.4 Check Valve
A check valve, clack valve, non-return valve or one-way valve is a mechanical device,
a valve, which normally allows fluid (liquid or gas) to flow through it in only one
direction.
Check valves are two-port valves, meaning they have two openings in the
body, one for fluid to enter and the other for fluid to leave. There are various types of
check valves used in a wide variety of applications. Check valves are often part of
common household items. Although they are available in a wide range of sizes and
costs, check valves generally are very small, simple, and/or inexpensive. Check valves
work automatically and most are not controlled by a person or any external control;
accordingly, most do not have any valve handle or stem. The bodies (external shells)
of most check valves are made of plastic or metal.
An important concept in check valves is the cracking pressure which is the
minimum upstream pressure at which the valve will operate. Typically the check valve
is designed for and can therefore be specified for a specific cracking pressure.
Heart valves are essentially inlet and outlet check valves for
the heart ventricles, since the ventricles act as pumps.


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Types of check valves:
6.3.3.4.1 Ball Check Valve
A ball check valve is a check valve in which the closing member, the movable part to
block the flow, is a spherical ball. In some ball check valves, the ball is spring-loaded
to help keep it shut. For those designs without a spring, reverse flow is required to
move the ball toward the seat and create a seal. The interior surface of the main seats
of ball check valves are more or less conically-tapered to guide the ball into the seat
and form a positive seal when stopping reverse flow.
Ball check valves are often very small, simple, and cheap. They are commonly
used in liquid or gel minipump dispenser spigots, spray devices, some rubber bulbs for
pumping air, etc., manual air pumps and some other pumps, and refillable dispensing
syringes. Although the balls are most often made of metal, they can be made of other
materials, or in some specialized cases out of artificial ruby. High
pressure HPLC pumps and similar applications commonly use small inlet and outlet
ball check valves with both balls and seats made of artificial ruby, for both hardness
and chemical resistance. After prolonged use, such check valves can eventually wear
out or the seat can develop a crack, requiring replacement. Therefore, such valves are
made to be replaceable, sometimes placed in a small plastic body tightly-fitted inside a
metal fitting which can withstand high pressure and which is screwed into the pump
head.
There are similar check valves where the disc is not a ball, but some other
shape, such as a poppet energized by a spring. Ball check valves should not be

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confused with ball valves, which is a different type of valve in which a ball acts as a
controllable rotor to stop or direct flow.
6.3.3.4.2 Diaphragm check valve
A diaphragm check valve uses a flexing rubber diaphragm positioned to create
a normally-closed valve. Pressure on the upstream side must be greater than the
pressure on the downstream side by a certain amount, known as the pressure
differential, for the check valve to open allowing flow. Once positive pressure stops,
the diaphragm automatically flexes back to its original closed position.
6.3.3.4.3 Swing Check Valve
A swing check valve or tilting disc check valve is check valve in which the disc,
the movable part to block the flow, swings on a hinge or trunnion, either onto the seat
to block reverse flow or off the seat to allow forward flow. The seat opening cross-
section may be perpendicular to the centerline between the two ports or at an angle.
Although swing check valves can come in various sizes, large check valves are often
swing check valves. The flapper valve in a flush-toilet mechanism is an example of this
type of valve.
Tank pressure holding it closed is overcome by manual lift of the flapper. It
then remains open until the tank drains and the flapper falls due to gravity. Another
variation of this mechanism is the clapper valve, used in applications
such firefighting and fire life safety systems. A hinged gate only remains open in the
inflowing direction. The clapper valve often also has a spring that keeps the gate shut
when there is no forward pressure. Another example is the backwater valve (for
sanitary drainage system) that protects against flooding caused by return flow of

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sewage waters. Such risk occurs most often in sanitary drainage systems connected to
combined sewerage systems and in rainwater drainage systems. It may be caused by
intense rainfall, thaw or flood.
6.3.3.4.4 Stop-Check Valve
A stop-check valve is a check valve with override control to stop flow regardless of
flow direction or pressure. In addition to closing in response to backflow or insufficient
forward pressure (normal check-valve behavior), it can also be deliberately shut by an
external mechanism, thereby preventing any flow regardless of forward pressure.
6.3.3.4.5 Lift-Check Valve
A lift-check valve is a check valve in which the disc, sometimes called a lift, can be
lifted up off its seat by higher pressure of inlet or upstream fluid to allow flow to the
outlet or downstream side. A guide keeps motion of the disc on a vertical line, so the
valve can later reseat properly. When the pressure is no longer higher, gravity or
higher downstream pressure will cause the disc to lower onto its seat, shutting the
valve to stop reverse flow.
6.3.3.4.6 In-Line Check Valve
An in-line check valve is a check valve similar to the lift check valve. However, this
valve generally has a spring that will 'lift' when there is pressure on the upstream side
of the valve. The pressure needed on the upstream side of the valve to overcome the
spring tension is called the 'cracking pressure'. When the pressure going through the
valve goes below the cracking pressure, the spring will close the valve to prevent
back-flow in the process.

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6.3.3.4.7 Duckbill Valve
A duckbill valve is a check valve in which flow proceeds through a soft tube that
protrudes into the downstream side. Back-pressure collapses this tube, cutting off
flow.
6.3.3.4.8 Duck-Bill Check Valve
The rubber Duck-bill check valve is all rubber reinforced. It consists in an elastomer
sleeve flattened in one end. The Duckbill valve can only be opened when the forward
flow lifts the sealing flattened side of the sleeve that, otherwise its natural position is
to be closed.
The rubber check valve requires no external power sources and because there
is not mechanism it doesn't require maintenance, therefore it can be more competitive
than other valves used for the same function such as gate valves.
Some elastomers can hand corrosive or abrasive fluids such as raw sewage,
sludge or slurries. The operating temperature of the valve is limited by the elastomer
temperature capacity.


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6.3.3.4.9 Tilting Disc Check Valve
The tilting disc check valve, as check valve is opened when flow goes through one
direction and closes at backflow Thanks to the fast closure of this versatile valve,
pump protection is one of its main applications. It is used for gases and liquids, bus it
is not recommended when there are solids in suspension. The head drop is relatively
low


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6.4 Introduction to Safety Valve and Relief Valve
A safety valve is a valve mechanism for the automatic release of a substance from
a boiler, pressure vessel, or other system when the pressure or temperature exceeds
preset limits.
It is part of a bigger set of pressure safety valves (PSV) or pressure relief
valves (PRV). The other parts of the set are relief valves, safety relief valves, pilot-
operated relief valves, low pressure safety valves, and vacuum pressure safety valves.
Safety valves were first used on steam boilers during the industrial revolution.
Early boilers without them were prone to accidental explosion.
In the petroleum refining, petrochemical, chemical manufacturing, natural gas
processing, power generation, food, drinks, cosmetics and pharmaceuticals industries,
the term safety valve is associated with the terms pressure relief
valve (PRV), pressure safety valve (PSV) and relief valve. The generic term is Pressure
relief valve(PRV) or pressure safety valve (PSV) It should be noted that PRVs and
PSVs are not the same thing, despite what many people think; the difference is that
PSVs have a manual lever to open the valve in case of emergency.
Relief valve (RV): automatic system that is actuated by static pressure in a
liquid-filled vessel. It specifically opens proportionally with increasing pressure.
Safety valve (SV): automatic system that relieves the static pressure on a gas.
It usually opens completely, accompanied by a popping sound.
Safety relief valve (SRV): automatic system that relieves by static pressure on
both gas and liquid.

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Pilot-operated safety relief valve (POSRV): automatic system that relieves on
remote command from a pilot to which the static pressure (from equipment to
protect) is connected
Low pressure safety valve (LPSV): automatic system that relieves static
pressure on a gas. Used when the difference between the vessel pressure and
the ambient atmospheric pressure is small.
Vacuum pressure safety valve (VPSV): automatic system that relieves static
pressure on a gas. Used when the pressure difference between the vessel
pressure and the ambient pressure is small, negative and near the atmospheric
pressure.
Low and vacuum pressure safety valve (LVPSV): automatic system that relieves
static pressure on a gas. The pressure is small, negative or positive and near
the atmospheric pressure.
RV, SV and SRV are spring-operated (even said spring-loaded). LPSV and VPSV are
spring-operated or weight-loaded.


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6.5 Relief Concepts
Pressure relief systems are required for the following reasons:
1. to protect personnel from the dangers of overpressurizing equipment,
2. to minimize chemical losses during pressure upsets,
3. to prevent damage to equipment,
4. to prevent damage to adjoining property,
5. to reduce insurance premiums, and
6. to comply with governmental regulations.
6.6 Location of Reliefs
The procedure for specifying the location of reliefs requires the review of every
unit operation in the process and of every process operating step. The engineer
must anticipate the potential problems that may result in increased pressures.
Pressure relief devices are installed at every point identified as potentially hazardous,
that is, at points where upset conditions create pressures that may exceed the MAWP.
The type of questions asked in this review process are:
1. What happens with loss of cooling, heating, or agitation?
2. What happens if the process is contaminated or has a mischarge of a catalyst
or monomer?
3. What happens if the operator makes an error?
4. What is the consequence of closing valves (block valves) on vessels or in lines
that are filled with liquids and exposed to heat or refrigeration?

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5. What happens if a line fails, for example, a failure of a high-pressure gas line
into a low pressure vessel?
6. What happens if the unit operation is engulfed in a fire?
Guidelines for Specifying Relief Positions:
1. All vessels need reliefs, including reactors, storage tanks, towers, and drums.
2. Blocked-in sections of cool liquid-filled lines that are exposed to heat (such
as the sun) or refrigeration need reliefs.
3. Positive displacement pumps, compressors, and turbines need reliefs on the
discharge side.
4. Storage vessels need pressure and vacuum reliefs to protect against pumping
in or out of a blocked-in vessel or against the generation of a vacuum by
condensation.
5. Vessel steam jackets are often rated for low-pressure steam. Reliefs are
installed in jackets to prevent excessive steam pressures due to operator
error or regulator failure.


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6.7 Relief Types
Specific types of relief devices are chosen for specific applications, such as for
liquids, gases, liquids and gases, solids, and corrosive materials; they may be
vented to the atmosphere or vented to containment systems (scrubber, flare,
condenser, incinerator, and the like). In engineering terms the type of relief device
is specified on the basis of the details of the relief system, process conditions,
and physical properties of the relieved fluid.
There are two general categories of relief devices:
1. spring-operated
2. rupture discs)
Two major types of spring-operated valves:
1. conventional
2. balanced-bellows


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6.7.1 Spring-Operated Valves
On spring-operated valves the adjustable spring tension offsets the inlet pressure.
The relief set pressure is usually specified at 10% above the normal operating
pressure. To avoid the possibility of an unauthorized person changing this setting, the
adjustable screw is covered with a threaded cap. For a conventional spring-operated
relief, the valve opens based on the pressure drop across the valve seat; that is,
the set pressure is proportional to the pressure drop across the seat. Thus, if the
backpressure downstream of the valve increases, the set pressure will increase
and the valve may not open at the correct pressure. In addition, the flow through
the conventional relief is proportional to the difference in pressure across the seat.
The flow through the relief, therefore, is reduced as the backpressure increases.
6.7.2 Balanced-Bellows
For the balanced-bellows design the bellows on the backside of the valve seat
ensures that the pressure on that side of the seat is always atmospheric. Thus
the balanced-bellows valve will always open at the desired set pressure. However,
the flow through the balanced-bellows relief is proportional to the difference in
pressure between the inlet and the outlet of the valve. Therefore the flow is
reduced as the backpressure increases.


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6.7.3 Rupture Discs
Rupture discs are specially designed to rupture at a specified relief set pressure.
They usually consist of a calibrated sheet of metal designed to rupture at a well-
specified pressure. They are used alone, in series, or in parallel to spring-loaded
relief devices. They can be made from a variety of materials, including exotic
corrosion-resistant materials. An important problem with rupture discs is the flexing
of the metal as process pressures change. Flexing could lead to premature failure
at pressures below the set pressure. For this reason some rupture disc systems are
designed to operate at pressures well below the set pressure. In addition, vacuum
service may cause rupture disc failure if the relief system is not specifically
designed for this service.
Another problem with rupture disc systems is that once they open, they
remain open. This may lead to the complete discharge of process material. It
may also allow air to enter the process, leading to a possible fire and/or
explosion. In some accidents discs were ruptured without the process operator
being aware of the situation. To prevent this problem, rupture discs are available
with embedded wires that are cut when the disc ruptures; this can activate an
alarm in the control room to alert the operator. Also, when rupture discs rupture,
pieces of the disc may become dislodged, creating potential downstream plugging
problems. Recent advances in rupture disc design have minimized this problem.
In all these examples the problems are eliminated if the rupture disc and
system are specified and designed appropriately for the specific operating
conditions of the process.

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Rupture discs are available in much larger sizes than spring-operated relief
valves, with commercial sizes available up to several feet in diameter. Rupture discs
typically cost less than equivalently sized spring-operated relief valves.
Rupture discs are frequently installed in series to a spring-loaded relief:
1) To protect an expensive spring-loaded device from a corrosive environment,
2) To give absolute isolation when handling extremely toxic chemicals (spring-
loaded reliefs may weep),
3) To give absolute isolation when handling flammable gases,
4) To protect the relatively complex parts of a spring- loaded device from
reactive monomers that could cause plugging, and
5) To relieve slurries that may plug spring-loaded devices.
When rupture discs are used before a spring-loaded relief, a pressure gauge is
installed between the two devices. This telltale gauge is an indicator that shows when
the disc ruptures. The failure can be the result of a pressure excursion or of a pinhole
caused by corrosion. In eiher case the telltale gauge indicates that the disc needs to
be replaced.
There are three subcategory types of spring-loaded pressure reliefs:
1) The relief valve is primarily for liquid service. The relief valve (liquid only)
begins to open at the set pressure. This valve reaches full capacity when the
pressure reaches 25% overpressure. The valve closes as the pressure
returns to the set pressure.

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2) The safety valve is for gas service. Safety valves pop open when the
pressure exceeds the set pressure. This is accomplished by using a discharge
nozzle that directs high-velocity material toward the valve seat. After
blowdown of the excess pressure, the valve reseats at approximately 4%
below the set pressure; the valve has a 4% blowdown.
3) The safety relief valve is used for liquid and gas service. Safety relief
valves function as relief valves for liquids and as safety valves for gases


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6.8 P&ID for Reactor (Major Equipment)
6.8.1 P&ID for Reactor (Major Equipment)

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6.8.2 Justification of The Control System Applied to the Reactor (Major)
Temperature control is important in the reactor as it will affect the reaction rate of the
process. Reactor may not be able to withstand the temperature beyond its maximum
allowable working temperature and thus rupture. If the temperature is too low, the
reactant may not be able to react and convert to the product.
A ratio flow control on two of the inlets is recommended. With this, ratio of
propylene to benzene can be controlled at the right aount. A change in the flow rate
of propylene will change the flow of the feed benzene following a preset ratio
immediately.


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6.8.3 Justification of the Selection of the Type of Valve and Safety Valve to the Reactor (Major Equipment)
Type of
valve
Location of installation Justification
Ball
valve
Installed before and after
every equipment such as
pump, control valve, inlet
to reactor and so on as
shown in the PID. The
purpose is to ease the
maintenance of each
equipment. For emergency
shut down and so on.
Ball valves are excellent in chemical applications, including the most challenging services
(e.g., dry chlorine, hydrofluoric acid, oxygen). Readily available in a wide variety of
configurations, 3-piece, end entry and top entry, these valves range from commodity type
valves to high performance valves.

Advantages of ball valves include ease of operation, standard face-to-face dimensions,
high flow capacity, high pressure/temperature capabilities and ability to handle severe
service chemicals. The quarter turn operation is desirable to most operators and fairly
easy to automate.

The face-to-face dimensions comply with ASME, making the ball valve easy to retrofit

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and replace in line with most other ball valves and plug valves. Also compliant with ASME
is the flange rating, either 150, 300, 600, 900 # or occasionally higher classes, enabling
high performance ball valves to withstand up to 2250 psi. The ball valve temperature
which is primarily dependent on seats and seals may be rated as high as 550 F.

Higher temperatures are permitted when using metal seats.
Ball valves, available in reduced port and full port designs are considered high recovery
valves, meaning a low pressure drop and relatively high Cv, [coefficient of flow (gpm per
1 psi pressure drop)]. The benefits of these desirable flow parameters are reduced pump
size and less system wear due to lower velocity.
The ability to provide fire safe protection and handle severe service chemicals are two of
the significant advantages of the ball valve.
Source: http://www.engvalves.com


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Relief
valve
-installed at discharge
point of every pump to
prevent pressure build up
-installed at jacket
-installed on top of the
reactor to prevent
pressure build up
A spring operated valve is selected because rupture disk type will cause losing of the
entire content. Propylene, benzene and cumemne is an expensive. Besides, it may allow
air to enter the process, leading to a possible pump damage, fire or explosion. Propylene,
benzene and cumemne is highly flammable. Relief valve is selected because of this relief
is in a liquid service line. A conventional relief device is satisfactory.


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6.9 P&ID For Cumene Column (Minor Equipment)
6.9.1 P&ID For Cumene Column (Minor Equipment)


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6.9.2 Justification Of The Control System Applied To The Cumene Column
Since, column is a complex unit. Various flow meter, pressure meter and temperature
meter are installed along the inlet or outlet pipeline at different location to monitor the
operation condition. With this, it ease the engineer or operator to notified which point
of the process are in trouble.
A flow control on the inlets is recommended. With this, ratio of propylene to
benzene can be controlled at the right amount. Temperature control is important in
the column as it will affect the reaction rate of the process. Column may not be able
to withstand the temperature beyond its maximum allowable working temperature
and thus rupture. If the temperature is too low, the reactant may not be able to react
and convert to the product.


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6.9.3 Justification Of The Selection Of The Type Of Valve And Safety Valve To The Cumene Column (Minor)
Type of
valve
Location of
installation
Justification
Ball
valve
Installed before and
after every
equipment such as
pump, control
valve, inlet to
reactor and so on
as shown in the
PID. The purpose is
to ease the
maintenance of
each equipment.
Ball valves are excellent in chemical applications, including the most challenging services (e.g.,
dry chlorine, hydrofluoric acid, oxygen). Readily available in a wide variety of configurations, 3-
piece, end entry and top entry, these valves range from commodity type valves to high
performance valves.

Advantages of ball valves include ease of operation, standard face-to-face dimensions, high
flow capacity, high pressure/temperature capabilities and ability to handle severe service
chemicals. The quarter turn operation is desirable to most operators and fairly easy to
automate.

The face-to-face dimensions comply with ASME, making the ball valve easy to retrofit and

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For emergency shut
down and so on.
replace in line with most other ball valves and plug valves. Also compliant with ASME is the
flange rating, either 150, 300, 600, 900 # or occasionally higher classes, enabling high
performance ball valves to withstand up to 2250 psi. The ball valve temperature which is
primarily dependent on seats and seals may be rated as high as 550 F.

Higher temperatures are permitted when using metal seats.
Ball valves, available in reduced port and full port designs are considered high recovery valves,
meaning a low pressure drop and relatively high Cv, [coefficient of flow (gpm per 1 psi
pressure drop)]. The benefits of these desirable flow parameters are reduced pump size and
less system wear due to lower velocity.
The ability to provide fire safe protection and handle severe service chemicals are two of the
significant advantages of the ball valve.
Source: http://www.engvalves.com


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Relief
valve
-installed at
discharge point of
every pump to
prevent pressure
build up
-installed at jacket
-installed on top of
the reactor to
prevent pressure
build up
A spring operated valve is selected because rupture disk type will cause losing of the entire
content. Propylene, benzene and cumemne is an expensive. Besides, it may allow air to enter
the process, leading to a possible pump damage, fire or explosion. Propylene, benzene and
cumemne is highly flammable. Relief valve is selected because of this relief is in a liquid service
line. A conventional relief device is satisfactory.


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7.0 HAZOP ANALYSIS
7.1 HAZOP Analysis For Major Equipment - Reactor
Line : L-1
Intention : To Propylene into the reactor
Guide word Deviation Possible cause Possible consequences Action recommended
No/None Flow - Blockage of
pipeline
- control valve 1
fails to open
- Failure of
controller
- Failure of pump

- No feed supply to the
reactor
- No reaction occur in
Reactor R-100
- The ratio of propylene to
benzene is not at the right
ratio
- Check maintenance procedure and
schedule for valve, pipeline,
controller and pump
- Install a back-up control valve or
a by-pass across manual valve
- Install a pump in parallel to the
existing pump
- Install a level indicator on the
reactor
- Install a flow indicator on the
pipeline
- Install a strainer in the pipeline
- Install a low-level alarm on the
reactor to alert the operator

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- Check the emergency shutdown
system
Less Flow - Partial blockage
of pipeline
- Leaking of
pipeline
- Control valve 1
fails to respond
- Partial failure of
controller
pump

- Less feed supply to the
reactor
- Incomplete reaction in
Reactor R-1
ratio
schedule for valve, pipeline,
controller and pump
existing pump
- Install a strainer in the pipeline
reactor
pipeline
- Install a low-level alarm on the

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system
More Flow - Failure of
control valve 1
- Failure of the
controller
- More feed supply to the
reactor
Reactor R-1
ratio
- Flooding of the reactor
schedule for valve and controller
reactor
pipelinE
- Install a high-level alarm on the
system
Reverse Flow - Failure of
pump
- Possible back flow - Check maintenance procedure and
schedule for pump

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- Reactor
pressure is
higher than the
delivery
existing pump
- Install a non-return valve
- Install a pressure indicator on the
reactor
system

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Line : L-2
Intention: To transfer Benzene into the reactor
Guide
word
Deviation Possible cause Possible consequences Action recommended
No Flow - Blockage of pipeline
- Failure of flow controller
- Failure of pump

- No benzene supply in
the reactor
the reactor
- Low level of mixture in
the reactor
schedule for pipeline, controller and
pump.
- Install a back-up pump
- Install a level indicator on the reactor
- Install a flow indicator on the pipeline
- Install a low-level alarm on reactor to
alert the operator
- Check the emergency shutdown system
Less Flow - Partial blockage of
pipeline
- Leaking of pipeline
- Partial failure of flow
controller
- Partial failure of pump
- Less benzene supply
in the reactor
the reactor
- Low level of mixture in
the reactor
schedule for pipeline, controller and
pump.

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- Install a low-level alarm on reactor to
alert the operator
More Flow - Failure of the controller
- Failure of the pump
- More benzene supply
to the reactor
- Flooding of the reactor
- Excess benzene in the
final product
schedule for controller
- Install a high-level alarm on the reactor to
alert the operator
Reverse Flow - Failure of pump
- Reactor pressure is
higher than the delivery
- Possible back flow - Check maintenance procedure and
schedule for pump
- Install a pressure indicator on the reactor


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Line : L-3
Intention: to transfer the product to the next process
Guide
word
No Flow - Blockage of pipeline
- Failure of pump

- No flow to storage tank
- Reactor overflow
- Check maintenance procedure and schedule for
pipeline, and pump.
- Install a pump in parallel to the existing pump
- Install a level indicator on storage tank
- Install high level alarm on reactor
Less Flow - Partial blockage of
pipeline
- Leaking of pipeline
pump

- Reactor overflow
- Reactor overflow
- Check maintenance procedure and schedule for
pipeline, and pump.
- Install a level indicator on storage tank
- Install high level alarm on reactor
More Flow - High pressure
condition in the
- Overflow of storage
tank
- Check maintenance and schedule for valve.
- Install level indicator on storage tank.

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reactor

- Install high level alarm on storage tank
Reverse Flow - Failure of pump
- Storage tank
pressure is higher
than the delivery
- Possible back flow - Check maintenance procedure and schedule for
pump


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Line : L-4
Intention: To supply hot water into the reactor . (heating fluid)
Guide
word
No Flow - Failure of the hot
water tank.
- Control valve 2
fails to open
- Failure of
temperature
controller
- No heat supply to the
reactor
- Low temperature in the
reactor
- Slow reaction in the
reactor
the reactor
- Product degradation
- Check maintenance procedure and schedule
for hot water tank, valve and controller
- Install backup steam generator
- Install a back-up control valve or a by-pass
across manual valve
- Install Low temperature alarm on the reactor
Less Flow - Partial failure of
the hot water
tank..
control valve 2
- Less heat supply to the
reactor
reactor
- Slow reaction in the
reactor
for hot water tank., valve and controller
across manual valve

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controller - Incomplete reaction in
the reactor
- Install Low temperature alarm on the reactor
More Flow - Control valve 2
fails to close
- Failure of the
controller
- High temperature in the
reactor
- Denature of the enzyme
the reactor
- High pressure in the
pipeline
for control valve and controller.
across manual valve
- Install a flow and pressure indicator on the
pipeline
- Install high temperature alarm on the reactor
More Pressure - Failure of the hot
water tank.Control
valve fails to close
- Failure of the
controller

- More steam supply to
the reactor
- Possible explode of
pipeline

for hot water tank., control valve and
controller.
- Install a pressure indicator on the pipeline
across manual valve

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Less Pressure - Failure of the hot
water tank.Control
valve fails to open
- Failure of the
controller

- Less steam supply to
the reactor
for hot water tank, control valve and controller.
- Install a pressure indicator on the pipeline
across manual valve
More Temperature - Failure of the hot
water tank.
- High temperature in the
reactor.
for hot water tank.Install backup steam
generator
- Install a temperature indicator on the pipeline
- Install a high temperature alarm on the reactor
Less Temperature - Failure of the hot
water tank.
reactor.
for hot water tank.Install backup steam
generator
- Install a temperature indicator on the pipeline
- Install a low temperature alarm on the reactor

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As well
as
Hot water in
reactor
- Leak in heating
coils, pressure in
reactor is lower
than pressure in
coil
- Dilution of contents
- Product ruined
- Possible contamination
of product
As well
as
Storage
product in
coils
- Leak in coils with
reactor pressure is
greater than coils
pressure
- Product lost through
coils
- Loss of product yield
- Reduction in heating
function
- Install upstream check valve in hot water
source
Reverse Reverse
heating flow
- Back flow due to
back pressure
- Improper heating - Install check valve in hot water source


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Line : L-5
Intention: To remove the cool water from the jacket in the reactor and recycle back to the hot water tank
Guide
word
No Flow - Blockage of
pipeline

- Cool water cannot be removed and
accumulated in the jacket
- Pressure in the jacket increases
- Blasting of the jacket
- Back flow of the cool water and cause
damage to the control valve
- Low temperature in the reactor
schedule for pipeline, valve.

Less Flow - Partial blockage
of pipeline

- Cool water hardly be removed and
accumulated in the jacket
- Pressure in the jacket increases
- Blasting of the jacket
- Back flow of the cool water and cause
damage to the control valve
- Low temperature in the reactor
schedule for pipeline and steam trap.
- Install a by-pass manual valve across
the steam trap


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7.1.1 Recommendation HAZOP For Reactor
For reactor, installation of high/low temperature alarm and high/low flow alarm are
recommended. Temperature control is important in the reactor as it will affect the reaction
rate. High temperature condition will spoil its content and the material used to make
reactor may not be able to withstand the high temperature and thus melt. Lastly, an
installation of a ratio flow control on three of the inlets is recommended. With this, ratio of
propylene to benzene can be controlled. A change in the flow rate of propylene will change
the flow of the feed benzene by following a preset ratio immediately.


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7.2 HAZOP Analysis For Minor Equipment - Cumene Column

Equipment : Cumene Column
Intention : To separate cumene from DIPB
Line : L27
Intention : To transfer mixture of cumene and DIPB to Cumene Column
Item
No
Guide
Word
Deviation Possible cause Possible consequences Action required
27A No Flow - Failurein pump P303
- Control valves CV307 fails
closed
- Controller fails and closed
valves
- Air pressure to drive valve
fails, closing valve
- No feed to distillation column
(separator)
- Incomplete of separation
- Temperature and pressure in
separator increase
- Possible of explosion
- Check maintenance
procedure and schedule
for pump
- Install alarm system for
level and temperature
monitor
- Install relief/bypass system
- Install low flow alarm
- Install by pass control
valve


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27B Less Flow - Partially failure of pump
P303
to respond
- Insufficient feed to separator
- Incomplete separation
- Temperature and pressure
increase in separator
- Possible of explosion
- Check maintenance
procedure and schedule for
pump
- Install alarm system for
level and temperature
monitor
- Install relief/bypass system
27C More Flow - Overflow in line L22
to respond
- Overfeed to the distillation
column
- Pressure in line L27 increases
- Pressure in distillation column
increases
- Possible explosion

- Select valve to fail close
- Install high temperature
and pressure alarm
- Install high flow alarm
- Fit high-level alarm with
automatic pump shut-
down
- Fit second valve
- Install a bypass valve

27D Reverse Flow - Failure of pump P303
- Reactor pressure higher
- Back flow of mixture into
distillation column
- Install non-return valve

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than delivery

Line : L28
Intention: To transfer the bottom product from cumene Column (C302) to the steam reboiler for burning purpose.
Item
No
Guide
Word
28A No Flow - Failure in CV308 and
CV309
- Failure in temperature
recorder and controller
- No heat supply in distillation
column
- Transfer of the bottom heavy
product could not be done and
will caused higher mixture
concentration at cumene
Column

- Install backup control valve
- Place controller on critical
instrument list
- Maintenance of the control
valve CV308 and CV309
need to be done

28B Less Flow - Failure in control valve
CV308 and CV309

- Less bottom product was
unable to transfer back to
column which cause inefficient
- Install backup control valve
instrument list
- Maintenance of the CV308

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separation due to poor
reboiling of the separation.
- Increase of pressure at C404
and CV309 need to be
done
- Existence of valve CV308,
CV309, CV310 will stop the
flow and maintenance of
the Pump P304 need to be
done
28C More Flow - Failure in controller and
- fail to close
- Possible rupture of line L28
- Too much bottom product was
separation due to poor
reboiling of the separation.
- Increase of the pressure at
cumene Column

alarm
- Maintenance of the CV308
and CV309 need to be
done
- Existence of valve CV308,
CV309, CV310 will stop the
flow and maintenance of
the Pump P304 need to be
done
28E More Temperature - Temperature control in
distillation column failed
- Possible rupture of separator
alarm

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control - Place controller on critical
instrument list

28F Less Temperature - Failurein boiler
- Failure in control valve
CV308 and CV309
- Incomplete separation - Check maintenance and
schedule for boiler
28G More

Pressure

- Controller failure to open

- Rupture of C302
- Runaway reaction

instrument list
- Install relief system
- Install high pressure alarm

28H Reverse Flow - Failure of pump P304

- back flow of the bottom
product into cumene Column



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Line : L29
Intention: to transfer heavies from distillation column (separator) to heavies collector tank
Item
No
Guide
Word
29A No Flow - Failure in pump P304
- Control valve fails to
close
- Malfunction in
distillation column
- No flow to heavies collector tank
- Rupture in distillation column
- Transfer of the acetone product
could not be done and will
caused higher mixture
concentration at C302

- Check maintenance and
schedule for pump
- Install back-up control valve
- Select valve to fail open
instrument list
29B Less Flow - Partially failure of
pumpP304
- Control valve partially
open
- Controller fail and
valve fail to respond
- Slow process flow
- Heavies will flow into line L29
- Less phenol product was unable
to transfer to the tank which
causes inefficient separation.
- Failure of separation process

- Install bypass
schedule for pump
instrument list

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29C More Flow - Controller fail to open
valve CV310 and
CV311
- Heavies storage tank
- Flood
- Incomplete separated phenol
product was to transfer to the
tank which causes inefficient
separation.

instrument list.
29D Reverse Flow - Failure in pump P304
- Reactor pressure
higher than delivery

- Back flow of heavies into
distillation column
29E Less

Pressure

- Partial open valve
CV309
- Low gas transfer to Fuel gas
centre
- Ensure sufficient digestion
occur
- Maintenance on pump, pipe
line and valve
29F More

Pressure

- Controller fail to open
valve 310

- Rupture of Heavies storage tank
- Runaway reaction

instrument list


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Line : L30
Intention: To transfer the overhead product from cumene Column (C302) to the fuel gas system and reflux stream.
Item
No
Guide
Word
- Failure of control
valve CV 313
- Failure in distillation
column
- No flow to acetone product
column receiver
- Overhead product was unable to
transfer back to column which
cause inefficient separation due
to poor reflux of the separation.
- Caused the pressure at cumene
Column to increase

schedule for pump
- Install flow indicator at a feed
line

pump P305
- Insufficient flow to acetone
product column receiver
- Install bypass

280 | P a g e

- Less overhead product was
separation due to poor reflux of
the separation.
Column to increase

schedule for pump
- Install low flow alarm indicator

valve CV313
- cumene column receiver flood
- Too much overhead product was
transferred back to column which
cause inefficient separation due
to over reflux of the separation.
Column to increase
- Increase of pressure along the
pipe will cause explosion.
instrument list.
- Install level control indicator

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30D Reverse Flow - Failure inpump P305
- Acetone product
column receiver flood
pressure higher than
delivery

- Back flow of Acetone product
column condenser
- Flow of mixture back to cumene
Column
30E More Temperature - Temperature control
in distillation column
failed control
- Possible rupture of line L30
- Maintenance of the Pump
P305 need to be done
- Install high temperature alarm
30F Less

Pressure

- Partial open valve
CV313
- Low gas transfer to Fuel gas
centre
- Ensure sufficient digestion
occur
- Maintenance on pump, pipe
line and valve
30G More

Pressure

- Controller fail to open
controller valve
CV313

- Rupture of cumene column
receiver
- Runaway reaction

instrument list
30H More Temperature - Malfunctioning of - Increase temperature in cumene - Install High temperature alarm

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Condenser (E302) Column
- Increase Pressure in cumene
Column

- Maintenance of condenser
(E302) need to be done


283 | P a g e

Line : L 31
Intention: To transfer acetone from distillation column (separator) to acetone tank
Item
No
Guide
Word
- Control valve CV314
fails to close
- Failure in distillation
column
- No flow to acetone tank
- Rupture in distillation column
- cumene will flow into line L31
schedule for pump
instrument list
pump
P306
- Control valve CV314
partially open
- Controller fail and
valve fail to respond
- Slow process flow
- cumene will flow into line L31
- Install bypass
schedule for pump
instrument list
valve CV314
- cumene Tank flood - Place controller on critical
instrument list.

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31D Reverse Flow - Failure in Pump P306
- Reactor pressure
higher than delivery
- Back flow of acetone into
distillation column


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7.2.1 Recommendations HAZOP For Cumene Column
In HAZOP studies, the case of distillation column is evaluated considering that the risk of any
unwanted event is reduced by the installation of safety systems, and especially in the case of
loss of cooling capacity, the usual safety barrier is the steam valve closure. However, for
some distillation systems, where the difference of volatility of the components is high, the
simple safety chain suggested might not be enough to guarantee a safe unit shut down. The
dynamic effect of cumulated heat in the system might provide energy enough causing the re-
vaporization of the most volatile compound. Pressure relief system, level controller system
and temperature controller system must be installed on the acetone product column to
prevent the explosion and severe damage to the acetone product column. Other controllers
are desirable to be installed.Regular maintenance and equipment basic care activities are
required for all the main equipments to ensure a safer and more efficient plant operation.

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8.0 EXPLOSION ANALYSIS
8.1 Introduction to Fire and explosions
Fire and explosions are the dominant hazards in many industry sectors,
including cumene plant. Accident fires and explosions generally occur when
combustibles are produced, transported, or utilized in a hostile environment
or under unsafe conditions. Proper investigation of such accidents is essential
for determining their cause and assessing life or property loss and for
preventing their recurrence. This requires a methodical and through
investigation, knowledge of the basic properties of pertinent materials,
understanding of the ignitability and flammability characteristics of the
combustible-oxidant system, and understanding of combustion or explosion
principles. The management and control of such hazards is becoming
increasingly important from human, economic, environmental and legislative
view points.
One important tool available for the efficient management of fire and
explosion hazards is Fire and Explosion Analysis. It provides a structured and
quantified approach towards minimizing the effects of fire and explosion
hazards on cumene plant.
Fire and Explosion Risk Analysis can be carried out at various levels of
detail, depending on the intended application and study requirements. Any

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particular study can be tailored to the requirements from the main features
outlined as follows:
Identify flammable inventories and locations
Establish consequence of fire and explosion events in terms of
severity and escalation potential
Assess the effectiveness of existing safeguards from the prevention,
control and mitigation of flammable hazards
Identify main contributions to flammable risk

8.2 Distinction Between Fires And Explosions
The major distinction between fires and explosions is the rate of energy
release. Fires release energy slowly, whereas explosions release energy
rapidly, typically on the order of microseconds. Fires can also result from
explosions, and explosions can result from fires.


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8.3 Mechanism Of Fire And Explosion
Explosion behavior is difficult to characterize. Many approaches to the
problem have been undertaken, including theoretical, semiempirical, and
empirical studies. Despite these efforts, explosion behavior is still not
completely understood. Practicing engineers, therefore, should use
extrapolated results cautiously and provide a suitable margin of safety in all
designs.
An explosion results from the rapid release of energy. The energy
release must be sudden enough to cause a local accumulation of energy
at the site of the explosion. This energy is then dissipated by a variety of
mechanisms, including formation of a pressure wave, projectiles, thermal
radiation, and acoustic energy.
The damage from an explosion is caused by the dissipating energy.
If the explosion occurs in a gas, the energy causes the gas to expand
rapidly, forcing back the surrounding gas and initiating a pressure wave
that moves rapidly outward from the blast source. The pressure wave
contains energy, which results in damage to the surroundings. For chemical
plants much of the damage from explosions is due to this pressure
wave.
Thus, in order to understand explosion impacts, the dynamics of the
pressure wave must be well understood. A pressure wave propagating in air

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is called a blast wave because the pressure wave is followed by a strong
wind. A shock wave or shock front results if the pressure front has an
abrupt pressure change. A shock wave is expected from highly explosive
materials, such as TNT, but it can also occur from the sudden rupture of a
pressure vessel. The maximum pressure over ambient pressure is called
the peak overpressure.

8.4 Fire Triangle
Fire, or burning, is the rapid exothermic oxidation of an ignited fuel. The fuel
can be in solid, liquid, or vapor form, but vapor and liquid fuels are generally
easier to ignite. The combustion always occurs in the vapor phase; liquids
are volatized and solids are decomposed into vapor before combustion.
The essential elements for fire and explosion are fuel, an oxygen (air)
sources, and an ignition source. These elements are illustrated by the fire
triangle, shown in Figure 8.1.
When fuel, oxidizer, and an ignition source are present at the
necessary levels, burning will occur. This means a fire will not occur if:
(1) Fuel is not present or is not present in sufficient quantities
(2) An oxidizer is not present or is not present in sufficient quantities
(3) The ignition source is not energetic enough to initiate the fire.

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Figure 8.1 Expanded Fire Triangle

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8.5 Sources And Causes Of Fire And Explosion In Cumene Plant
8.5.1 Sources Of Fuel
Anything that can burn is potential fuel for a fire or, in some cases, an
explosion in cumene plant. These include:
Paper (including stored documents);
Cardboard (including packaging);
Plastics (including electronic media, X-ray plates, packaging etc);
Other stored materials or items;
Spirits;
Wood;
Diesel;
Mineral oils and grease;
Rubbish and other waste material;
Bottled gases e.g. acetylene, propane.


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8.5.2 Sources Of Ignition
A source of ignition is anything that has the potential to get hot enough to
ignite a material, substance or atmosphere in the workplace of cumene palnt.
These sources of heat might include:
Electrical and mechanical machinery and equipment, including;
Electrical sparking and hot surfaces from electrical equipment and
distribution systems;
Short circuits and earth faults on electrical equipment and
distribution systems;
Internal combustion engines exhaust systems, air inlets, hot
surfaces;
Friction; for example from seized brakes on vehicles;
Natural sources, for example electrostatic discharges and lightning;
Hot work burning, welding, and grinding;
Smokers materials, e.g. cigarettes, lighters and matches.


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In 1987/88 a study of 668 chemical industry fires and explosions in the US
identified the following most common causes:
Causes Percentages
Open Flames 39.1
Hot work 18.0
Electrical current 10.5
Hot surfaces 7.2
Smoking 5.7
Friction 5.4
Spontaneous Combustion 3.9
Auto-ignition 3.7
Hot particles 3.0
Static Electricity 2.8
Other 0.7


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8.5.3 Sources of Oxygen
The main source of oxygen for a fire or explosion is in the general body of air.
Unless a fire or explosion occurs in an enclosed space, such as a small
storeroom or within pipe work, it is safe to assume that it will always have a
ready supply of oxygen as the mines ventilation system will continue to draw
air around the workings.
Gases: oxygen, fluorine, chlorine
Liquids: hydrogen peroxide, nitric acid, perchloric acid
Solids: metal peroxides, ammonium nitrite


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8.6 How To Identify Potential Fire And Explosion Sources
This section covers the first step of a field-level assessment of fire and
explosion hazards, which is the identification of potential fuel-hydrocarbon,
oxygen-air, and energy-ignition sources based on the expanded fire triangle
(see FIGURE 7 pg.21). The assessment is the responsibility of the supervisor.
The OHS Code in some jurisdictions states that assessments must be written
and that workers must be involved in conducting worksite hazard
assessments. There need to be several results from this action. Figure 8.2
shows the types of questions should identify in fire and explosion system.
1. Identification of the on-site sources which could combine to
create a fire or explosion.
2. Identification of critical risk factors
3. Identification of changing job scope or operating conditions
which could increase the possibility of these sources combining. This
involves considering how the components are affected by different
conditions such as temperature, pressure, exposure to air etc.


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Figure 8.2 : Fire and explosion system.

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Points to Remember
1. Anytime all three sides of the fire triangle can co-exist, there is real
potential for a fire or explosion.
2. There are critical risk factors that increase the probability of a fire and
explosion significantly.
3. The system is dynamic and circumstances change over time. As a result,
safe situations may become unsafe.


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8.6.1 Fuel-Hydrocarbon Sources: Identifying And Documenting
Hazards

It is recommended that the steps outlined below be taken before any work
begins. Fuel and hydrocarbon sources on the work site need to be identified
and the properties of each understood and considered by those responsible
for the fire and explosion hazard assessment. At a minimum, those identifying
fuel hazards should consider the questions below taking into account the list
of fuels in the expanded fire triangle (See FIGURE 8.1).

Step 1: Identify and document fuels/hydrocarbons
A. Which operations require or will encounter fuels/hydrocarbons?
B. What are the properties of these fuels/hydrocarbons and how do they
potentially create a fire and explosion hazard?
C. How can these properties be confirmed? How can they be measured?
D. How are these properties affected by surface versus downhole
operations?
E. Are there fuels/hydrocarbons present now? Were fuels/hydrocarbons
present at any time previously? If so, could residual amounts still be
present?
F. Have the fuels/hydrocarbons been removed? What evidence is this
based on?

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G. Do operations involve adding fuels/hydrocarbons?
H. If fuels/hydrocarbons are present, what form are they in? Can they
change? How?
I. Is there something unique about the state and/or types of
fuels/hydrocarbons that may make them more or less dangerous?

Step 2: Determine and document hazards based on responses to Step 1.

Step 3: Consider the fuel-hydrocarbon hazards identified in the fire and
explosion prevention planning process.

8.6.1.1 Assessing Controlled Fuel Releases And Potential For
Uncontrolled Releases
If a controlled release of hydrocarbons is planned as part of the scope of
work, this should automatically trigger the need for a fire and explosion
prevention plan for the specific operation. It is also critical to consider the
potential hazard should an uncontrolled release of fuels or hydrocarbons into
the work environment occur.


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8.6.2 Oxygen Sources: Identifying And Documenting Hazards
begins. If the use of oxygen is planned as part of the scope of work, this
should automatically trigger the need for a fire and explosion prevention plan
for the specific operation.
At a minimum, those identifying oxygen hazards should consider the
questions below taking into account the list of oxygen sources in the
expanded fire triangle (see FIGURE 8.1).

Step 1: Identify and document oxygen-air sources
A. How can oxygen-air be combined with a fuel?
B. How could a fuel source be released to an oxygen-air containing
atmosphere?
C. Will oxygen-air be deliberately combined with a fuel source?
D. Can oxygen-air be inadvertently introduced into a closed system
containing a fuel source?
E. Can the fuels-hydrocarbons contain or be exposed to chemicals or
products that are potential oxygen sources such as: weathered
hydrocarbons, chemical additives, ester-based greases or on-site
generated nitrogen?


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Step 2: Determine and document hazards.

Step 3: Consider the oxygen-air hazards identified in the fire and explosion
prevention planning process.

8.6.3 Energy-Ignition Sources: Identifying And Documenting
Hazards

begins. Possible energy-ignition sources need to be identified and the
properties of each understood and considered by those responsible for the
fire and explosion hazard assessment. As a minimum, those identifying
hazards should consider the questions below taking into account the list of
energy-ignition sources in the expanded fire triangle (see FIGURE 7, pg. 21).

Step 1: Identify and document energy-ignition sources
A. Have all obvious sources such as open flames, sparks, heat sources
been identified?

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B. Have non-obvious energy sources been considered, such as pressure
increases (also known as the dieseling effect), sudden
depressurization, static discharge, and chemical reactions?
C. Have all classified areas been identified, as per the Canadian Electrical
Code? Does the equipment to be used meet electrical code
requirements?
D. If there is the potential for low-grade ignition sources (i.e. static
charges), will there be sufficient energy to ignite a flammable mixture?

**Incidents show that it is extremely difficult to account for all possible
energy ignition sources on a work site. For this reason, the elimination of
ignition sources should not be used as the only basis for safety.

Step 2: Determine and document hazards
A. What operations could create non-obvious energy sources such as
changes in operating pressures and static electricity through equipment
movements?
B. What is the potential for changing conditions to affect minimum
ignition energy as shown in FIGURE 8.2. For example: Static charges
may not have enough energy to ignite a dry gas mixture because of
the high minimum ignition energy. However, if liquid hydrocarbons are

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introduced, the minimum ignition energy is significantly reduced,
making it important to consider static electricity as an ignition source.

Step 3: Consider the energy-ignition hazards identified in the fire and
explosion prevention planning process.


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8.7 Reasons Why It Is Not Possible To Eliminate All Sources In Fire
Triangle

The fire triangle in FIGURE 7 shows the three critical components required for
combustion. It is widely understood that to remove the potential for a fire or
explosion, one of the three sides of this triangle must be eliminated. Given
the nature of upstream oil and gas operations, this is not as simple as it
seems:
1. There is always potential for flammable/combustible substances to be
present especially in our cumene plant. More importantly, their
properties can vary based on history and operating conditions.
2. There is a wide range of oil and gas operations with an equally wide
range of circumstances where oxygen-air can be combined with our
materials. The accidental release of hydrocarbons into a work area is
an ongoing concern. As is the planned or accidental entry of air into a
closed system.
3. There is a wide range of energy-ignition sources. Some ignition
sources, such as static electricity, adiabatic compression (dieseling
effect), and/or sudden decompression, are not well understood and are
even more difficult to identify and control.


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The ability to develop effective solutions for improving industry safety
depends on training which results in a better understanding of these elements.
A fire triangle with expanded parameter lists is therefore provided. The fire
triangle should be used to guide the identification of potential fuel, oxygen,
and energy sources.
It is important to remember that even though all sides of the fire
triangle co-exist, there is not 100 per cent certainty that a flammable mixture
will ignite; the ingredients need to be present in the right amounts and in
the vicinity of each other. Conducting an operation on the basis that is has
been completed safely numerous times previously without incident can
provide a false sense of security. Factors to consider include:
Upper and Lower Explosive Limits: The mixture must be within the
explosive range. If the mixture is below the Lower Explosive Limit
(LEL) or the above the Upper Explosive Limit (UEL), no ignition will
take place. The LEL and UEL are affected by the chemical nature of the
fuel, the fuel concentration, the oxygen concentration, and the
presence of any diluents such as inert gases.
Minimum Ignition Energy (MIE): The most important variable is
the minimum level of energy required to ignite a flammable mixture.
The critical risk factors can significantly affect the MIE, frequently
increasing the probability of ignition. Temperature and pressure as well
as relative humidity have key impacts on the MIE requirements.

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Other Important Properties of Flammable Substances: In
addition to the flammability limits, every flammable substance has a
number of important physical characteristics that affect worker safety.
These include: vapour pressure, flashpoint, fire point auto-ignition
temperature. These are normally detailed in the Material Safety Data
Sheet for a substance.
Available Ignition Energy: The level of energy associated with the
ignition source must also be considered. The ignition source must have
sufficient temperature, be of sufficient size, and be applied for a
sufficient length of time for ignition to occur. An ignition source with a
high level of energy has an increased probability of igniting. FIGURE
8.3: FACTORS AFFECTING IGNITABILITY OF FLAMMABLE MIXTURES
depicts these relationships.
System Geometry: This is the most complex issue and explanations
of it cannot be simplified. Key considerations include: vessel/piping
size, wall material, flow velocity and turbulence, and other physical
factors that can affect the ignitability.

For the reasons listed above, it is important to heed any warning signs
and near misses. Attention is required because small events signal that the
right components co-exist but conditions are not yet perfect. A more serious
event may be imminent.

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8.8 Factors Affecting Ignitability Of Flammable Mixtures

Figure 8.3 : Factors Affecting Ignitability of Flammable Mixtures


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This graph illustrates the impact of the various risk factors on a flammable
mixture and does not represent an actual substance.
1. The explosive limits (LEL/UEL) can vary significantly for different
substances. The wider the explosive envelope the greater the
probability of encountering the right conditions for a fire or explosion.
2. The Probability of ignition of a mixture may not be zero even below the
estimated LEL or above the UEL depending on a number of factors
including the exact properties of the mixture, nature of the ignition
sources, and the presence of any critical risk factors.
3. Even at ideal conditions, the probability of a fire or explosion is not
100% as illustrated by the gap at the top of the graph.
4. The introduction of the critical risk factors can significantly expand the
explosive range increasing the probability of a fire or explosion over
the entire range of the explosive envelope as represented by the red
band.
5. Low energy ignition sources can reduce the probability of ignition of an
explosive mixture as illustrated by the line inside the explosive range.


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8.9 Type Of Explosion Normally Happened In Cumene Plant
A confined explosion occurs in a confined space, such as a vessel or a
building. The two most common confined explosion scenarios involve
explosive vapors and explosive dusts. However, The most dangerous and
destructive explosions in the chemical process industries are vapor cloud
explosions (VCEs). These explosions occur in a sequence of steps:
1. Sudden release of a large quantity of flammable vapor (typically this
occurs when a vessel, ontaining a superheated and pressurized liquid,
ruptures),
2. Dispersion of the vapor throughout the plant site while mixing with
air
3. Ignition of the resulting vapor cloud.


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8.10 Fire And Explosion Analysis For Major Equipments
In all chemical plant, the equipment most likely to caught fire and explosion
should be determine, analyze and generate safety prevention strategies
associates with it. The equipment associated with US hydrocarbon/chemical
industry fires and explosions between 1970 and 1999 included:

Type of equipment Fires and explosion percentage
Piping 20
Vessel 20
Tankage 12
Pump 6
Heater 4
Heat exchanger 4
Compressor 2
Other 32


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From the above table, we found out the type of equipment that are
most likely to caught in fires and explosion are piping, vessel and tank. Piping
will be checked regularly so it will not be discussed in here. Hence, from our
process flow diagram, we found out our reactor and cumene column will likely
to undergo fire and explosion. Hence, these equipments will be discussed.


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8.10.1 Fire And Explosion Analysis For Reactor
Uncontrolled or unrealized pressure build up in the reactor may cause the
reactor to rupture or explode. The content of the reactor is highly flammable.
Rupture of the reactor cause the content leak or spill to the surrounding
environment. If any ignition source present, it can cause fire to occur. If the
fire continues to expand due to the present of sufficient fuel (reactor content)
and the air to the other area such as cumene storage tank, benzene storage
tank and so on, it may cause explosion of the storage tank to occur. If the fire
and explosion is not under controlled immediately, it may cause the whole
cumene plant exploded.
Besides, the uncontrolled temperature rise in the reactor due to the
runaway reaction, failure of the heating system and so on may cause
explosion to occur too. Continuous of the reactor will cause the reactor
content that is the mixture of propylene, benzene, cumene and so on to
vaporize. It is then release into the environment through any opening of the
reactor and mix with the air. If the concentration of the flammable vapor
exceeds its lower flammability limit and with the present of ignition source
such as sparks, explosion may occur. If the reactor is fully enclosed, increase
in the temperature will cause the pressure to increase too.
The cause of pressure build up and temperature rise was stated in the
Hazop analysis on Chapter 7.

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8.10.2 Fire And Explosion Analysis For Cumene Column
The fire and explosion analysis on the cumene column is almost same with
the reactor. However, likelihood of the fire and explosion of the column is
higher than the reactor. It is because of the structure of the cumene column
is far more complicated than the reactor. Hence, there are more measure
instrument such as flow meter, pressure indicator, temperature indicator
installed on the column as shown in the process and instrumentation diagram
on chapter 6.
Besides, there is high potential for fire and explosion of the reboiler
which attacted to the column since igh pressure and temperature steam is
used to heat the reboiler.


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8.11 Identify Flammable Inventories And Locations In Cumene
Plant
For the Cumene processing plant, the major flammable inventories are
chemicals, which are:
1. Propylene
2. Benzene
3. Di-isoproply benzene
4. Cumene
5. Propane

8.11.1 Flammable Inventory: Propylene
Propylene or methylethylene, is an unsaturated organic compound having
thechemical formula C3H6. It has one double bond, and is the second simplest
member of the alkene class ofhydrocarbons, and it is also second in natural
abundance. At room temperature and atmospheric pressure, propene is a
gas, and as with many other alkenes, it is also colourless with a weak but
unpleasant smell.
Propene has a higher density and boiling point than ethylene due to its
greater mass. It has a slightly lower boiling point than propane and is thus
more volatile. It lacks strongly polar bonds, yet the molecule has a
small dipole moment due to its reduced symmetry (its point group is Cs).

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Propene has the same empirical formula as cyclopropane but their atoms are
connected in different ways, making these molecules structural isomers.
Flammable properties:

Liquid releases flammable vapors at well below ambient temperatures
and readily forms a flammable mixture with air. Dangerous fire and explosion
hazard when exposed to heat, sparks or flame. Vapors are heavier than air
and may travel long distances to a point of ignition and flash back. Container
may explode in heat or fire. Runoff to sewer may cause fire or explosion
hazard.


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8.11.2 Flammable Inventory: Benzene
Benzene is a widely used chemical formed from both natural resources
(volcanoes and forest fires) and human activities. It is a highly flammable
colorless liquid that evaporates quickly. Relatively soluble in water, it can be
mixed with some polar solvents (alcohol, chloroform, and carbon
tetrachloride) without separating into two phases.
Its chemical formula is C6H6 and it is made up of 92.3%carbon and
7.7% hydrogen. The Benzene molecule is represented by six sets of carbon
and hydrogen atoms connected as a hexagon and held together with
alternating single and double bonds.

Vapors may be ignited rapidly when exposed to heat, spark, open
flame or other source of ignition. Flowing product may be ignited by self-
generated static electricity. When mixed with air and exposed to an ignition
source, flammable vapors can burn in the open or explode in confined spaces.
Being heavier than air, vapors may travel long distances to an i gnition
source and flash back. Runoff to sewer may cause fire or explosion hazard.

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8.11.3 Flammable Inventory: Di-Isoproply Benzene

Flammable liquid and vapor. Vapor may cause flash fire. Vapors may
accumulate in low or confined areas, travel considerable distance to source of
ignition and flash back. Runoff to sewer may create fire or explosion hazard.


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8.11.4 Flammable Inventory: Cumene
Cumene is, an organic compound that is an aromatic hydrocarbon. It is a
constituent of crude oil and refined fuels. It is a flammable colorless liquid
that has a boiling point of 152 C. Nearly all the cumene that is produced as a
pure compound on an industrial scale is converted to cumene hydroperoxide,
which is an intermediate in the synthesis of other industrially important
chemicals, primarily phenol and acetone.

Flammable Liquid! This material releases vapors at or below ambient
temperatures. When mixed with air in certain proportions and exposed to an
ignition source, its vapor can cause a flash fire. Use only with adequate
ventilation. Vapors are heavier than air and may travel long distances along
the ground to an ignition source and flash back. A vapor and air mixture can
create an explosion hazard in confined spaces such as sewers. If container is
not properly cooled, it can rupture in the heat of a fire.


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8.11.5 Flammable Inventory: Propane
Propane is a three-carbon alkane with the molecular formula C3H8, normally a
gas, but compressible to a transportable liquid. Aby-product of natural
gas processing and petroleum refining, it is commonly used as a fuel
for engines, oxy-gas torches,barbecues, portable stoves, and
residential central heating.
A mixture of propane and butane, used mainly as vehicle fuel, is
commonly known as liquefied petroleum gas (LPG or LP gas). It may also
contain small amounts of propylene and/or butylene. All commercial propane
fuels include an odorant, almost alwaysethanethiol, so that people can easily
smell the gas in case of a leak.
Liquid releases flammable vapors at well below am bient temperatures
and readily forms a flammable mixture with air. Dangerous fire and
explosion hazard when exposed to heat, sparks or flame. Vapors are heavier
than air and may travel long distances to a point of ignition and flash back.
Container may explode in heat or fire. Runoff to sewer may cause fire or
explosion hazard.

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8.12 Consequence Of Fire And Explosion Events
The effects of accidental fires or explosions can be devastating in terms of
lives lost, injuries, damage to property and the environment, and to business
continuity. Working with flammable liquids, dusts, gases and solids is
hazardous because of the risk of fire and explosion.
Explosion can cause Missile Damage. An explosion occurring in a
confined vessel or structure can rupture the vessel or structure, resulting
in the projection of debris over a wide area. This debris, or missiles, can
cause appreciable injury to people and damage to structures and process
equipment.
Unconfined explosions also create missiles by blast wave impact and
subsequent translation of structures. Missiles are frequently a means by
which an accident propagates throughout a plant facility. A localized
explosion in one part of the plant projects debris throughout the plant.
This debris strikes storage tanks, process equipment, and pipelines,
resulting in secondary fires or explosions.
Besides, People can be injured by explosions from direct blast effects
(including overpressure andthermal radiation) or indirect blast effects (mostly
missile damage).


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8.13 Fire And Explosion Prevention And Control
The standard of housekeeping, implementation and supervision of
management controls are significant fire prevention and reduction measures.
The objective of fire and explosion control measures is to avoid any fire
or explosion risks by eliminating either the potential ignition sources or
potential fuel sources, or both. However, it is likely that some potential fuels
and some ignition sources will remain, so these need to be reduced by:
Minimising the inventory of potential fuels
Minimising the number of potential ignition sources
Keeping potential ignition sources apart from potential fuel


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8.13.2 Minimization of Potential Amount Of Fuel
Although the undertaking of some storage mines is to store flammable
materials such as paper documents ,it should still minimise the potential
amount of fuel by:
Limiting the amount of other flammable materials taken below
ground;
Where reasonably practicable, using fire resistant fluids instead of
mineral oils;
Ensuring that rubbish and other flammable waste material is
removed regularly;
Progressively replacing any oil-filled electrical equipment and
bitumen-filled electrical cable couplers and joints with safer
alternatives;
Keeping to a practical minimum flammable material in structures
below ground.


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8.13.2 Minimization Of Potential Sources Of Ignition
Sources of ignition in all mines can be minimised by:
Using ignition-protected electrical distribution systems;
Reducing the number of plug and socket electrical connections; for
example, cable couplers;
Closely monitoring any remaining oil-filled electrical equipment and
bitumen-filled couplers;
Using battery-powered vehicles instead of those with internal
combustion engines;
Avoiding hot surfaces and frictional sparking through good design,
installation, commissioning and by regular inspection, testing and
maintenance, including the periodic and effective monitoring of brakes,
motors etc;
Checking that moving parts are not unintentionally rubbing against
fixed objects;
Ensuring proper lubrication;
Removing ignition sources from equipment that is out of use; for
example, vehicle batteries;
Prohibiting the use of flame cutting unless safety precautions are in
place;
Banning or controlling smoking below ground. Fuel and potential ignition
sources can be kept apart by:

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Minimising the amount of electrical equipment in zones where
flammable materials are used or stored;
By delineating adequate clear zones of at least 2m in any plane around
electrical equipment and other potential ignition sources;
Avoiding the use of internal combustion engines in zones where
flammable materials are used or stored;
Where diesel vehicles are used, separating electric cables, fuel and
hydraulic pipes from hot components in engine compartments by
routing and the provision of physical barriers.
Shrouding or enclosing any hot components (such as diesel exhausts,
space heaters etc).


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8.14 Additional Control Measures
Where the risk assessments indicate that the control measures already in
place are not sufficient then the next step is to identify what additional control
measures are needed, for example by:
Increasing the level of monitoring of plant and equipment that pose
ignition risks;
Increasing the number of fire detectors in vulnerable places;
Reducing compartment sizes to prevent or reduce further the
spread of heat, smoke and fumes;
Improving the fire resistance rating of walls and doors;
Installing automatic fire suppression equipment.
Avoiding or minimising the inventory of materials that give off very
toxic fumes when burnt such as polythene, some types of shrink
wrap, polyurethane foams and urea-formaldehyde foams.


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8.15 Dust Control
Dust control recommended for cumene plant :
Minimize the escape of dust from process equipment or ventilation
systems;
Use dust collection systems and filters;
Utilize surfaces that minimize dust accumulation and facilitate
cleaning;
Provide access to all hidden areas to permit inspection;
Inspect for dust residues in open and hidden areas, at regular
intervals;
Clean dust residues at regular intervals;
Use cleaning methods that do not generate dust clouds, if ignition
sources are present;
Only use vacuum cleaners approved for dust collection;
Locate relief valves away from dust hazard areas; and
Develop and implement a hazardous dust inspection, testing,
housekeeping, and control program (preferably in writing with
established frequency and methods).


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8.16 Ignition Control
Ignition control recommended for cumene plant:
Use appropriate electrical equipment and wiring methods;
Control static electricity, including bonding of equipment to ground;
Control smoking, open flames, and sparks;
Control mechanical sparks and friction;
Use separator devices to remove foreign materials capable of
igniting combustibles from process materials;
Separate heated surfaces from dusts;
Separate heating systems from dusts;
Proper use and type of industrial trucks;
Proper use of cartridge activated tools; and
Adequately maintain all the above equipment.


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8.17 Damage Control
Damage control recommended for cumene plant :
Separation of the hazard (isolate with distance);
Segregation of the hazard (isolate with a barrier);
Deflagration venting of a building, room, or area;
Pressure relief venting for equipment;
Provision of spark/ember detection and extinguishing systems;
Explosion protection systems (also refer to NFPA 69, Standard on
Explosion Prevention Systems);
Sprinkler systems; and
The use of other specialized suppression systems.


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8.18 Training Of Employees
Workers are the first line of defense in preventing and mitigating fires and
explosions. If the people closest to the source of the hazard are trained to
recognize and prevent hazards associated with combustible dust in the plant,
they can be instrumental in recognizing unsafe conditions, taking preventative
action, and/or alerting management. While OSHA standards require training
for certain employees, all employees should be trained in safe work practices
applicable to their job tasks, as well as on the overall plant programs for dust
control and ignition source control. They should be trained before they start
work, periodically to refresh their knowledge, when reassigned, and when
hazards or processes change.

8.19 Management team
A qualified team of managers should be responsible for conducting a facility
analysis (or for having one done by qualified outside persons) prior to the
introduction of a hazard and for developing a prevention and protection
scheme tailored to their operation. Supervisors and managers should be
aware of and support the plant dust and ignition control programs. Their
training should include identifying how they can encourage the reporting of
unsafe practices and facilitate abatement actions.


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9.0 ENVIRONMENT ANALYSIS
9.1 Introduction
Cumene (CAS no. 98-82-8) is a water-insoluble petrochemical used in the
manufacture of several chemicals, including phenol and acetone. It readily volatilizes
into the atmosphere from water and dry soil. Cumene is expected to adsorb
moderately to strongly to soil/sediments and to undergo biodegradation in water and
soil.
Cumene is metabolized primarily to the secondary alcohol, 2-phenyl-2-
propanol, in both humans and animals. This alcohol and its conjugates are readily
excreted by both rodents and humans.
Increases in organ weights, primarily kidney weights, are the most
prominent effects observed in rodents repeatedly exposed to cumene by either the
oral or inhalation route. No adverse effects were observed in rat or rabbit fetuses
whose mothers had been exposed to cumene during fetal development. Although no
multigenerational reproductive studies have been performed using cumene, its rapid
metabolism and excretion, coupled with lack of effects on sperm morphology in a
subchronic study, suggest that it has a low potential for reproductive toxicity. A
guidance value for oral exposure of 0.1mg/kg body weight per day has been derived,
based on the no-observed-adverse-effect level (NOAEL) of 154 mg/kg body weight
per day for increased kidney weight in female rats in a 6- to 7-month oral study; the
NOAEL was adjusted for the dosing schedule, and a total uncertainty factor of 1000

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was applied. Guidance values for the general population of 0.4 mg/m
3
and 0.09
mg/m
3
were derived for inhalation exposure, based on alternative NOAELs derived
from the same subchronic inhalation study; again, the NOAELs were adjusted to a
continuous exposure, and a total uncertainty factor of 1000 was applied.
No data are available with which to quantify human exposure to cumene.
It is not possible to assess cumene's potential for carcinogenicity in humans,
because long-term carcinogenicity studies with cumene have not been performed.
Most genotoxicity test data with cumene are negative.
Inadequate data, especially measured exposure information, exist to allow a
quantitative evaluation of the risk to populations of aquatic or terrestrial organisms
from exposure to cumene. Based on existing data, however, cumene is anticipated
to be of relatively low risk. Values indicate a slight potential for bioconcentration of
cumene in fish. There are no data on bioaccumulation through food chains
(biomagnification).


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9.2 Analytical Methods
For sampling and measurement of cumene in air, Method 1501 of the US National
Institute for Occupational Safety and Health (NIOSH,1994)includes use of a solid
sorbent tube (coconut shell charcoal) sampler with a gas chromatography/flame
ionization detector measurement technique. The detection limit of this method is 1
mg/m
3
(0.2 ppm).
US EPA (1996) methods for detecting cumene in media other than air
include the use of gas chromatography using photoionization Method 8021B, which
is applicable to nearly all types of samples, regardless of water content. The method
detection limit for cumene is 0.05g/litre, and the applicable concentration range for
this method is approximately 0.1-200 g/litre. The standard recovery using this
method is 98%, with a standard deviation of 0.9%. Another commonly used gas
chromatographic assay for volatiles including cumene is Method 8260B (US EPA,
1996), with a general estimated quantitation limit of approximately 5 g/kg wet
weight for soil/sediment samples,0.5 mg/kg wet weight for wastes, and 5 g/litre for
groundwater.


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9.3 Emission Sources Of Cumene
Cumene is emitted to the atmosphere via both natural and anthropogenic sources.
Cumene is a naturally occurring constituent of crude oil and may be released to the
environment from a number of anthropogenic sources, including processed
hydrocarbon fuels. Crude oils typically contain approximately 0.1 wt% of cumene,
but concentrations as high as 1.0 wt% have been reported. Measurements of
various grades of petrol revealed that cumene concentrations range from 0.14 to
0.51 vol% and that the average cumene concentration was 0.3 vol%. Premium
diesel fuel contains 0.86 wt% of cumene; furnace oil (no. 2) contains 0.60 wt%.
These emissions sources, as well as ambient concentration levels, are described in
more detail in the following sections.
SRI International (1986) reported the 1985 Western European cumene
production levels (in tonnes) for the following producer countries:
Table 9.1 Western European cumene production levels (in tonnes) for the
producer countries.
Producer Countries Cumene production levels
(in tonnes)
Federal Republic of Germany 438 000
Finland 70 000

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France 370 000
Italy 335 000
Netherlands 240 000
Spain 120 000
United Kingdom 220 000


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9.3.1 Anthropogenic Sources
Anthropogenic sources of cumene to the atmosphere are largely the result of
emissions from manufacturing and processing plants, and emissions during its
transport (HSDB, 2004). As cumene occurs in crude oil and fuels, the transport,
distribution and incomplete combustion of these fuels also lead to releases of
cumene (HSDB, 2004). It was estimated that the releases of cumene as a result of
the above-mentioned sources represented 21 million pounds annually (Jackson et al.
cited in HSDB, 2004).
Other anthropogenic sources of cumene include leather tanning, iron and
steel manufacturing, paving and roofing, paint and ink formulation, printing and
publishing, ore mining, coal mining, organics and plastics manufacturing, pesticide
manufacturing, electroplating and pulp and paper production (Shakelford et al. cited
in HSDB, 2004). Cumene may also be released from the vulcanization of rubber
(Cocheo et al. cited in HSDB, 2004), building materials (Moelhave, cited in HSDB,
2004), jet engine exhaust (Katzman and Libby, cited in HSDB, 2004), outboard
motor operation (Montz et al. cited in HSDB, 2004), solvent use (Levy, cited in HSDB,
2004), pharmaceutical production (Brown et al. HSDB, 2004), textile plants (Gordon
and Gordon, cited in HSDB, 2004) and cigarette tobacco (WHO, 1999).
According to the National Pollutant Release Inventory (NPRI), the industrial
sectors contributing to cumene emissions are the crude petroleum and natural gas
industries, refined petroleum and coal products industries, the chemical and
chemical products industries and the plastic products industries (NPRI, 2004).

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9.4 Environmental Transport, Distribution, And Transformation
9.4.1 Cumene In Atmosphere
In the atmosphere, cumene is expected to exist almost entirely in the vapour phase
(Eisenreich et al., 1981). Cumene does not absorb ultraviolet light at wavelengths
greater than 290 nm (US EPA, 1987), which suggests that cumene would not be
susceptible to direct photolysis. In one study, the estimated half-life of cumene in
the atmosphere from photolysis alone was approximately 1500 years (Parlar et al.,
1983). Cumene is not susceptible to oxidation by ozone in the atmosphere (US EPA,
1987). Thus, reaction with ozone and direct photolysis are not expected to be
important removal processes. Rather, reaction with photochemically generated
hydroxyl radicals appears to be the primary degradation pathway (t = 1-2 days)
(Lloyd et al., 1976; Ravishankara et al., 1978). Small amounts of cumene may be
removed from the atmosphere during precipitation. Cumene has been assigned a
Photochemical Ozone Creation Potential (POCP) value of 35 relative to ethylene at
100 (Derwent & Jenkin, 1990). POCP values represent the ability of a substance to
form ground-level ozone as a result of its atmospheric degradation reactions.


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9.4.2 Cumene In Water
In water, important fate and transport processes are expected to be volatilization (t
4 h from a typical river) and aerobic biodegradation (Kappeler & Wuhrmann, 1978;
Sasaki, 1978; Van der Linden, 1978). Chemical hydrolysis, oxidation, photolysis, and
reaction with hydroxyl radicals are not expected to be important fate processes in
water (Mill et al., 1978, 1979, 1980). Using an aerobic freshwater sediment/water
test system, Williams et al. (1993) demonstrated that 10 days after addition of
radiolabelled cumene (2.5mg/litre) to the system, 46.9% was trapped as
radiolabelled carbon dioxide and another 21.8% was recovered as radiolabelled
organics, the overall recovery of cumene ranging from 56.8% to 88.3%. The
disappearance half-life based on these results was 2.5 days. During a 20-day
incubation of cumene at 10 mg/litre under aerobic conditions in either fresh water or
salt water, Price et al. (1974) observed 70% degradation in fresh water but only
about 2% degradation in seawater. Cumene was, however, observed to be degraded
to a significant extent by microorganisms isolated from ocean sediment samples
incubated in seawater, as Walker et al. (1976) noted decreases in cumene (gas
chromatographic analysis) ranging from 37% to 60% of initial amounts over a
period of 21 days in three separate incubations with seawater and microorganisms
isolated from Atlantic Ocean sediments. On the other hand, cumene was found to be
essentially non-biodegradable under anaerobic conditions by Battersby & Wilson
(1989), who noted that cumene produced only about 2% of theoretical gas
production when incubated at 50 mg carbon/litre sludge for 60 days at 35C under
anaerobic conditions; compounds at 80% of theoretical gas production under these

338 | P a g e

conditions were assumed to represent complete degradation, whereas compounds at
less than 30% production were considered persistent.


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9.4.3 Cumene In Soil
In soil, it appears that cumene might biodegrade fairly rapidly under aerobic
conditions, because a number of microorganisms capable of degrading cumene have
been isolated (Yamada et al., 1965; Jamison et al., 1970; Omori et al., 1975).
Regression equations based on the limit of cumene water solubility (50 mg/litre)
predicted Koc (soil sorption coefficient standardized to organic carbon) values
ranging from 513 to 1622. For equations based instead on log octanol/water
partition coefficients (log Kow) for cumene, predicted Koc values were in a similar
range, from 589 to 3890 (Lyman et al., 1982). Other estimates of Koc values at 884
(Jeng et al., 1992) and 2800 (US EPA, 1987) were also in this range. These Koc
values indicate that cumene is expected to adsorb moderately to strongly to soil and
have only slight mobility. The relatively high vapour pressure of cumene suggests
that volatilization of this compound from dry soil surfaces would be significant.

Measured and estimated bioconcentration factors (BCFs) suggest a slight
potential for cumene to bioconcentrate in fish species. A BCF of 36 for cumene in
goldfish ( Carassius auratus) has been measured (Ogata et al., 1984), and a BCF of
356 was estimated from the log Kow and a linear regression correlation equation (log
BCF = 0.76 log Kow - 0.23) by the US EPA (1987). This value was concordant with
the BCF of 316 calculated for fish species in general exposed to cumene (Sabljic,
1987). Cumene was detected at levels of 0.5-1.4 ng/g wet weight (detection limit
0.5 ng/g wet weight by gas chromatography/ mass spectrometry) in 12 of 138

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sampled fish (various species) from several locations near a potential emission
source (Japan Environment Agency, 1987). Cumene has been detected in "oakmoss"
( Evernia prunastri (L.) Ach.) (Gavin et al., 1978) and marsh grass (Mody et al.,
1974a,b).


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9.5 Environmental Levels And Human Exposure
9.5.1 Environmental Levels
Cumene has been found as a contaminant in various industrial effluents and in
groundwaters. Significant levels of cumene have been recorded in groundwater near
chemical plants (1581 g/litre, Botta et al., 1984; 360 g/litre, Teply & Dressler,
1980; 11 g/litre, Pellizzari et al., 1979), around outboard motor operations (700
g/litre, Montz et al., 1982), near coal gasification facilities (up to 54 g/litre,
Steurmer et al., 1982), and around petroleum plants and petroleum refineries (5
g/litre, quantification method not clear; Snider & Manning, 1982). Cumene was
detected in 8 of 135 samples of surface water (detection limit 0.03 g/litre with gas
chromatography/mass spectrometry) at concentrations ranging from 0.09 to 0.44
g/litre in several locations near a potential emission source in the 1986 monitoring
of the general environment in Japan (Japan Environment Agency, 1987). Cumene
levels in sediments and biota in Puget Sound, Washington, USA, ranged from 0.02 to
19 g/g, with a mean concentration of 2.3 g/g (Brown et al., 1979). A cumene
level of 140 g/litre was found in seawater near an offshore drilling platform in the
Gulf of Mexico (Sauer, 1981). Cumene was detected in 6 of 111 sediment samples at
concentrations ranging from 0.58 to 11 ng/g dry weight (detection limit 0.5 ng/g
with gas chromatography/mass spectrometry) in several locations near a potential
emission source (Japan Environment Agency, 1987).


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Reports of air sampling in the USA indicate the mean concentration of
cumene to be about 14.7 g/m
3
(3 ppb) in urban settings and as high as 2.5 g/m
3

(0.5 ppb) in rural settings. Samples taken in Los Angeles, California, in 1966
averaged 14.7g/m
3
(3 ppb) (Lonneman et al., 1968), and samples taken in Houston,
Texas, in 1973-1974 averaged 12.15 g/m
3
(2.48 ppb) (Lonneman et al., 1979). The
US EPA (1987) reported a mean concentration of 16.7 g cumene/m
3
(3.4 ppb) in
undated samples from Los Angeles. In samples taken in the fall of 1981 in Los
Angeles, Grosjean & Fung (1984) did not detect cumene, although a minimum
detection level of 9.8 g/m
3
(2 ppb) was reported. Although a number of sampling
attempts in rural and remote areas reported no detectable levels of cumene in air
(detection limit <0.05 g/m
3
[<0.01 ppb]), two attempts were positive: Seila (1979)
reported mean levels of 2.5 g/m
3
(0.5 ppb) in samples taken in a rural area near
Houston, Texas, in 1978, and Arnts & Meeks (1980, 1981) reported 0.25 g/m
3

(0.05 ppb) in samples taken near campfires in the Great Smokey Mountains, USA, in
1978.

Average atmospheric concentrations of cumene in Europe are reported to
be somewhat less than those in the USA, although concentrations in urban areas are
also consistently much higher than those in rural areas. Isodorov et al. (1983)
recorded an average cumene level of 8.3 g/m
3
(1.7 ppb) in the urban atmosphere
of Leningrad, USSR, in 1977-1979, with a maximum of 11.8 g/m
3
(2.4ppb).
Ambient air concentrations for the Netherlands in 1980 were reported to average
0.5-1.0 g/m
3
(0.1-0.2 ppb), with maxima ranging up to 34.8 g/m
3
(7.1 ppb)

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(Guicherit & Schulting, 1985). An annual average of 1.6 g/m
3
(0.3 ppb) (maximum
3.9 g/m
3
[0.8 ppb]) was reported from the Grenoble area in France in 1987 (Foster
et al., 1991).


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9.5.2 Human Exposure
Humans can be exposed to cumene via industrial emissions, petrol station or motor
vehicle emissions, accidental releases, food, cigarette smoke, and drinking-water (US
EPA, 1987).
Brugnone et al. (1989) reported cumene as measurable in all alveolar air
samples collected (single breath; range 1-81 g/m
3
[0.2-17 ppb], method detection
limit not given) from among two groups of workers ( n = 86, gender not specified)
exposed to <0.1 mg cumene/m
3
(<0.02 ppm) through the work shift. These authors
analysed for but were unable to detect any significant differences in cumene
concentrations between smokers and non-smokers in either alveolar air or blood
samples. In another study, gases collected from 60 min of normal continuous
respiration from each of eight male volunteers (three smokers) were analysed for
trace organic constituents (Conkle et al., 1975).
Only two reports of cumene quantification in drinking-water were found in
the available literature. Coleman et al. (1984) detected cumene in Cincinnati, Ohio,
USA, drinking-water at a level of 0.014 g/litre (quantification method not clear).
Keith et al. (1976) reported 0.01 g cumene/litre drinking-water in Terrebonne-
Parish, Louisiana, USA, but found none in the drinking-water of nine other cities
across the USA. These concentrations are considerably below the 0.5 g/litre
detection limit reported by Westrick et al. (1984), who found no cumene in 945 US
drinking-water systems, 479 of which were selected because of known
contamination problems. Burmaster (1982) and Burnham et al. (1972) reported

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unquantified levels of cumene/ alkylbenzenes in drinking-water obtained from
groundwater. Based on the results of these studies, it may be concluded that
cumene contamination above 0.5 g/litre is uncommon in drinking-water in the USA.
One industrial hygiene survey (US EPA, 1988) reported that approximately
739 US workers were occupationally exposed to cumene. Personal exposure data in
this report consisted of 1487 air samples taken over the course of 12 years (1973-
1984), of which 6 were in the range of 20-150 mg/m
3
(4-30 ppm), 4 in the range of
15-20 mg/m
3
(3-4 ppm), and 25 in the range of 5-10 mg/m
3
(1-2 ppm), with the
remaining samples below 5 mg/m
3
(1 ppm) (US EPA, 1988).
Based on available monitoring data, it appears that the general population
would be exposed to cumene primarily by inhalation, although occupational
populations may be reasonably anticipated to be exposed by the dermal route. Minor
exposure may result from contact with refined petroleum products and ingestion of
contaminated foods and possibly drinking-water.


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9.6 Comparative Kinetics And Metabolism In Laboratory Animals And
Humans
Cumene has been shown to be absorbed after inhalation exposure in humans and
after inhalation, oral, and dermal exposure in animals (Senczuk & Litewka, 1976;
Research Triangle Institute, 1989). Tests conducted in humans indicate that cumene
is absorbed readily via the inhalation route, that it is metabolized efficiently to water-
soluble metabolites within the body, and that these metabolites are excreted
efficiently into the urine with no evidence of long-term retention within the body;
these results concur with the results of animal studies.
Senczuk & Litewka (1976) exposed human volunteers (five men and five
women) head only to one of three different concentrations of cumene vapours (240,
480, or 720 mg/m
3
[49, 98, or 147 ppm]) for 8 h every 10 days. Exhaled breath
samples (10 cm
3
) were collected near the beginning and at the end of the exposure
from a tube placed in the breathing zone. The total amount of cumene absorbed
during exposure, calculated from retention, ventilation, and exposure duration, was
nearly twice as high at all exposure levels in the males (466-1400 mg) as in the
females (270-789 mg). The respiratory tract absorption ranged from 45% to 64%
depending on the time of exposure, with the overall mean retention estimated at
50%. In rats, inhalation studies (nose only for 6 h at 510, 2420, or 5850 mg/m
3

[104, 494, or 1194 ppm]) indicate rapid absorption, with detectable levels of cumene
appearing in the blood within 5 min of the beginning of exposure at all three
exposure levels (Research Triangle Institute, 1989). Gavage studies in rats showed
that cumene was absorbed readily via this route, with maximum levels in blood

347 | P a g e

occurring at the earliest time point sampled (4 h) for a lower dose (33 mg/kg body
weight) and at 8-16 h for a higher dose (1350 mg/kg body weight) (Research
Triangle Institute, 1989). Dermal absorption of cumene was demonstrated in rats
and rabbits (Monsanto Co., 1984).

The human data reported by Brugnone et al. (1989) regarding cumene
distribution suggest that the cumene concentration was about 40 times higher in
blood than in alveolar air, a figure concordant with the reported human blood/air
partition coefficient of 37 (Sato & Nakajima, 1979; Table 1). Cumene was widely
distributed in rats, and distribution, presumably determined immediately after
exposure, was independent of administration route (inhalation, oral, or
intraperitoneal in 10% aqueous Emulphor). Adipose, liver, and kidney were all
shown to have elevated tissue/blood ratios of cumene following all doses and routes
of exposure (Research Triangle Institute, 1989). Fabre et al. (1955) demonstrated
that after rats inhaled cumene vapour for up to 150 days, cumene was distributed to
the endocrine organs, central nervous system, bone marrow, spleen, and liver.

The patterns of cumene disappearance (as total radioactivity) from the
blood in the nose-only inhalation studies were fitted with a monoexponential model,
with the half-lives increasing with dose, from 3.9 h at 490 mg/m
3
(100 ppm) to 6.6 h
at 5880 mg/m
3
(1200 ppm). The half-life of cumene in the blood in gavage studies
with rats was calculated to be between 9 and 16 h.

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Metabolism of cumene by cytochrome P-450 is extensive and takes place
within hepatic and extrahepatic tissues, including lung (Sato & Nakajima, 1987), with
the secondary alcohol 2-phenyl-2-propanol being a principal metabolite. Metabolites
excreted in urine of rats and rabbits include 2-phenyl-2-propanol and its glucuronide
or sulfate conjugates, conjugates of 2-phenyl-1,2-propanediol, and an unknown
metabolite, possibly the dicarboxylic acid that would result from complete oxidation
of the 1- and 3-alkyl carbons of phenylmalonic acid (Research Triangle Institute,
1989; Ishida & Matsumoto, 1992; MAK, 1996).

Senczuk & Litewka (1976) also conducted excretion studies with human
volunteers exposed to cumene vapours (240, 480, or 720 mg/m
3
[49, 98, or 147
ppm]) for 8 h every 10 days. These authors reported excretion of the metabolite 2-
phenyl-2-propanol in the urine as biphasic, with a rapid early phase (t 2 h) and a
slower later phase (t 10 h); excretion of this metabolite in the urine (about 35% of
the calculated absorbed dose) was maximal after 6-8 h of exposure and approached
zero at 40 h post-exposure. With rats, the extent of elimination across routes of
administration (inhalation, oral, or intraperitoneal) and exposure concentrations was
very similar, with urine being the major route of elimination, about 70% in all cases
(Research Triangle Institute, 1989). Total body clearance in the rats was rapid and
complete, with less than 1% of the absorbed fraction being present in the body 72 h
after the highest exposure regime examined (5880 mg/m
3
[1200 ppm] for 6 h).
Following oral administration of cumene in rabbits, 90% was recovered as
metabolites in the urine within 24 h (Robinson et al., 1955).

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9.7 Effects On Humans, Animals And Vegetation
The following is a summary of the available toxicological and epidemiological studies
on the health effects of cumene following inhalation. Effects following oral and
dermal exposure were not reviewed in detail. The primary literature sources were
taken from international peer reviewed assessments of the health effects of cumene
by the European Chemicals Bureau (ECB, 2001), the World Health Organization
(WHO, 1999), and the U.S. Environmental Protection Agency (US EPA, 1997).
Exposure-response data from key toxicological studies were summarized in
table form to provide a quick reference to health effects observed in critical
receptors over a defined period of inhalation exposure to cumene. The relevance of
this data to public health was then discussed.


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9.7.1 Overview of Chemical Disposition
Cumene was rapidly absorbed, metabolized, and excreted by Fischer F-344 rats
exposed via inhalation to a single nose-only dose of 100, 500, or 1500 ppm
(Research Triangle Institute, cited in ECB, 2001). Cumene was detected in the blood
within 5 minutes of exposure and was distributed to adipose tissue, liver, and
kidneys. Over 70% of the absorbed dose was excreted in the urine. Elimination via
expired breath and faeces occurred to a smaller extent (more evident at higher
doses). The major metabolite produced was 2-phenyl-2-propanol and its glucuronide
or sulphate conjugates (50% or more); other metabolites identified were 2-phenyl-
1,2-propanediol and 2-phenylproprionic acid. Similar urinary metabolites were
reported in rabbits exposed to cumene by gavage and following in vitro exposure of
rabbit liver soluble enzyme fraction (Robinson et al. Chakraborty and Smith, cited in
ECB, 2001). Cumene was detected in endocrine organs, central nervous system,
bone marrow, spleen, and liver of rats exposed via inhalation to cumene vapour for
up to 150 days (Fabre et al. cited in WHO, 1999).
In several human exposure studies, cumene was reported to be associated
with human metabolism as it was detected in the breath of non-smoking (urban)
men and women having no occupational exposure to the chemical (Conkle et al.
Krotoszynski et al. cited in ECB, 2001).
Cumene was detected in the urine, blood, and alveolar air of individuals
exposed to mean air concentrations of 6 g cumene/m3 (Parbellini et al. cited in ECB,
2001). Ten healthy male and female human volunteers were exposed under

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controlled conditions to cumene vapour concentrations of 249, 480 or 720 mg/m3
(49, 98, 147 ppm) for 8 hour periods every 10 days (Senczuk and Litewka, cited in
WHO, 1999 and US EPA, 1997). The mean respiratory tract absorption of cumene
was 50% (ranging from 45 to 64%), with males absorbing nearly twice as much as
females. Cumene excretion was measured by levels of 2-phenyl-2-propanol in the
urine. Maximum excretion occurred after 6 to 8 hours of exposure and dropped off
to near zero 40 hours post exposure. It was estimated that 35% of the absorbed
dose was excreted in the urine as 2-phenyl-2-propanol. In a study of alveolar and
blood cumene concentrations, Brugnone et al. (cited in ECB, 2001) reported alveolar
cumene retention from 70.4 % in hospital staff to 77.8% in chemical workers
(benzene manufacturing) exposed to mean air concentrations of 6.4 g cumene/m3
and 10.7 g cumene /m3, respectively.


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9.7.2 Genotoxicity
Numerous in vitro and in vivo assays for genotoxicity have been conducted using
cumene in various test systems (ECB, 2001; WHO, 1999; US EPA, 1997). With one
exception, all of the assays were negative for genotoxicity.
Results were negative for in vitro Ames tests in Salmonella Typhimurium (TA98,
TA100, TA1535, and TA1537) conducted with and without metabolic activation
(Lawlor and Wagner, Florin et al. cited in ECB, 2001; WHO, 1999, and; U.S. EPA,
1997). In vitro studies on DNA damage were also negative for cell transformation in
BALB/3T3 mouse embryo cells without metabolic activation (Putnam, cited in ECB,
2001 and U.S. EPA, 1997), gene mutations or chromosomal aberrations in Chinese
hamster ovary cells with and without metabolic activation (Yang, Putnam, cited in
ECB, 2001; WHO, 1999, and; U.S. EPA, 1997), and, unscheduled DNA synthesis in
primary rat hepatocytes (Curren, cited in ECB, 2001; WHO, 1999, and; U.S. EPA,
1997).
Mixed results were reported in micronucleus assays conducted following in
vivo exposure of mice (Gulf Oil Corporation, cited in ECB, 2001; WHO, 1999 and U.S.
EPA, 1997) and rats (NTP, cited in WHO, 1999 and U.S. EPA, 1997) to cumene. The
Gulf Oil Corporation reported that cumene was not clastogenic following in vivo
exposure of mice to cumene at 250, 500, or 1000 mg/kg body weight/day for 2 days.
The study conducted by the NTP reported weakly positive results (without evidence
of dose-response) for rats exposed by a single intraperitoneal injection to up 2,500

353 | P a g e

mg cumene/kg body weight. It should be noted that the highest dose used in this
study resulted in 50% death of the test animals (U.S. EPA, 1997).

9.7.3 Acute and Sub-Acute Effects
Acute effects usually occur rapidly as a result of short-term exposures and are
of short duration generally for exposures less than 24 hours. Sub-acute effects
usually occur as a result of exposures that are of an intermediate duration
generally for exposures lasting a few days to no greater than one month (Eaton and
Klaasson, 1996).

9.7.3.1 Acute and Sub-Acute Human Effects
No studies on the effects of cumene in humans following acute or sub-acute
exposures were identified.

9.7.3.2 Acute and Sub-Acute Animal Effects
Table 9.2 lists the No-Observable-Adverse-Effect-Levels (NOAELs) and Lowest-
Observable-Adverse-Effect Levels (LOAELs) reported in the literature from acute and
sub-acute exposures of animals to cumene. Further discussion of these effects is
provided following the table.

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Table 9.2 Effects of Acute and Sub-Acute Cumene Inhalation
(Experimental Animals)
Effects Reported Air Concentration
Ppm(mg/m3)
Exposure
Period
Species
Death (LC50): 25000 (121,000) 2 hours Mice
8000 (40,000) 4 hours Rat
2000 (10,000) 7 hours Mice
Systemic:
Respiratory tract irritation:
RD50
(50% reduction in
respiratory rate)
2,058 (10,084) 30 min Mice
2,900 (14,255) Not specified Mice
NOAEL
Depressed respiratory
frequency
580 (2,850) 6 hours Rat
LOAEL 2,000 (9,800) 6 h/d, Rat

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Laboured respiration 5 d Fischer 344
Neurological:
NOAEL
CNS Depression
(behavioural function)
100 (490) 6 hours Rat
NOAEL
CNS Depression
100 (490) 6 hours Rat
Fischer 344
LOAEL
CNS Perturbations
2000 (9,800) 6 h/d,
5 d
Rat
Fischer 344
NOAEL
CNS Perturbations
251 (1,230) 6 h/d,
5 d/wk,
2 wks
Rat
Fischer 344
LOAEL
CNS Perturbations
105 (515) 6 h/d,
5 d/wk,
4 wks
Rat
Sprague-
Dawley

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9.7.3.2.1 Respiratory Effects
Two studies reported RD50 values (a 50% decrease in respiratory rate) of 10,084
mg/m3 and 14,255 mg/m3 for mice exposed via inhalation to cumene (Kristiansen,
et al. cited in ECB, 2001; WHO, 1999 and Nielsen Alarie, cited in ECB, 2001). These
effects occurred at lethal air concentrations (LC50 of 10,000 mg/m3) for mice
exposed for 7 hours to cumene (Werner et al; Dow Chemical Company, cited in ECB,
2001). Respiratory paralysis is one of the causes of death reported in animals
acutely exposed via inhalation to cumene (also pulmonary edema and hemorrhaging)
(Gerarde, Werner et al. Dow Chemical Company, cited in ECB, 2001).
Groups of 3 male and 3 female rats were exposed via inhalation to a single
dose of 0, 2,850 mg/m3, or 7,275 mg/m3 cumene (Research Triangle Institute, cited
in ECB, 2001). A significant decrease in respiratory frequency as well as severe
motor impairment and narcosis was observed in rats exposed to 7,275 mg/m3
cumene, however, no respiratory effects were observed at 2,850 mg/m3.


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9.7.3.2.2 Neurological Effects
Groups of 10 rats were exposed (nose-only) for 6 hours to a dose of cumene vapour
at concentrations of 0, 490, 2,450 or 5,880 mg/m3 (Bushy Run Research Centre,
1989, cited in ECB, 2001). Acute behavioural effects (i.e., gait abnormalities,
decreased rectal temperature, and increased activity) were observed 1 hour after
exposure in the two highest dose groups, but subsided within 6 or 24 hours
following exposure.
Groups of Fischer-344 rats were exposed (whole body) for 6 hours to a single
dose of 0, 490, 2,430, or 5,980 mg cumene/m3 (Cushman et al. cited in WHO,
1999). Gait abnormalities, decreased rectal temperature, and decreased activity
were reported 1 hour post-exposure for rats exposed to the highest dose only.
Decreased activities also occurred in females exposed to 2,430 mg cumene/m3. A
decreased response to toe pinch was reported six hours post-exposure, but only in
males from the highest dose group.
Acute neurobehavioural effects (including changes in posture, gait, mobility,
strength and psychomotor coordination) were also reported in mice exposed by
whole body inhalation for 20 minutes to single high concentrations of cumene (9,800
mg/m3, 19,600 mg/m3, and 39,200 mg/m3) (Tegeris and Balster, cited in WHO,
1999; ECB, 2001). Recovery was reported within minutes of removal from exposure.
Male and female Sprague-Dawley rats exposed (whole body) to cumene
vapour concentrations of 0, 515, 1,470 or 2,935 mg/m3 for 6 hours/day, 5
days/week, over a 4 week period were observed for neurobehavioural effects (i.e.,

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side to side head movements, head tilt and arched back) (Monsanto Co, cited in
WHO, 1999). Dose-related increases in side-to-side head movements and head tilt
were reported for all groups.
Groups of 15 male and 15 female Fischer 344 rats exposed (whole body) to 0,
9,800 or 24,500 mg/m3 cumene vapour for 6 hours a day were observed over a 5
day exposure period (Gulf Oil Corporation, cited in WHO, 1999; ECB, 2001). All rats
in the highest exposure dose group died within 2 days. At the low dose, central
nervous system effects observed in exposed animals included hypothermia,
staggering, laboured respiration, and lethargy).
Another study on Fischer 344 rats exposed (whole body) groups of 10 male
and 10 female to 0, 1,230, 2,680, 5,130, or 6,321 mg/m3 cumene vapour for 6
hours a day, 5 days a week over a two week period (Chemical Manufacturers
Association, cited in WHO, 1999). Neurological effects (decreased motor activity or
hyperactivity, ataxia) occurred in all but the lowest dose group.

9.7.4 Sub-Chronic and Chronic Effects
Sub-chronic effects generally occur following one to three months of exposure, while
chronic effects occur as a result of repeated exposures for a period greater than 3
months (Eaton and Klaassen, 1996).


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9.7.4.1 Chronic Human Effects
No recent studies on the chronic or sub-chronic exposure of humans to cumene
were identified EPA, 1997; WHO, 1999). However, in 1948 the Dow Chemical
Company reported no toxic injury from daily exposure over 1-2 years to readily
tolerated cumene concentrations; presumably below 400 ppm (1,966 mg/m3) as
most persons exposed to higher concentrations experienced eye and upper
respiratory tract irritation (Dow Chemical Company, cited in ECB, 2001).

9.7.4.2 Sub-Chronic and Chronic Animal Effects
Table 9.3 lists the NOAELs and LOAELs reported in the literature from sub-chronic
and chronic exposures of animals to cumene. Further discussion of these effects is
provided following the table.
Table 9.3 Effects of Sub-Chronic Cumene Inhalation (Experimental
Animals)
Effects Reported Air
Concentration a
ppm (mg/m3)
Exposure
Period
Species
Systemic:
NOAEL 4 (18) 90 days Rat, guinea

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Body weight, haematology,
Clinical chemistry, histopathology
continuous pig, dog,
monkey
NOAEL
Respiratory tract tissue,
lung weights
1202 (5,890) 6 h/d
5d/wk
13 weeks
Rat
Fischer 344
Neurological:
LOAEL 496 (2,430) 6 h/d Rat
NOAEL
Motor activity and systemic
effects
100 (490) 5d/wk
13 weeks
Fischer 344
LOAEL 1,202 (5,909) 6 h/d Rat
NOAEL
Motor activity and systemic
effects
496 (2,438) 5d/wk
13 weeks
Fischer 344
Reproductive/Developmental:
NOAEL 1202 (5,890) 6 h/d
5d/wk

Rat

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13 weeks Fischer 344
NOAEL
Developmental effects
1,211 (5,934) 6 h/d
Days 6-15
Rat

NOAEL
Maternal effects
99 (485) of gestation Sprague-
Dawley
NOAEL
Developmental and maternal
effects
1,206 (5,909) 6 h/d
Days 6-18
of gestation
abbit

9.7.4.2.1 Respiratory Effects
Two sub chronic inhalation studies were performed on Fischer-344 rats (Cushman et
al. cited in US EPA, 1997; WHO, 1999). In the first study, male and female rats
(22/sex) were exposed via whole body inhalation to cumene vapours at 0, 490, 2430,
or 5890 mg/m3 for 6 hrs/d, 5 d/week for 13 weeks. In the second study, fewer rats
(15/sex) were exposed and a low-dose group (245 mg/m3) was added. The exposed
rats were evaluated for neurological function, clinical signs of toxicity, body weight,
food and water consumption, hematology and serum chemistry, organ weights,
auditory brain stem responses, ophthalmology, sperm count and morphology, gross

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pathology and histopathology (including respiratory tract tissue). No significant
effects on respiratory tract tissue or lung weights were reported in either study (US
EPA, 1997).

9.7.4.2.2 Neurological and Systemic Effects
In the first of the two sub chronic inhalation studies performed on groups of male
and female Fischer-344 rats (Cushman et al. cited in US EPA, 1997; WHO, 1999;
ECB, 2001), a statistically significant exposure-related decrease in motor activity was
reported for male rats exposed to the two highest doses (2,430 mg/m3 and 5,890
mg/m3) for 6 hours a day, 5 days a week for 13 weeks. These results were not
reproduced in the second study; however, various other effects were also reported
in the rats exposed to 2,430 mg/m3, including increased water consumption, effects
on haematological and serum parameters, and sporadic weight increases in adrenals
(males) and kidneys (females) and clinical effects (WHO, 1999; ECB, 2001).
Alterations in relative and absolute weights of adrenals (both sexes) and
kidneys (females) were statistically and biologically significant at 5,890 mg
cumene/m3 (Cushman et al. cited in US EPA, 1997). The US EPA (1997) viewed the
effects occurring at 2,430 mg/m3 as not biologically and statistically significant,
defining this exposure dose as the NOAEL and the highest exposure dose (5,890
mg/m3) as the LOAEL for sub-chronic cumene inhalation exposure. This NOAEL of
2,430 mg/m3 was used by the US EPA (1997) to develop a Reference Concentration
(RfC) of 400 g/m3 for chronic inhalation exposure to cumene.

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The WHO (1999) and ECB (2001) reviewed the results of the study by
Cushman et al. and conclude that the effects occurring at 2,430 mg/m3 in the first
study could be potentially adverse indications of the more significant effects which
occurred at the next highest exposure dose, resulting in their recommendation of a
LOAEL of 2,430 mg/m3 and a NOAEL of 490 mg/m3 for sub-chronic exposure to
cumene.

9.7.4.2.3 Reproductive and Developmental Effects
An inhalation study was conducted in female Sprague-Dawley rats exposed (whole
body) to 0, 485, 2,391 or 5,934 mg cumene/m3 for 6 hours/day on days 6 through
15 of gestation (Darmer et al. cited in WHO, 1999). No significant adverse effects on
reproductive parameters or fetal development were reported, resulting in the
recommendation of a developmental NOAEL of 5,934 mg/m3 for cumene inhalation
(WHO, 1999). Maternal toxicity (hypoactivity, blepharospasm, and decreased food
consumption) was significant at 2,391 mg/m3, resulting in a maternal NOAEL of
485mg/m3 (WHO, 1999).
It should be noted that the LOAEL (2,391 mg/m3) and NOAEL (485 mg/m3)
determined for maternal toxicity in rats are very similar to the LOAEL (2,430 mg/m3)
and NOAEL (490 mg/m3) identified above by WHO (1999) and ECB (2001) for
neurological and systemic effects in rats.

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The same authors conducted an inhalation study on New Zealand White
rabbits exposed (whole body) to 0, 2,418, 5,928, or 11,292 mg cumene/m3 for 6
hours/day on days 6 through 18 of gestation (Bushy Run Research Center, cited in
US EPA, 1997 or Darmer et al. cited in WHO, 1999). The highest exposure dose
resulted in maternal mortality (2 deaths) and one abortion as well as significant
reductions in body weight and food consumption, clinical signs of toxicity, lung
colouration, and increased liver weights. Gestation parameters affected at this dose
(concurrent with maternal toxicity although not significant) included increased
nonviable implants, early resorptions, and decrease in the percent of live fetuses.
The highest dose (11,292 mg/m3) was considered a LOAEL and the next highest
dose (5,928 mg/m3) was considered a NOAEL for maternal and developmental
effects (US EPA, 1997; WHO, 1999).
No reproductive effects were reported in either male (sperm count and
morphology) or female (weight changes or histopathology of reproductive organs)
Fischer-344 rats exposed in the first of two sub chronic inhalation studies to cumene
vapours at 0, 490, 2430, or 5890 mg/m3 for 6 hours a day, 5 days a week for 13
weeks (Cushman et al. cited in US EPA, 1997; WHO, 1999).


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9.7.4.2.4 Other Effects
No significant adverse effects were reported in several species of mammals (rats,
guinea pig, dog, and monkey) following continuous exposure for 90 days to cumene
vapours at concentrations of 0, 18, or 147 mg/m3 (Jenkins et al. cited in US EPA,
1997; WHO, 1999; ECB, 2001). Parameters analysed included body weight,
haematology, clinical chemistry and histopathology.

9.7.5 Summary of Adverse Health Effects of Cumene Inhalation
The weight of evidence from numerous genotoxicity assays (following in vivo and in
vitro exposure to cumene) suggests that cumene is not genotoxic. There was no
long-term exposure data available to determine the potential carcinogenicity of
cumene.
Acute inhalation studies using lethal exposure doses (7,000 to 10,000 mg
cumene/m3) reported respiratory effects in mice and rats, including 50% decrease
in respiratory rate, severe motor impairment, and narcosis. No respiratory effects
were reported in rats exposed for 6 hours to cumene vapours at 2,850 mg/m3.
Acute neurobehavioural effects were reported in rats acutely exposed for 6
hours to cumene at air concentrations ranging from 2,430 to 5,980 mg/m3 and in
mice exposed for 20 minutes to cumene concentrations ranging from 9,800 to
39,200 mg/m3. In all cases, symptoms subsided following withdrawal from exposure;

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recovery was quicker in animals exposed to lower air concentrations of cumene or
exposed for short time periods (i.e., 20 minutes).
Neurobehavioural effects were reported in rats sub-acutely exposed to
cumene vapour concentrations of 9,800 mg cumene/m3 (6 hours/day, 5 days),
2,680 to 6,321 mg cumene/m3 (6 hours a day, 5 days/week, 2 weeks), and from
515 to 2,935 mg cumene/m3 (6 hours/day, 5 days/week, 4 weeks).
The only documentation of human effects following inhalation exposure to
cumene (a 1948 report by the Dow Chemical Company) reported no toxic injury
from daily exposure over 1-2 years to cumene concentrations presumably
(depending on individual sensitivity) below 1,966 mg/m3. Exposure to
concentrations >1,966 mg/m3 typically (depending on individual sensitivity) resulted
in acute irritation of the eyes and upper respiratory tract.
In sub-chronic inhalation studies on rats (6 hours/day, 5 days/week, 13
weeks) a NOAEL of 5,890 mg/m3 was reported for effects on respiratory tract tissue,
lung weights, and reproductive parameters. This same dose (5,890 mg/m3) was the
LOAEL for significant alterations in adrenal tissue and kidney weights. A LOAEL of
2,430 mg/m3 was reported for decreased motor activity, increased water
consumption, effects on haematological and serum parameters, and sporadic weight
increases in adrenals and kidneys. The NOAEL for these effects was 490 mg/m3.
In several species of mammals (rats, guinea pig, dog, and monkey), no
adverse effects were reported following continuous exposure for 90 days to cumene
vapours of 18, or 147 mg/m3.

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Studies in female rats exposed via inhalation to cumene vapours for 6
hours/day on days 6 through 15 of gestation, reported a developmental NOAEL of
5,934 mg/m3, a maternal LOAEL of 2,391 mg/m3 and a maternal NOAEL of 485
mg/m3. This LOAEL and NOAEL are comparable to the LOAEL (2,430 mg/m3) and
NOAEL (490 mg/m3) reported for neurological and systemic effects in rats.
In female rabbits, a NOAEL of 5,909 mg/m3 was reported for maternal and
developmental effects following exposure to cumene vapours for 6 hours/day on
days 6 through 18 of gestation.


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9.7.6 Effects on Vegetation
Little is known about the direct effects of volatile organic compounds (VOCs) on
plants. A search of ecological databases (i.e., Web of Science, Biological Abstracts,
Toxnet (available at http://toxnet.nlm.nih.gov/), and Ecotox (available at
http://www.epa.gov/ecotox/)) was conducted for literature describing the effects of
cumene on terrestrial and aquatic vegetation.
The search resulted in the identification of only two research article on the
effect of cumene in liquid media on algae, whereas nothing has been reported on
effects on terrestrial vegetation.
Hutchinson et al. (1980) evaluated the effect of a number of different
compounds on the photosynthesis of the algal species Chlorella vulgaris (strain 260,
Indiana Culture Collection) and Chlamydmonas angulosa (strain 680, Indiana Culture
Collection). Photosynthesis activity was calculated as a function of 14CO2 uptake.
Both strains were grown in Bolds Basal Media (pH 6.5) at 19C, in axenic conditions,
with a light intensity of 400 foot candles. Cumene treatments were at 0, 20, 50, and
100 percent saturation level in Bolds Basal Media. The algal cultures were grown to
exponential phase for all experiments. Cell concentrations for treatments were at 5 x
104 and 20 x 104 for Chlamydomonas angulosa and Chlorella vulgaris, respectively.
It was reported that a 50% decrease of photosynthesis was observed with a
cumene treatment (3h exposure) of 73 mmol/m3 for Chlamydomonas angulosa and
177 mmol/m3 for Chlorella vulgaris. Galassi et al. (1988) evaluated the effect of

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cumene on the alga Selenastrum capricornutum. Cumene treatment of 2.6 mg dm3
(EC50) for 72h treatment inhibited 50% exponential growth.


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10.0 COMMERCIAL VALUE
10.1 Cumene Market Survey
10.1.1 Cumene Market Overview
As feedstock costs continue to increase and downstream demand remains flat, the
global cumene market is expected to face challenges in the coming months.
Production costs for cumene are expected to continue increasing. Global crude
oil prices prices is pushing up on feedstock benzene and feedstock propylene is
increasing in the US due to the supply tightness and gasoline aklyation values.
However, downstream demand for cumene, polycarbonate (PC), nylon, epoxy
resins and methyl methacrylate(MMA)-through phenol/acetone production is expected
to remain stable to slightly higher. This is not enough to support the increases in
upstream chemical costs.
This is because consumers are pushed to cut back on spending for electronics,
automotives and new homes or remodeling projects due to the continued global
economic concerns, as well as a soft construction industry in the US.
As US and European producers look to build up some inventory ahead of the
expected shutdown of Sunocos 545,000tonnes/year Philadelphia cumene unit in
Pennsylvania, this potential disconnected could lead to volatility in the cumene market.


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10.1.1 Market Survey In Year 2010 (Price Report)
There is some reports that US cumene prices extend gains on strong benzene,
propylene values in year 2010. As production costs were estimated as high as 465
cents/gal this week, spot cumene prices continued to move higher on the back of
continued gains in propylene and benzene.
Spot refinery grade propylene (RGP) has increased throughout the year. The
RGP traded for December is at 67 cents/lb, and was up nearly 16 cents/lb from early
December. This is due to outages at Shell and Petrologistics. Furthermore, the market
was tightened as a third supplier was heard to be producing off-spec material.
Cumene prices which was poised to touch a 27 month high on stronger January
values have also been bolstered by rising spot benzene. Offers were heard as high as
400 cents/gallon FOB USG while January benzene bids were seen as high as 380
cents/gallon DDP USG. Due to delayed imports, Benzene values have been supported
by rising energy prices and tightness in the prompt market.
The gains in both propylene and benzene have resulted in an approximately 74
cents/gal increase in cumene prices since the beginning of the month. The gains were
putting upward pressure on the entire chain and downstream acetone makers were
heard to have nominated a 10 cents/lb increase on January contracts. The December
acetone contract settled at $910/mt (41.27 cents/lb).


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Global cumene demand growth is attributed in year 2011, to a large extent, to the
come-back of pre-crisis construction and automobile industries performance. The
growth index for cumene consumption rested at approximately 3,5% per year, being
disrupted however by the downfall period during the last five years.
Today's global cumene demand growth is attributed, to a large extent, to the
come-back of pre-crisis construction and automobile industries performance. During
the last five years the growth index for cumene consumption rested at approximately
3,5% per year, being disrupted however by the downfall period. In cumene market
development, phenol derivatives activity is traditionally cited as key factor. Recently
the cumene industry has reached healthy growth rates that are compatible to that of
phenol.
USA is the head of the key cumene exporters list nowadays. However, the
largest producing base is proved to be the Chinese one with China enjoying the
position of the most promising cumene market.


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On February, US cumene prices appear set to surge by as much as 31% on higher
feedstock costs. Cumene prices is at 6365 cents/lb ($1,3891,433/tonne, 1,056
1,089/tonne) FOB (free on board) in February. January US cumene
prices were assessed by ICIS at 4850 cents/lb FOB.
Depending on when a cost point for feedstock refinery-grade propylene (RGP)
is used, cumene contracts will vary throughout the month. Spot RGP prices were at
an average of 63.50 cents/lb at the start of February, , up by an average of 19.50
cents/lb in the past four weeks. Moreover, in the past two months the contract price
on feedstock benzene has surged by $1.20/gal .
As downstream phenol-acetone producers have lowered their operating rates
because of weak export demand, cumene demand in the US is stable-to-soft. Cumene
producers was forced to make a decision on operating rates due to the surging
feedstock costs.
Supply will tighten in the US as Sunoco expected to shut down its 545,000
tonne/year Philadelphia cumene unit in July. This will put pressure on cumene
producers to have inventory for buyers.
However, supply would be mostly balanced in the US, rather than short, if
demand does not pick up, as was expected at the start of the year. Major US cumene
producers include CITGO, Flint Hills Resources, Georgia Gulf, Marathon, Shell Chemical
and Sunoco. ($1 = 0.76) US April cumene contract prices were assessed at a rollover
on Friday, tracking higher and lower feedstock costs. US April cumene prices

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were assessed by ICIS at 65-67 cents/lb ($1,433-1,477/tonne, 1,103-1,137/tonne)
FOB, flat with March prices.
April benzene contract prices fell by 11 cents/gal, but spot RGP prices for April
have moved higher by 2.25-3.00 cent/lb. Sources said the cumene market continues
to be mostly driven by feedstock benzene and refinery-grade propylene (RGP) prices.
Sources said because of lower-than-normal operating rates at
downstream phenol-acetone plants, cumene demand was stable in March and likely
to remain consistent for the coming months. When we looked at the feedstock
changes for April, our numbers were almost exactly the same, a cumene buyer said.
Phenol producers dont have room to crank up their operating rates until Asian
demand comes back, a phenol buyer said. They certainly cant increase the rates
just to make more acetone.
Cumene supply is snug, but could tighten considerably after the expected
shutdown of Sunocos 545,000 tonne/year Philadelphia cumene unit in Pennsylvania
in June. Sources said supply would be tight, but not constrained, as most phenol
buyers have made plans to deal with the loss of production.
However, if operating rates increase to service the Asian market, that added
tightness, combined with a possible increase in demand, is likely to push cumene
higher. Major US cumene producers include CITGO, Flint Hills Resources, Georgia Gulf,
Marathon, Shell Chemical and Sunoco. One producer said it thinks that those factors
could push other producers to raise their premium over cumene feedstock costs to 3-
4 cents/lb, rather than the 2-3 cent/lb range most are using now.

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10.2 Cost Estimation & Economics
10.2.1 Background & Objectives
Being located in Teluk Kalung Industrial Area, Kemaman, Terengganu, Malaysia, the
feasibility study established that a cumune plant would be advantaged. By using data
from recently constructed plant or available plants, a capital cost estimate can be
obtained. In this chapter, project economic evaluation is carried out by the calculations
of the total investment amount, total production cost, cash flow diagrams, tax and
depreciation, discounted cash flow (time value of money), payback period, the rate of
return (ROR), discounted cash flow rate of return, allowing for inflation, and sensitivity
analysis.
10.2.2 Cost Evaluation
Table 10.1 shows the details that are needed to build a phenol plant.
1. Current Chemical Price:
Propylene (November 2011,
http://www.icispricing.com):
Benzene (November 2011,
Cumene (November 2011,

$ 1210/tonne

$ 910/tonne

$ 1212.54/tonne
2. Cumene Sales Per Year
=
$1215.54
tonne
RM3.04
$1
1,015,050 tonne
year

RM3,750,855.00/year
RM3.76 billion/year

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3. Conversion Rates:
( May, 2012,
http://themoneyconverter.com/USD/M
YR.aspx)
1 U.S.dollar =RM3.04
1 British Pound Sterling =RM4.91
4. Plant Specifications:
Production rate
Efficiency
Operation
Maintenance duration
Land Price
Land Size

= 1,015,050 tonne/year
= 90 %
= 335days/year or 8040
hours/year
= 30days/year or 720hours/year
= RM17,424,000.00
= 20 acres 80,937 m
2


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10.2.3 Investment
Recent prices paid for similar equipment should be used to estimate the cost of the
equipment. Alternatively, factorial method of cost estimation can be used to calculate
the cost of purchased equipment. Therefore, a more accurate estimate should be
made by sizing and costing individual pieces of equipment. (Refer to Appendix for
calculation of individual equipment costs)
Cost of cumene plant of capacity 400 TPD in 1990 is RM 26,698,537.81
Therefore cost of 3030 TPD in 1990 is:
C1
= C2 (Q1/Q2)
0.6

= 26.6 million(3030/400)
0.6

= RM70.49million

Chemical Engineering Plant Cost Index:
Cost index in 1990 = 357.6
Cost index in 2012 = 446.4
Thus, Present cost of Plant = (original cost) (present cost index)/(past cost index)
= (RM70.49million) (446.4/357.6) = RM88 million
i.e., Fixed Capital Cost (FCI) = RM RM88 million


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10.2.3.1 Estimating Plant Equipment Purchase Cost (Pce)
Purchased equipment cost (PEC): (15-40% of Fixed-capital investment)
Consider purchased equipment cost = 25% of Fixed-capital investment
i.e., PEC = 25% of RM88 million
= 0.25 RM88 million
= RM22 million.
10.2.3.2 Total Investment Required
For the typical factors for estimation of project fixed cost
Table 10.2: Typical factors for estimation of total physical plant cost.
Item Factor (Fluids)
f1, Equipment erection 0.40
f2, Piping 0.70
f3, Instrumentation 0.20
f4, Electrical 0.10
f5, Building 0.15
f6, Utilities 0.50
f7, Storages 0.15
f8, Site development 0.05
f9, Ancillary building 0.15

Total physical plant cost (PPC) = PCE (1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 + f8 + f9)

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Table 10.3: Typical factors for estimation of project fixed capital cost
Item Factor (Fluids)
f10, Design and engineering 0.30
f11, Contractors fee 0.05
f12, Contingencies 0.10

Fixed capital = PPC ( 1 + f10 + f11 + f12)
Table 10.4 shows the calculation of Operating Cost (Operating Direct
Supervision Electrical Cost)
No. Job
Salary Per
Person
No. Pay/Month(RM)
1 Head Of Department 15000 1 15000
2 Production Manager 6500 4 26000
3 Assistant Manager 4500 8 36000
4 Shift Engineer 3500 8 28000
5 Shift Operator 2000 7 14000
6 Chemist 2000 3 6000
7 Unskilled Operator 1500 8 12000
8 Maintenance Engineer 3000 6 18000
9 Maintenance Staff 2000 6 12000
10 Clerical Staff 1460 10 14600
Total - 61 181,600

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Considering the inflation rate of 3% per annum, the current fixed capital cost for
Phenol plant for year 2012
Fixed Capital
1. Total Plant Equipment
purchase cost (PCE) in
2012
$7,078,400 =RM21,518,223
RM22million
2. Total Physical Plant Cost
(PPC)

= PCE (1 + f1 + f2 + f3 + f4 +
f5 + f6 + f7 + f8 + f9)
=PCE(3.4) (Fluids)
=RM73,161,958
RM74 million
3. Fixed Capital = PPC ( 1 + f10 + f11 + f12)

Considering the inflation rate
of 3% per annum
= RM106,084,839
RM107 million
=RM109,267,384
RM110 million
Working Capital
1. For Petrochemical plants,
working capital = 15%
Fixed Capital
= 0.15 (RM109,267,384)

= RM16,390,107
RM17million
Total investment Required
1. Fixed Capital + Working
Capital + Land
Purchased
= RM (109,267,384+
16,390,107+ 17,424,000.00)
= RM 139,898,947
RM 140million


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10.2.3.3 Estimation of Production Cost
10.2.3.3.1 Fixed Cost
From our plant specifications, we are assuming this plant operates 8040hours/year.
We refer to Sinnott Table 6.6 to make our fixed cost estimation.
Fixed Cost
1. Maintenance (10% of fixed capital) RM 10,608,483
2. Operating
Labour
Refer to Appendix E-Table 4 RM 2,179,200
3. Laboratory
Costs
(20% of Operating Labour) RM 435,840
4 Supervision (20% of Operating Labour) RM 435,840
5 Plant Overheads (50% of Operating Labour) RM 1,089,600
6 Capital Charges (10% of fixed capital) RM 10,608,483
7 Insurance (1% of fixed capital) RM 1,060,848
8 Local Taxes (2% of fixed capital) RM 2,121,696
9 Royalities (1% of fixed capital) RM 1,060,848
Total Fixed Cost RM29,600,814 RM30million


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10.2.3.3.2 Variable Cost
Variable Cost
Main raw
material
Price (RM)/tonne Quantity
tonne/year
Total (RM)/year
Benzene and
Propylene
RM2000 150,000 RM 300,000,000
Miscellaneous
materials
(10% of
maintenance)
= RM 14,108,470 X
0.10
RM 1,060,848
Utilities Unit Cost Per Unit Amount
Electricity 170 KWH/tonnes RM0.26/KWH RM
5,105,100/year
Water 290 m
3
/tonnes RM0.90/ m
3
RM
30,145,500/year
Total Variable
Cost
- - RM336,229,688
RM337
million


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10.2.3.3.3 Production Cost
Production Cost
1. Direct Production
Cost
Fixed Cost + Variable Cost RM 367,830,529
2. Sales Expenses (30% of direct production cost) RM 55,174,159
3. Annual Production
Cost
= Direct Production Cost + Sales
Expenses
RM 422,479,688
4 Production cost
RM/ton
Annual Production Costs
Annual Production Rate

RM988.76 /ton


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10.2.3.3.4 Calculation of Payback Period
Production rate ( Cumene) 1,0150,050 Tonne/yr
Production cost 1088.76 MYR/tonne
Retail Price (Cumene) 1212 MYR/tonne
Gross Profit 124 MYR/tonne
Plant Asset Life, t 20 Years
Construction Duration 3 Years
Annual Production Cost, APC 522,479,688 MYR
Annual Revenue, AR ( Retail Price x
Production rate)
(For cumene)
704,152,969 MYR
Annual Gross Profit, AGP (AR-APC) 181,673,281 MYR
Annual Profit after Taxation of 26%
APAT(AGP x 0.74)
134,438,230 MYR
Investment Capital, IC 139,898,947 MYR

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10.2.4 Project Economic Evaluation
10.2.4.1 Cash Flow Diagram

The cash flows are based on the best investments, operating costs, sales volume and
sales price that can be made for the project. It is proposed to build the plant to
produce the phenol. The estimated investment required is RM140 million and the
timing of the investment will be
Year 1 Design Cost RM13 million
Year 2 Construction Cost RM 55 million
Year 3 Construction Cost RM 55 million
Year 4 Working Capital RM17 million
-200
0
200
400
600
800
1000
1200
1400
1600
0 5 10 15 20
C
u
m
u
l
a
t
i
v
e

C
a
s
h

F
l
o
w

Time /years
Cumene Plant Cash Flow Diagrams

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The plant will be start up in Year 4. The forecast sales price, sales volume, and
raw material costs are shown in Table below. The fixed operating costs are estimated
to be: RM30 million per year up to Year 9; RM40 million per year from Year 9 to 13;
RM45 million per year from Year 13. The variable operating costs are estimated to be
RM 3100 per ton of product up to Year 13 and RM 3200 per ton of product from Year
13. In this diagram, it is found that the maximum investment for this phenol plant is
RM121 million which is located at the lowest point of this graph, and the pay back
period is 2.2 years as it is found that starting from 5.2 years, the cash flows turns
from negative to positive. It means that the plant is gaining profit after 2.2 years of
operation. For the first three years is construction period. Normally, payback time of
2-5 years will be expected from such projects. For The Tables-Summary Of Data And
Results, please refer to the AppendixG.
For Year 4:
Investment (negative cash
flow)
- RM17 million
Ssles income (from phenol
and acetone)
RM (5196 x 100,000)+( 4222
x45,000)
RM709 million
Raw material costs - RM553 million
Fixed operating costs - RM30million
Variable operating costs - RM590 million
Net cash flow Sales income-costs-
investment
-RM57.7 million
Discounted cash flow( at 15
percent)

(1 +)
=
57.7
(1.15)
4

-RM33 million

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For Year 9:
Investment (negative cash
flow)
- nil
Sales income (from
phenol and acetone)
RM (5300.7 x
102000)+( 4307.1x 46.136)
RM741million
Raw material costs - RM553 million
Fixed operating costs - RM40million
Variable operating costs RM591.5 million
Net cash flow Sales income-costs RM109.61million

10.2.4.2 Tax and Depreciation
In this calculation, there is no account needs to be taken of tax; or the scrap value of
the equipment and value of the site at the end of the project life. The project is
considered as an isolated system and taxes on profit and the effect of depreciation of
the investment are not considered.
10.2.4.3 Time Value of Money (Discounted Cash Flow)
For the discounting calculation, cash flow can be assumed to occur at the end of the
year in which they actually occur and the discount rate is considered as 15%.
10.2.4.4 Rate of Return
Rate of return, ROR
=
Cumulative Net Profit at the end of the project
Plant Asset Life Original Investmetn Capital
x 100%

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=
(5AGP)+[(t5)APAT]IC
tIC
100%
= 52.35%
The rate of return is often calculated for the anticipated best year of the project, where
the cash flow is the highest. The data used for calculated the ROR is shown in Table
in 7.4. Compared to the cash flow table, we get rate of return of 53.3%. It is found
that the value for both calculation are similar to each other.
10.2.4.5 Discounted Cash Flow Rate Of Return (DCFRR)
This is done by trial and error calculations. The present worth has been calculated at
the discount rates of 10, 20, 30, 40, and 50 percent. From the results shown in Table
below, it will be seen that the rate to give the zero present worth will be around 45
percent. This is the discounted cash flow rate of return for the project.


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10.3 Cumene Commercial Value Report
CONTRACT PRICES
Click for Price
History
Price Range One
year ago
USD/MT
FOB US OCT US
CTS/LB
-
10.00
53.00-
55.00
-
10.00
51.00-
52.00
1168.45-
1212.54

10.3.1 US October cumene prices remain stable amid quiet trade
Market sources expect to see prices weaken in line with those for feedstocks and
cumenes primary end-use markets, phenol and acetone but the US cumene contract
price was stable in the week ending on 11 November.
Both phenol and acetone prices were experiencing some severe downward
pressure because of weak demand and lengthening supplies but both held steady
during the week.
The US barge acetone contract price for October fell 15 cents/lb ($331/tonne,
231/tonne) DEL to 46 cents/lb from the September settlement of 61 cents/lb on
propylene prices and softened demand.
US phenol prices were feeling downward pressure from lower benzene values
as well as weak demand.
Market sources said US cumene values were expected to drop to around 46-48
cents/lb in the near future.

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Demand for cumene is also reduced as phenol/acetone producers try to keep
inventories at a minimum ahead of year-end inventory tax assessments.
10.3.2 US benzene and RGP markets are quiet
The US aromatics and olefins markets were relatively quiet in feedstocks this week.
The US spot benzene price range was quoted around $3.23-3.27/gal FOB mid-week,
but dropped back down to $3.16-3.19/gal FOB by Friday.
The US November benzene contract price settled at $3.15/gal, down 18
cents/gal below October contract prices on weaker spot pricing and softened domestic
demand.
The spot refinery-grade propylene (RGP) bid/offer range for November was
heard at around 45-47 cents/lb, down from a 4 November bid of 48 cents/lb.


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10.4 Cumene Value Chain
Currently, there are more than 90% of the worlds phenol production technology based
on the cumene hydroperoxide route. Today, the cumene hydroperoxide route is by far
the dominant process. Phenol and acetone are key components in the cumene value
chain as illustrated in Figure below.

Figure10.1: The Cumene Value Chain
In 2001, worldwide phenol production was nearly 6.4 million metric tons. More
than 99% of phenol produced worldwide is form synthetic process. The predominant
uses of phenol are in bisphenol A, phenolic resins caprolactam, aniline and
alkylphenols. Caprolactam and bisphenol A are intermediates in the manufacture of
nylon and epoxy resins, respectively.
PROPYLENE

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As a conclusion, cumene market analysis, improvements for the cumene
technologies falls along the lines of improved yield, process safety, and economy or
costs for the cumene technologies which will be discussed in the later part of this
feasibility study.


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10.5 World Demand Of Cumene
Demand for cumene is strongly tied to the phenol market. This is because all world
cumene is consumed for the production of phenol and acetone. Trade in cumene
accounts for only 4% of world production. United States (to Germany) and Japan (to
the Republic of Korea) are the largest exporters of cumene. Taiwan also imports large
volumes of cumene for phenol production.
As of early 2011, as a result of a shortage of feedstock propylene, the U.S.
cumene market was tight. Phenol and acetone plant operating rates have been
reduced significantly due to the cumene shortages,, which in turn has restricted phenol
exports to Europe and higher-demand regions such as Asia and South America.
Scheduled plant maintenance by several large cumene manufacturers was also
planned for early to mid-2011.


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The following pie chart shows world consumption of cumene:

Figure 10.2: World Consumption of Cumene 2010
Strong demand for phenol, particularly in Asia (excluding Japan) is due to the
increased demand for bisphenol. Thus, consumption of cumene for phenol is forecast
to grow at approximately 8% per year in the region. China alone is expected to add
over a million metric tons of cumene capacity during 20112015 (with most capacity
coming onstream in 2013) to supply its phenol/acetone plants that are slated to come
onstream during that period. Overall, during 20102015, worldwide cumene
consumption for the production of phenol/acetone is forecast to grow at an average
annual rate of about 4.5%.

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10.6 Current Market Situation
In year 2010, North America and Europe have seen strong domestic phenol demand
rebound but neither returned to the volume levels seen in 2007. Interestingly, both
regions experienced strong increases in demand into the nylon chain; not because of
domestic nylon demand but rather for export to Asia.
Besides that, bisphenol A demand saw a quick and sustained rebound for both
regions. Northeast Asia, on the other hand, did not suffer the contractions in the
phenol chain seen in most parts of the world and not only grew in 2010.
North American and European producers can export phenol to Asia at prices
higher than their domestic markets due to the strength in Asia, primarily China. This
leads to strong overall exports with volumes in many cases approaching the levels
seen in 2008.
However, not much supply can be shipped. This is due to raw material
availability for cumene coupled with some phenol production issues limited exports for
some producers both in North America and Europe.
Due to the freely negotiated nature of the Asian phenol markets, the phenol
price differential between the North American and European markets with the Asian
markets was made possible.
This freely negotiated environment allows prices to rise with higher demand
and limited supply in classic economics fashion. However, the North American and
European markets have a significant portion of their phenol volume moving on a

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formula basis with fixed margin that doesn't allow them to capitalize on tight market
conditions.
As the Asian balances being so tight, phenol prices for the Far East pushed
above $1,700 per ton quite easily. This was more than sufficient to pay for the freight
for the Western regions to ship to Asia and subsidized the relatively low acetone prices
that subsequently occurred with the higher phenol/acetone operating rates creating
length in the acetone markets.


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10.7 Cumene Market Outlook
What a difference a year makes. It was hard to imagine that 2010 could perform as
well as it did. In early 2009 it appeared the market was in ruin and while demand
improved throughout the year.
In future, the global cumene market expected would be over supplied. A sharp
recovery for operating rates leads to a better than expected rebound in demand and
less available phenol capacity resulting from shutdowns coupled with delayed
projects.
We must keep in mind that this was expected to eventually occur, the timing
was simply moved forward by better than expected demand and changes to the supply
side while the change in the outlook is different from a year ago.
During the time period 2010 to 2015, the forecast calls for global cumene
demand to increase by 3.6 percent. This may appear on the low side, however keep
in mind that 2010 is the base year of this forecast and we now believe the pent up
demand/rebound year was in 2010.
The expectation is that phenol operating rates on a global basis will reach 89
percent in 2012 before falling to the mid-80s thereafter. Cumene capacity additions
are very limited until 2013 when over 900 thousand metric tons of capacity will be
coming on line.
The market today and the outlook for the next two years calls for tight markets
and this will more than likely kindle expansion plans.

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10.8 Petrochemicals: Global Markets
Principal Feedstock's & Largest Consumers Basis: World Petrochemical Feedstock
Analysis CMAI (2005)

Figure 10.3: Principal Feedstock's & Largest Consumers Basis: World
Petrochemical Feedstock Analysis CMAI (2005)

Benzene
Ethylbenzene
(55%)
Cumene (17%)
Cyclohexane
(14%)
Remaining
Alkylbenzene 3%
Nitrobenzene 6%
Others 5%
Mixed
Xylenes
Paraxylene
(70%)
Ortho Xylene
(12%)
Solvents (14%)

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10.9 Feedstock Requirements
A feedstock requires
1. Rapid demand growth in Asia
2. Changes to gasoline regulations
3. The influence of feedstock availability on capacity growth.
This is perhaps one of the most important differences between the world of olefins
and the world of aromatics.
Aromatics products and feedstocks, such as benzene, toluene and naphtha,
are liquids and are much easier and less expensive to transport than light feedstocks
(ethane, propane, and butane) for olefins.
Supplies of naphtha will increases with the rapid increase in condensate
production in the Middle East. This is because some of the condensate will be
processed in the Middle East thereby increasing naphtha exports while the balance
will be marketed in Asia where it will be used to produce petrochemicals.
Naphtha trade as a percentage of reported production is about 20 percent. The
potential naphtha yield is about 50 percent. There is some trade in aromatic (high
N+A) naphtha but most naphtha trade is feed for olefins plants. Most of the naphtha
trade occurs between producers in the Middle East and consumers in Asia. South
America, Africa and the FSU are also net exporters whereas Asia, North America and
Europe are net importers.
Over the next 15 years, world demand for naphtha for petrochemical
manufacture will grow at a rate of about 2.5 percent per year. Olefin naphtha (high in

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paraffins) will grow slower at just over 2 percent per year and high N+A naphtha
demand for aromatics manufacture will increase at a rate of about 3 percent.
The rapid increase in ethane and LPG use in the Middle East causing the slow
growth for olefins manufacture.
In particular, Asia is expected to have strong demand for polyester, particularly
for synthetic fibers and bottle resin. As a result, nearly 60 percent of the forecast
growth in aromatics capacity will be in Asia, with Northeast Asia accounting for the
largest share of this, with nearly 50 percent of total global growth in capacity. The
expected trend in aromatics markets is for capacity to be added in regions with high
demand for aromatics derivatives.

Figure 10.4: Aromatic Catalyst (Sources: The Catalyst Group Resourcs)

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Basically all cumene is used to produce phenol and acetone via the cumene
hydroperoxide process. Cumene is also produced by the alkylation of benzene, this
time with propylene. The use of traditional Friedel-Craft type of alkylation catalysts is
being superceded by zeolites.
The growth in demand, also averaging about 3% AAGR, is largely driven by
phenol demand for polycarbonate production (via bisphenol A), and to a lesser degree,
phenolic resins, nylon, alkylphenols and polyphenylene oxide. The total value of
cumene catalysts in 2001 is about $11 million. The co-product acetones growth is also
related to polycarbonates, as well as methylmethacrylate. The cumene catalyst market
is expected to reach $13 million by 2009.
The value of all other aromatics catalysts, including hydrodealkylation of
toluene (a large volume, low value catalyst market), adsorbents used in aromatics
separation, etc. totals around $69 million in 2001. If growth is as predicted, just short
of 3% AAGR, the sales of all other aromatics catalyst will reach $83 million in 2009.
The value of all aromatics catalyst markets in 2001, including those itemized in Table
III-12, total about $164 million. The projected total aromatic catalyst market in 2009
is $199 million.


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10.10 Case Study
Table 1.6.4 in the next page showing the summary of the cost investment and utility
consumption for a new Q-Max unit producing 200,000 MTA of cumene from extracted
benzene and chemical-grade propylene is shown in Table 1.6.3. The estimated erected
cost for the Q-Max unit assumes construction on a U.S. Gulf Coast site in 2002. The
scope of the estimate includes basic engineering, procurement, erection of equipment
on the site, and the initial load of QZ-2000 catalyst.
Table 1.6.3: Representative Cumene Product Quality


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Table 1.6.4: Investment and Operating Cost for 200,000 MTA Q-Max Unit

Normally, the utility requirements for a Q-Max unit depend on the project environment
(i.e., feed, product specifications, and utility availability). Q-Max units are often
integrated with phenol plants where energy use can be optimized by generating low-
pressure steam in the Q-Max unit for utilization in the phenol plant.

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10.11 Commercial Experience
In year 1996, the first Q-Max unit went on-stream. Since that time, there are total of
nine Q-Max Unit that has licensed by UOP throughout the world having a total plant
capacity of 2.3 million MTA of cumene. There are six Q-Max units have been
commissioned and three more are in various stages of design or construction. 35,000
to 700,000 MTA of capacities of cumene was produced. Several of these units have
been on-stream for more than 5 years without performing a single catalyst
regeneration.


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Contents
10.0 COMMERCIAL VALUE ................................................................................ 370
10.1 Cumene Market Survey .......................................................................... 370
10.1.1 Cumene Market Overview ................................................................ 370
10.2 Cost Estimation & Economics ................................................................. 375
10.2.1 Background & Objectives ................................................................. 375
10.2.2 Cost Evaluation ............................................................................... 375
10.2.3 Investment ..................................................................................... 377
10.2.4 Project Economic Evaluation ............................................................. 385
10.3 Cumene Commercial Value Report .......................................................... 389
10.3.1 US October cumene prices remain stable amid quiet trade ................. 389
10.3.2 US benzene and RGP markets are quiet ............................................ 390
10.4 Cumene Value Chain ............................................................................. 391
10.5 World Demand Of Cumene .................................................................... 393
10.6 Current Market Situation ........................................................................ 395
10.7 Cumene Market Outlook ........................................................................ 397
10.8 Petrochemicals: Global Markets .............................................................. 398
10.9 Feedstock Requirements ........................................................................ 399
10.10 Case Study .......................................................................................... 402
10.11 Commercial Experience ........................................................................ 404


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11.0 CONCLUSION AND RECOMMENDATIONS
An efficient process can be designed for the manufacturing of cumene by the
alkylation of benzene by making use of zeolite catalysts available today. Simple
adiabatic reactor technology is appropriate, but the operating pressure should be
sufficiently high to ensure only liquid - phase reaction. To limit the formation of
byproducts by consecutive polyalkylation a large ratio benzene/propylene is used,
which in turn implies large benzene recycle and considerable energy consumption.

The energy spent for benzene recycling can be reduced considerably by heat
integration, namely by double - effect distillation. In addition, the heat developed by
reaction can be advantageously recovered as medium - pressure steam. The
performance indices of the conceptual design based on literature data are in
agreement with the best technologies.

A modern alternative is the use of reactive distillation. At first sight appealing,
this raises a number of problems. The reaction rate is considerably reduced with
respect to a homogeneous liquid process because of the lower propylene
concentration due to phase equilibrium. In addition, the countercurrent flow of
reactants and products favors the formation of secondary polyalkylation species.
Therefore, catalytic distillation becomes economically interesting only if a suitable
catalyst is available. This should ensure much higher activity and better selectivity

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compared to a liquid - phase process. If these conditions are fulfilled the catalytic
distillation is superior by more compact equipment and better use of energy.

Oil is the largest segment of our energy raw materials use, being 40 percent,
while coal use accounts for 27 percent, gas 21 percent, and hydroelectric/nuclear 12
percent. It uses approximately 18 million barrels of oil per day. Worldwide
production is about 56 million barrels per day. With known reserves, this level of
worldwide production could remain constant for only 43 years. But there are large
volumes of unconventional petroleum reserves, such as heavy oil, tar sands, and oil
shale. These are located in the Western Hemisphere. Improvements in recovery
methods must be made, and the cost of production must decrease, for these
sources to become more important providers of energy.

Petroleum is vital to many industries, and is of importance to the maintenance
of industrialized civilization itself, and thus is critical concern to many nations. Oil
accounts for a large percentage of the world's energy consumption, ranging from a
low of 32% for Europe and Asia, up to a high of 53% for the Middle East. Other
geographic regions' consumption patterns are as follows: South and Central America
(44%), Africa (41%), and North America (40%). The world at large consumes 30
billion barrels (4.8 km) of oil per year, and the top oil consumers largely consist of

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developed nations. In fact, 24% of the oil consumed in 2004 went to the United
States alone, though by 2007 this had dropped to 21% of world oil consumed.

Today, about 90% of vehicular fuel needs are met by oil. Petroleum also
makes up 40% of total energy consumption in the United States, but is responsible
for only 2% of electricity generation. Petroleum's worth as a portable, dense energy
source powering the vast majority of vehicles and as the base of many industrial
chemicals makes it one of the world's most important commodities.
The increasing world energy demand has pushed the oil producing countries,
Middle East Countries, to start exploiting heavy oil reservoirs, which had been
neglected or little used and to increase the oil exploration activities. Currently,
some heavyweight producers such as Saudi Arabia, Venezuela and Iran produce
large quantities of heavy ( API < 20) sour crude with high sulfur content. Others
such as Nigeria, the United Arab Emirates, Angola and Libya pump a higher quality,
light sweet crude, with low sulfur content.

It is known that the global energy demand is increasing and this is putting
pressure on the oil producing countries to increase their production capacities. With
regard to Middle East Countries,, the production capacity is expected to reach 4
million barrels per day (MBPD) by the year 2020.

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In order for Middle East Countries, to maintain its market share, not only the
production capacity must increase but also heavy crude oil (API < 20) must be used
as gap filler.

These current events are facing the oil industry in Middle East Countries with
many decisions and technological challenges, including counteracting expected
increased risk of corrosion and equipment failures during the production and refining
of heavy crude oil. The most damaging impurities are inorganic salts, organic
chlorides, organic acids, and sulfur compounds.

To make matters worse, many of the compounds are unstable during refining
operations and they break into smaller components or combine with other

Most of the world refineries, including Kuwait, are equipped with alloys
capable of handling sweet light crude, which is most suitable for refining into petrol,
gas oil and heating oil. On the other hand, refining of heavy crude is difficult and is
associated with operational problems.


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The problems arise from the increased risk of corrosion, equipment failures,
and downtime of process units. These effects are caused primarily by the high sulfur
and salt contents of these crudes, including organic chlorides.

To make matters worse, many of the compounds are unstable during refining
operations and they break into smaller components or combine with other

Commercial production of cumene is by FriedelCrafts alkylation of
benzene with propylene. Previously, solid phosphoric acid (SPA) supported
on alumina was used as the catalyst. Since the mid-1990s, commercial production
has switched to zeolite-based catalysts.

distilling. The chemical is also flammable and incompatible with strong oxidizing
agents. Environmental laboratories commonly test isopropyl benzene using a Gas

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In recent years, producers have been under increasing pressure to improve
cumene product quality so that the quality of the phenol produced downstream (as
well as acetone and alpha-methylstyrene, which are coproduced with phenol) could
be improved. Twenty-five years ago, most phenol was used to produce phenolic
resins, and acetone was used primarily as a solvent.

Today, both phenol and acetone are used increasingly in the production of
polymers such as polycarbonates and nylon. Over the years, improvements to the
SPA producers still sought an improved cumene process that would produce a
better-quality product at higher yield.

Because zeolites are known to selectively perform many acid-catalyzed
reactions, UOP began searching for a new cumene catalyst that would overcome the
limitations of SPA.

UOPs objective was to develop a regenerable catalyst that would increase the
yield of cumene and lower the cost of production. More than 100 different catalyst
materials were screened, including mordenites, MFIs, Y-zeolites, amorphous silica-
aluminas, and betazeolite.

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The most promising materials were modified to improve their selectivity and
then subjected to more-rigorous testing. By 1992, UOP had selected the most
promising catalyst based on beta-zeolite for cumene production and then began to
optimize the process design around this new catalyst. The result of this work is the
Q-Max process and the QZ- 2000 catalyst system.

The commercial capacity of the cumene plant was 1 M ton of cumene per
annum. The yield of the cumene plant was 97.31% or 129,051kg/hr or 126,790.5
standard cubic feet per day.

Over the years, improvements in aromatic alkylation technology have come in
the form of both improved catalysts and improved processes. This trend is expected
to continue into the future.

Beta-zeolite catalyst is also an extremely effective catalyst for the
transalkylation of DIPB to produce cumene.

Due to the high activity of beta-zeolite, transalkylation in the Q-Max process
can be accomplished at very low temperatures to achieve high conversion and
minimum side products such as heavy aromatics and additional n-propylbenzene.

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As a result of the high activity and selectivity properties of beta-zeolite, the
same catalyst (eg, QZ-2000) is specified for both the alkylation and transalkylation
sections of the process.

With both of these reactors working together to take full advantage of the
QZ-2000 catalyst, the overall yield of cumene is increased to at least 99.7 wt%.

Cumene processes based on zeolites are environmentally friendly, offering
high productivity and selectivity. The most important are listed in Table 6.2. The
catalyst performance determines the type and operational parameters of the reactor
and, accordingly the flowsheet configuration. The technology should find an efficient

A process and instrumentation diagram was drawn for the reactor and
cumene column in the cumene plant. Process and Instrumentation diagrams (P&IDs)
is important as it describe the components of a plant and their logical connectivity.

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The motivation for interpretation of P&IDs is to build intelligent, symbolic
P&IDs for automated analysis, in support of retrofitting, for maintenance, for as-
built specification, and for compliance with regulations.
HAZOP analysis was done on the reactor and cumene column. HAZOP is a
hazard identification technique which considers system parts separately and
systematically examines the effects of deviations on each part.
An important benefit of HAZOP studies is that the resulting knowledge,
obtained by identifying potential hazards and operability problems in a structured
and systematic manner, is of great assistance in determining appropriate remedial
measures.
While a HAZOP is not appropriate in all circumstances one of the major
benefits that can be used to help justify the cost and time investment is that it also
helps to avoid operating problems and can thus provide a clear return on the
investment beyond the reduction in hazards.
Chemicals present a substantial hazard in the form of fires and explosions.
The combustion of one gallon of cumene can destroy an ordinary chemistry
laboratory in minutes; persons present may be killed. The potential
consequences of fires and explosions in pilot plants and plant environments are
even greater.


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The three most common chemical plant accidents are fires, explosions, and
toxic releases, Chemical and hydrocarbon plant losses resulting from fires and
explosions are substantial, with yearly property losses in the United States
estimated at almost $300 million (1997 dollars).' Additional losses in life and
business interruptions are also substantial.

To prevent accidents resulting from fires and explosions, engineers must be
familiar with the fire and explosion properties of materials, the nature of the
fire and explosion process, and procedures to reduce fire and explosion hazards.

Suspended solids can be removed by settling, using clarifiers. For some
effluents it will be possible to reduce the toxicity to acceptable level by dilution.
Other effluents will need chemical treatment. The oxygen concentration on water
course must be maintained at a level sufficient to support aquatic life. It is
measured by a standard BOD test.
All industrial processes produce waste products & full consideration must be
given to the difficulties & cost of their disposal. The disposal of toxic & harmful
effluents will be coverd by local regulations & the appropriate authorities must be
consulted during the initial site survey to determine the standards that must be met.
An environmental impact assessment should be made for each new project or
major modification or addition to an existing process.

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The power required for electrochemical processes, motor drives, lighting,
and general use maybe generated on site, but will more usually be purchased from
the local supply company.
The voltage at which the supply is taken or generated will depend on the
demand. For a large site the supply will be taken at a very high voltage, typically
11,000 or 33,000 V. Transformers will be used to step down the supply voltage to
the voltages used on the site.
In the United Kingdom a three phase 415V system is used for general
industrial purposes, and 240V single phase for lighting and other low power
requirements. If a number of large motors is used, a supply at an intermediate high
voltage will also be provided, typically 6000 or 11,000V.
The steam for heating is usually generated in water tube boilers using the
most economical fuel level available. The process temperatures required can usually
be obtained with low temperature steam typically 2.5 bar and steam distributed at a
relatively low pressure, typically around 8 bar (100 psig). Higher steam pressures, or
proprietary heat transfer fluids, such as dowtherm will be needed for high process
temperatures.
Cumene is a naturally occurring constituent of crude oil and may be released
to the environment from a number of anthropogenic sources, including processed
hydrocarbon fuels. Crude oils typically contain approximately 0.1 wt% of cumene,
but concentrations as high as 1.0 wt% have been reported.

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Measurements of various grades of petrol revealed that cumene
concentrations range from 0.14 to 0.51 vol% and that the average cumene
concentration was 0.3 vol%. Premium diesel fuel contains 0.86 wt% of cumene;
furnace oil (no. 2) contains 0.60 wt%.
In the atmosphere, cumene is expected to exist almost entirely in the vapour
phase (Eisenreich et al.,1981). Cumene does not absorb ultraviolet light at
wavelengths greater than 290 nm (US EPA, 1987), which suggests that cumene
would not be susceptible to direct photolysis. In one study, the estimated half-life of
cumene in the atmosphere from photolysis alone was approximately 1500 years
(Parlar et al., 1983).
Cumene is not susceptible to oxidation by ozone in the atmosphere (US EPA,
1987). Thus, reaction with ozone and direct photolysis are not expected to be
important removal processes. Rather, reaction with photochemically generated
hydroxyl radicals appears to be the primary degradation pathway (t l2 days)
(Lloyd et al., 1976; Ravishankara et al., 1978). Small amounts of cumene may be
removed from the atmosphere during precipitation.
Cumene has been assigned a Photochemical Ozone Creation Potential (POCP)
value of 35 relative to ethylene at 100 (Derwent & Jenkin, 1990). POCP values
represent the ability of a substance to form ground-level ozone as a result of its
atmospheric degradation reactions.


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ABB Lummus Global. 2005. Cumene Production Process.
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Levels (MRLs) for Hazardous Substances. ATSDR, Public Health Service, US
Department of Health and Human Services. Atlanta, GA. Available at:
http://www.atsdr.cdc.gov/mrls.html (accessed 6 November 2003).
Alberta Environment (AENV). 2000. Alberta Ambient Air Quality Guidelines
Environmental Sciences Division, Alberta Environment. Edmonton, AB.
February 2000. 3 pp.
Alkylation, AIChE Spring Meeting, New Orleans, March 2002
American Conference of Governmental Industrial Hygienists (ACGIH). 2003. 2003
TLVs and BEIs. Publication #0103. ISBN: 1-882417-49-6. ACGIH, Cincinnati,
OH. 224 pp.
Arizona Department of Health Services (DHS). 1999. 1999 Update Arizona Ambient
Air Quality Guidelines (AAAQGs). Report prepared for Arizona Department of
Environmental Quality, Air Programs Division. Arizona DHS, Office of
Environmental Health, Phoenix, AZ. 11 May 1999. 20 pp.
Aspen Plus, release 10, Aspen Technology, Cambridge, Massachusetts, USA
Batterman, S., T. Meets, P. Kalliokoski and E. Barnett. 2002. Low-Flow Active and
Passive Sampling of VOCs Using Thermal Desorption Tubes: Theory and
Application at an Offset Printing Facility. J. Environ. Monit. 4: 361-370.
Brown, R.H. and M.D. Wright. 1994. Diffusive Sampling Using Tube-type Samplers.
Analyst 119: 75-79.

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California Air Pollution Control Officers Association (CAPCOA). 1992. Air Toxics "Hot
Spots" Program Risk Assessment Guidelines, Prepared by AB2588 Risk
Assessment Committee of CAPCOA, Sacramento, CA. January 1992.
California Environmental Protection Agency (Cal EPA). 1999. Determination of Acute
Reference Exposure Levels for Airborne Toxicants. Office of Environmental
Health Hazard Assessment, Air Toxicology and Epidemiology Section, Cal EPA.
Oakland, CA. March 1999.
California Office of Environmental Health Hazard Assessment (OEHHA)/Air Resources
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