Documente Academic
Documente Profesional
Documente Cultură
GROUP MEMBERS:
KENNY THEN SOON HUNG (BK09110098)
LEE CHEE HOE (BK09110001)
DATE OF SUBMISSION:
29TH MAY 2013
LECTURER:
ASSOC. PROF. IR. OTHMAN BIN ABDUL HAMID
THE PROJECT: UOP Q-MAX CUMENE PRODUCTION PROCESS
TABLE OF CONTENTS:
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
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
REFERENCES
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
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
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
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
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.
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
in Sarawak, where oil was first discovered in 1909 and first produced in 1910. Prior
The companies then paid royalties and taxes to the government. This state of
explore and produce resources. The national oil company retains ownership and
Expenditure and profits are managed under instruments called Production Sharing
Contracts (PSCs). The Production Sharing Contractor assumes all risks and sources
all funds for all petroleum operations. The Contractor receives an entitlement
through production.
Each PSC may have different terms and conditions. For example, different
time periods are allowed for exploration of acreage, developing and installing
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.
Figure 1.2 Historical Crude Oil Production (bbls : barrels per day. SB :
contribution.)
standard cubic feet per day. Malaysia has 494,183km2 of acreage available for oil
and gas exploration, with 337,167 km2 in the offshore continental shelf area, and
63,968km2 in deepwater.
are currently operated by Petronas Carigali Sdn. Bhd. plus seven other multinational
oil companies.
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
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
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
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
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
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,
(Source: http://en.wikipedia.org/wiki/Oil_refinery)
(Source: http://en.wikipedia.org/wiki/Cumene)
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
most gasolines. It is the principal chemical used in the world wide production of
banded with phenolic resins, nylon-6, epoxy and polycarbonate resins and solvents,
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
cumene had been used extensively during warld war2. It is a curious fact that
chloride have been the standard methods of manufacture for many years ,the first
plan used sulphuric acid as a catalyst. This was a war time expedient arising from
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
Neither does it seem likely that any large scale plant would be installed for
on alumina was used as the catalyst. Since the mid-1990s, commercial production
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
Cumene
IUPAC name
(1-methylethyl)benzene
Other names
isopropylbenzene
2-phenylpropane
Identifiers
PubChem 7406
ChemSpider 7128
UNII 8Q54S3XE7K
KEGG C14396
ChEBI CHEBI:34656
Properties
Viscosity 0.777 cP at 21 °C
Hazards
R-phrases R10,R37,R51/53,R65
S-phrases S24,S37,S61,S62
Flash point 43 °C
Related compounds
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. Ūdris
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.
acid is often favored over aluminium halides. Cumene is formed in the gas-
Cumene is oxidized in air which removes the tertiary benzylic hydrogen from
Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and
tertiary benzylic hydrogen from cumene and hence forms a cumene radical:
cumene molecule.
This latter cumene converts into cumene radical and feeds back into
This is followed by a step in which the phenyl group migrates from the benzyl
is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion
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 1960’s and is prominent today. The first step of this
plywood and composition board (40% of the phenol produced) for the
for caprolactum, the starting material for nylon-6 (20%). Minor amounts are
4. The largest use for acetone is in solvents although increasing amounts are
of cumene.
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
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
3. Benzene pumped to the feed vessel which mixes with the recycled benzene.
4. This reactant mixture passed through a fired super heater where reaction
5. The vapor mixture is sent to the reactor tube side which is packed with the
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 40 oC in
a water cooler, propylene and propane are separated from the liquid mixture
the pressure is controlled by the vapor control value of the separator, the fuel
6. The liquid mixture is sent to the benzene distillation column which operates at
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,
8. The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %
10. The cumene product is 99.9 Wt. % pure and the heavy aromatics, which have
cumene.
11. The overall yields of cumene for this process are typically 97-98 Wt. % with
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
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.
Basically, The Abu Dhabi Oil Refining Company (Takreer) was established in 1999 in
the Abu Dhabi National Oil Company (ADNOC). There are several company’s areas of
operation which include the refining of crude oil and condensate, supply of petroleum
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
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
construction phase of a base oils plant at the Ruwais Industrial Complex in Abu Dhabi.
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
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
1976
Original Plant 15,000 BBL/day
1983
New Refinery 60,000 BBL/day
1996
Plant Expansion 85,000 BBL/day
Figure 2.2: history of the refineries in Abu Dhabi Refinery which consists
of 85000bbl/day
is shown in below:
1981
Hydro-skimmer units 120,000BBL/day
1985
Hydrocracker units
2000
Condensate units 280,000 BBL/day
2006
Gasoline Units
40000bbl/day
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
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
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
On 30th 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.
from the Refinery are as follows: Liquefied Petroleum Gases, Naphtha, Unleaded
Gasoline, Aviation Turbine Kerosene, Domestic Kerosene, Gas Oil, Straight Run
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
Crude Unit.
This unit has produced three products namely: Heavy Naphtha, Light Naphtha
Mercaptans was converted by the unit in the straight run kerosene into
disulphine in order to meet the final product quality for aviation kerosene.
The Reformer processes the Heavy Naphtha cut to improve its anti-knock
Gas oil sulphur content has been reduced by the Gas Oil Hydrodesulphurise to
In this unit, raw LPG from Naphtha Hydrodesulphuriser and Catalytic Reformer
Gasoline.
Besides that, the butane also can blended with Propane in order to form LPG
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.
The acid gases produced from Gas Sweetening Unit are converted to liquid
sulphur.
The Oil/Gas Separation Plant is designed to stabilize Crude from Jarn Yaphour
The separated gas is further treated to remove hydrogen sulphide, water and
Additional Effluent Water Treatment facilities were installed to adhere to rigid oil in
2.3.2.1 Utilities
Power and fresh was supplied from the adjacent plant of the Abu Dhabi Water
Steam, Air, Nitrogen and Sea Water for cooling are all provided by the Refinery's
own facilities.
The Refinery’s Fuel Gas supply is supplemented by Natural Gas from the GASCO
Main Network.
2.3.2.2 Off-sites
The storage capacity of Abu Dhabi Refinery Tank Farm is 500,000 cubic meters,
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.
Abu Dhabi Refinery completed the process of installing a fully integrated state-
1994.
In January 1993, the first level was achieved with the commissioning of a new
Activities.
On the other hand, the second level of the project includes the implementation
Computerization.
85 000 BPSD
From crude oil to fraction of
CRUDE DISTILLATION UNIT
naphtha, kerosene, gas oil and
straight run residue
22 795 BPSD
NAPHTHA From straight run naphtha to heavy
HYDRODESULPHURISER UNIT naphtha, light naphtha and sour
liquefied petroleum gaese
21 250 BPSD
KEROSENE MEROX UNIT
From mercaptans to disulphide
14 000 BPSD
CATALYTIC REFORMER UNIT From heavy naphtha cut to
gasoline blending component
22 500 BPSD
GAS OIL HYDRODESULPHURISER
Product: Reduced sulphur
UNIT content of gas oil
ABU DHABI
REFINERY
35 tons/day
SULPHUR RECOVERY UNIT From acid gases to liquid
sulphur
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)
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
795000
800000
700000
600000
500000
400000
300000
224000
200000 189000
178000
110000
100000
62000
32000
0
Gasoline Fuel oil Jet fuel & Gas oil LPG Naphta Total
kerosene
Based on the production of Abu Dhabi Oil Refining Company (refinery plant) at the
Table 2.2: Calculation of final product from 400 000 BPD Middle East
heavy crude
** This analysis is done based on a production rate from Abu Dhabi Oil Refining
140000
120000
100000
QUANTITY (BPD)
80000
60000
40000
20000
0
PRODUCT
Gasoline Fuel oil Jet fuel & kerosene Gas oil LPG Asphalt
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
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
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
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
other
motor gasoline
15%
15%
petroleum gases
jet fuel
7%
7%
kerosene
5%
fuel oil
23%
fuel oil
28%
motor gasoline jet fuel kerosene fuel oil fuel oil petroleum gases other
Table 2.4: Calculation of final product from 400,000 BPD Middle East
heavy crude
Gasoline Fuel oil Jet fuel Kerosene LPG Asphalt Residual fuel oil
120000
100000
80000
Quantity (BPD)
60000
40000
20000
0
Product
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
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
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
Basically, these current events are facing the oil industry in Middle East
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
Things might getting worst when many of the compounds are unstable during
refining operations and they break into smaller components or combine with other
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
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
on alumina was used as the catalyst. Therefore, since the mid-1990s, commercial
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.
taking about 7 – 8% from the total worldwide propylene consumption. Today, the
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
distillation.
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 with only 10% propane. As an exercise, the reader can examine the impact
General information about chemistry, technology and economics can be found in the
2008):
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
The synthesis can be performed in gas or liquid phase. Before 1990 gas – phase
alkylation processes dominated, but today liquid - phase processes with zeolite
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,
solution for using the reaction heat inside the process and and/or making it available
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
separation section, in this case a series of four distillation columns: propane (LPG)
kellogg 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
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
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
mixture
process for developing phenol and acetone from benzene and propylene. The term
stems from cumene (isopropyl benzene), the intermediate material during the process.
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.
acid is often favored over aluminium halides. Cumene is formed in the gas-
Cumene is oxidized in air which removes the tertiary benzylic hydrogen from
Cumene is a colourless liquid, soluble in alcohol, carbon tetra chloride, ether and
tertiary benzylic hydrogen from cumene and hence forms a cumene radical:
This cumene radical then bonds with an oxygen molecule to give cumene
This latter cumene converts into cumene radical and feeds back into
This is followed by a step in which the phenyl group migrates from the benzyl
is then transferred from the hydroxy oxygen to the ether oxygen, and finally the ion
The mechanism of benzene alkylation with propylene involves the protonation of the
stronger acid sites favors the formation of propylene oligomers and other hydrocarbon
reaction with benzene. Below, the chemical reactions of significance are listed:
Currently almost all cumene is produced commercially by two processes. The first type
UOP (Universal Oil Products Platforming Process). The second type is A homogeneous
Propylene feed fresh benzene feed and recycle benzene are charged to the upflow
reactor, which operates at 3-4 Mpa and at 200-260°C. The solid phosphoric acid
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
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
The overall yields of cumene for this process are typically 97-98 Wt. % with
3.4.1.1 Application
3.4.1.2 Description
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
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
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
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
3.4.1.3 Economics
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
Seven Q-Max units are in operation with a total cumene capacity of 2.3 million tpy,
3.4.2.1 Application
3.4.2.2 Description
and a distillation section. Liquid propylene and benzene are premixed and fed to the
reactor (2) where PIPB reacts to form additional cumene. The transalkylation and
alkylation effluents 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)
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
This process is essentially stoichiometric and product purity above 99.97% weight has
3.4.2.5 Economics
Estimated ISBL investment for a 300,000-MTPY unit on the Us Gulf Coast (2004
The utilities can be optimized for specific site conditions/economics and integrated
The first 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
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 135°C
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
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.
3.4.4.1 Overview
The CDCumene® process, marketed by ABB, produces ultra high purity cumene using
3.4.4.2 Application
using patented catalytic distillation (CD) Technology. The CD cumene process uses a
3.4.4.3 Description
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
phase is kept extremely low (<0.1 wt%) due to the higher volatility of propylene to
Overhead vapor from the CD column (1) is condensed and returned as reflux
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
features higher product yields, with a much lower capital investment, than the
The exceptional quality of the cumene product from the CDCumene process
easily surpasses current requirements of phenol producers, and may well define
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
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.
3.4.4.4 Advantages
3.4.4.7 Yields
100,000 metric tons (mt) of cumene are produced from 65,000 mt of benzene and
least 99.95% pure and has a bromine index of less than 2, without clay treatment.
3.4.4.8 Economics
Based on a 300,000-MTPY cumene plant located in the US Gulf Coast, the ISBL
The Q-Max process converts benzene and propylene to high-quality cumene by using
quality, low investment and operating costs, reduction in solid waste, and corrosion-
free environment.
Over the years, many different catalysts have been proposed for this alkylation
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
aviation gasoline. Today, cumene is no longer used as a fuel, but it has grown in
Although SPA is a highly efficient and economical catalyst for cumene synthesis,
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
improved. Twenty-five years ago, most phenol was used to produce phenolic resins,
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-
reactions, UOP began searching for a new cumene catalyst that would overcome the
limitations of SPA.
UOP’s 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
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-
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
3. Benzene pumped to the feed vessel which mixes with the recycled benzene.
4. This reactant mixture passed through a fired super heater where reaction
5. The vapor mixture is sent to the reactor tube side which is packed with the
production and the effluent from the reactor i.e., cumene, p-DIPB,
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
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
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,
8. The typical reactor effluent yield contains 94.8 Wt. % cumene and 3.1 Wt. %
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
to cumene.
11. The overall yields of cumene for this process are typically 97-98 Wt. % with
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
alkylation reactor. The fresh propylene feed is split between the four catalyst beds. An
oligomerization.
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
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
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
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.
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
alkylation, which can be accomplished by many different acid catalysts. The basic
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
The addition of the isopropyl group to the benzene ring weakly activates the
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
benzene molecule to form two molecules of cumene (Figure 3.15). The Q-Max process
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 %.
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):
the propyl carbonium ion with propylene to form a C6 olefin or even further
2. Alkylation of benzene with heavy olefins. Once heavy olefins have been
primarily at the meta and para positions, to make DIPB and heavier alkylates.
tertiary carbon on cumene can form a cumyl carbonium ion that may react
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
product.
Figure 3.17: Process Flow Diagram For The Production of Cumene Process
Figure 3.18: Process Flow Diagram For The Production of Cumene Process
Figure 3.19: Simple Process Flow Diagram For The Production of Cumene Process
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
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
3. Reactor section
Benzene (99.9%) and propane (95%) are stored in liquid state in storage tanks
added to the stream line of the feed inlet to the cascade of heat exchangers.
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
Finally after the heat exchanger a fired heater is used to vaporize and raise the
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 di- iso
propylbenzene (DIPB).
obtained from the reactor and the recovered benzene is recycled to the feed
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
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
The UOP process converts a mixture of benzene and propylene to high quality
exceptionally high yield, better product quality, less solid waste, decrease in
investment and operating costs and a corrosion free environment. The UOP process
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.
based cumene technologies, the UOP process provides the highest product quality and
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
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
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
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
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 2–4
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
Figure 3.20: Simple Process Flow Diagram For The Production of Cumene Process
Vapors are reacted over catalyst; temperature 350°C; pressure 25 atm.; 99%
Vapor is cooled to 40°C at 25 atm. pressure, separating essentially all of the benzene,
Overhead stream contains 98.1 mole% benzene, balance cumene; bottoms stream
Overhead stream contains 99.9 mole% cumene; bottoms stream contains pure DIPB
3.14.1 Stream 1
3.14.2 Stream 2
3.14.3 Stream 3
3.14.4 Stream 4
3.14.5 Stream 5
3.14.6 Stream 6
3.14.7 Stream 7
3.14.8 Stream 8
0 mole% benzene
3.14.9 Stream 9
3.14.10 Stream 10
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
The reaction mechanism and kinetics may vary depending on the catalyst used.
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
(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
include the population balance, energy balance and the somewhat more
complex entropy balance. These techniques are required for thorough design and
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.
follows:
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
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
This modified equation can be used not only for reactive systems, but for
given below. Note that it simplifies to the earlier equation in the case that the
In the absence of a nuclear reaction the number of atoms flowing in and out
Mass balances can be simplified with the assumption of steady state, where the
Propylene
Major Cumene
Equipment DIPB
Reactor Unreacted
Benzene
Benzene
The reactions for cumene production from benzene and propylene are as follows:
4.1.2.1 Assume 330 working days per year and 24 hours per day
(a) Assumption
(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.
= 1050.50 Kgmole/hr
(a) Assumption
(b) Justification
The complete conversion of the reactants to the cumene is very hard to achieve since
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
Hence:
Cumene required
= 1050.50/ 0.98
= 1071.94 Kgmoles/hr
= 128836.32 Kg/hr
Propylene required
(a) Assumption
Benzene required
= 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.
= 1105.09-1071.94
= 33.15/2 kmoles/hr
= 16.575 kmoles/hr
DIPB produced
Benzene in product
= 292.85 kmoles/hr
= 22820.85 kg/hr
Checking:
Input = output
Propylene
=46414.78kg/hr
Major Cumene=128836.32 kg/hr
Equipment DIPB=2685.15kg/hr
Reactor Unreacted
Benzene=22820.85kg/hr
Benzene
=107746.27kg/hr
removed in depropanising column and sent to reactor for quenching. Hence material
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
Minor
Feed, F
Equipment
= Cumene+Benzene+DIPB
Benzene
=154160 kg/hr
Column
D
= Benzene
F=D+W
154160 = D +W
F XF = DXD +WXw
XF = 22820.85/154160 = 0.1480
Taking,
XD = 0.9999
Xw = 0.05
D = 15969.41 Kg/hr
= Benzene
W = 154160 – 15969.41
= 138190.5 Kg/hr
= cumene + DIPB
Checking:
= 154160 kg/hr
Input = Output
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
= 154160 + 15969.5
= 170129.5 Kg/hr
W
= Cumene +DIPB
=138190kg/hr
Feed, F Minor
Equipment
= Cumene+Benzene+DIPB
Benzene
=154160 kg/hr
Column
D
= Benzene
=15969.41kg/hr
The function of cumene distillation column is to separate the cumene from DIPB.
W
= DIPB
Minor
Feed, F
Equipment
= Cumene +DIPB
Cumene
=138190.5 kg/hr
Column
D
= Cumene
F = D +W
138190.6 = D +W
XF =128836.3/138190.5 = 0.932
Taking
XD = 0.995
XW = 0.01
D = 129051 kg/hr
W = 138190.5 – 129051
= 9139.5 Kg/hr
Checking:
= 138190.5 Kg/hr.
Input = output
W
= DIPB
=9139.5 kg/hr
Minor
Feed, F
Equipment
= Cumene +DIPB
Cumene
=138190.5 kg/hr
Column
D
= Cumene
=129051kg/hr
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.
Where,
ΣEp= EP1 + EP2 + EP3 + ……. = Total Energy Leaving with Products
ΣEW = EW1 + EW2 + EW3 + … = Total Energy Leaving with Waste Materials
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,
pipes, the frictional losses appear as heat but the details of the heating need not be
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
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
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.
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
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
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.
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 ΔT). 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.
The gases viz. Propylene, propane, benzene enter at 25 °C and benzene enters at
80°C.
A Propylene 64.18
B Benzene 82.22
C Propane 73.89
Benzene in feed
= 1381.36 + 204.73
= 1586.09 kmoles/hr.
4.2.2.1 Assumption
Assuming that propylene is accompanied with propane as impurity in the ratio of 3:1.
Hence,
XA =0.3612 ,
XB = 0.5184 ,
XC = 0.1204
= 71.38 J/mole K
A Propylene 64.52
B Propane 70.17
C Benzene 98.20
or, T = 290C
P1 =1 atm, T 1= 290C
P2 = 25 atm, To find T 2
= 42.19 °C
m = cumene+DIPB+Benzene+propane
=1071.94+16.575+292.85+368.36
= 1749.72 kmoles/hr
Propane 107.76
Cumene 205.24
Propylene 97.60
Benzene 121.19
= 168.22 J/mole K
m= propylene+benzene+propane
= 1105.09+1586.09+368.36
= 3059.54 k moles/hr
T ≈ 200 °C
The reactants have to be further heated to the reaction temperature of 250 °C before
Propane 117.76
Propylene 97.60
Benzene 141.19
= 122.62 J/mole K
m Cp avg(250-100)=msteamλ
=106.63 x 106KJ/hr
= 6.3326 x 1010KJ/hr
= 5.796 x 1010KJ/hr
Hence,
= 368.36 kmoles/hr
= 368.36 x 44 kg/hr
= 16207.84 kg/hr
Q = m λ + m Cp (250 –68.4)
= 11.603 x 106KJ/hr
= 54.58 x 108KJ/hr
= Ql
Ql = m Cp (223.85 –25) + mλ
m = 1.713233 x 106kg/hr
To find the temperature at which the product stream is fed to propane distillation
column:
At P1 = 25 atm, T1 = 200 °C
At P2 =1 atm T2 = ?
Cp avg at 100 °C
=100(1/25)8.314 / 137.05
=82.260C
F=1749.72 kmoles/hr
D=368 kmoles/hr
W=1381.72 kmoles/hr
As propane is the major constituent that goes with the overhead, taking λ and Cp
values of Propane,
Hv =V [λ + Cp (Tb –To )]
T0=25 °C ;
Tb= 42.1 °C ,
Cp =2.41 KJ/kg °C
Therefore
HD =DCp(Tb–T0)
HL=L Cp (Tb–T 0)
=3.336 x 105KJ/hr
Qc = 10.325 x 106KJ/hr
Cp=4.18 KJ/kg °C
Therefore
H F + QB = H D + Q C + H W
To find HW:
By using
Tb = 1370C
= 174 J/mole K
= 174 kJ/kmole K
=1.5575 KJ/kg K
HF = 0 [ because TF = T0 ]
QB =HD + QC + H W - HF
QB = msteam λ
D = 15969.4 kg/hr
W = 138190 kg/hr
Benzene vapor from the top is recycled. Assuming very small propane content to be a
Hence,
T0 = TF = 137 °C
λ of benzene
=94.14cal/gm mole
= 393.8818 KJ/gm
= 1.2246 KJ/kg °K
= -1.1127 x 106KJ/hr.
HL = L Cp (Tb–T0)
Hv = QC + HL +HD
Cp=4.18 KJ/kg °C
Therefore,
HF + QB = HV + QC +Hw
To find HW :
w = 138190 Kg/hr
= 153.4 °C
= 1.91 KJ/kg °C
= 3.0774 x 106KJ/hr
QB = msteam λ
F = 138190 kg/hr
D = 129051 kg/hr
w = 9139 kg/hr
As the cumene is the major constituent that goes with the overhead, taking λ and C p
values of Cumene,
λ of cumene
=74.6 cal/gm
= 312.1264 KJ/kg
= 0.4047 cal/gm °K
= 1.6931 KJ/kg °K
V=D+L
= 129051 + 68655.1
=197706.1 kg/hr
= 61.3745 x 106KJ/hr
HD = D Cp (Tb–T0)
= -0.218496 x 106KJ/hr
HL = L Cp(Tb –T0 )
Hv = QC + HD +HL
Cp=4.18 KJ/kg °C
HF + QB = HV + QC +Hw
To find HW :
W = 9139 kg/hr
Hw = W Cp avg (Tb–T 0 )
T b at xw
= 0.2934 =184.5 °C
= 287.9584 J/mole °K
= 2.88795 KJ/kg °K
HF = 0 [ because TF = T0 ]
QB = HV + QC + HW - HF
QB = msteam λ
factor is 1
to process)
= 1075.43X1/1105.09
= 97.31%
kg 24hr m3 3.28ft 3
scfd = 129,051 hr × × 862kg × [ ]
day 1m
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
Pressure (bar) 1.00 11.66 1.01 31.50 31.50 31.25 30.95 30.75
Flowrate (tonne/h) 8.19 4.64 16.37 4.64 16.37 21.01 21.01 21.01
P-Diisopropyl Benzene - - - - - - - -
Total (kmol/h) 105.00 110.27 211.89 110.27 211.89 322.16 322.16 322.16
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
Vapor mole fraction 1.0 1.0 0.0 0.0 0.0 0.0 0.0
Table 4.2: Flow Summary Table for Utility Streams (Based on Figure 4.1)
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
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
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
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
of the Q-Max process. This will caused minimal overall butylbenzene formation.
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
containing less than 250 wt ppm NPB and maintaining an acceptable catalyst cycle
length.
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
alkylation environment can act as a Brønsted base. Unfortunately, water does not
have a detrimental effect at the typical feedstock moisture levels and normal
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
converted to products outside the boiling range of cumene. Thus, trace sulfur in the
considered for cumene production will normally result in cumene product sulfur
content that is within specifications (for example, 1 wt ppm). Thus, the sulfur
content of the cumene product does depend on the sulfur content of the propylene
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.
Propane entering the unit with the propylene feedstock is unreactive in the
In the late 1980’s, two new processes using zeolite based catalyst systems were
developed.
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
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.
4. Lower activity
5. Catalyst non-regenerability
1. Environmental hazard
3. High corrosion
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.
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.
high quality cumene using a regenerable zeolite catalyst. The Q-MAXTM 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
A very good cumene yield and quality has been produced by the Q-MAXTM
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
provides the highest product quality and great stability. QZ-2000 is non-corrosive
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.
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
alkylation. For example, the alkylation of benzene with n-propyl bromide gives
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
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
composition of matter in 1967 (63). Since that time, catalysts utilizing beta-zeolite
of-the-art catalysts such as the UOP EBZ-500 and QZ-2000 for ethylbenzene and
At the same time that the structure of beta was being investigated, extensive
research was being conducted to identify new uses for this zeolite.
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
of beta coupled with the high acidity of the material made it an ideal catalyst for
aromatic alkylation.
derivative products such as ethylbenzene and cumene with extremely high yields
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
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
Monsanto and
by UOP
In the late 1980, two new processes using zeolite-based catalyst systems
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
A typical reactor effluent yield contains 94.8 wt% cumene and 3.1 wt%
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
With transalkylation and 94–96 wt% without transalkylation, the overall yields
Generally, AlCl3 processes have been used more extensively for the production of
The overall yields of cumene for this process can be as high as 99 wt% based
and recycle, and propylene are mixed in the alkylation reaction zone with the AlCl3
transalkylation zone.
The strongly acidic catalyst is separated from the organic phase by washing
In the early 1980s, Unocal introduced a fixed-bed liquid-phase reactor system based
90 wt%.
cumene of 99 wt%.
The distillation requirements involve the separation of propane for LPG use,
cumene product.
Based on the concept of catalytic distillation, the second zeolite process was
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
Over the past decade, great progress has been made in improving and
optimizing catalyst formulations for use in both the EB and cumene alkylation
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
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
Through this work it has been found that with a Si/Al2 ratio of 25, the catalyst
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
to the Lewis acid function of the catalyst. Olefin oligomerization reactions can lead to
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
The most common mechanism for the formation of non framework alumina is
manufacturing process. By careful control of the temperature, time, and steam levels
upsets.
state-of-the-art formulation.
Si/Al2 ratio of the beta-zeolite structure in which the dominating influence of this
parameter is evident.
Stabilizing the zeolitic structure through careful process and chemical means
results in a catalyst system that is extremely robust, highly regenerable, and tolerant
to similar conclusions.
For example, Enichem finds that beta-zeolite is the most effective catalyst for
synthesis of MCM-22.
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
aromatics that distill with cumene (including olefins, which are analyzed as Bromine
butylene in the propylene feed, there is always the potential for butylbenzene
in the feed.
feedstock typically contains <15 wt-ppm butylbenzenes. The Q-Max process typically
The DIPB is fractionated from the cumene and reacted with recycle benzene
same catalyst (eg, QZ-2000) is specified for both the alkylation and transalkylation
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%.
that any significant impurities in the cumene product are governed largely by trace
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
solution for using the reaction heat inside the process and and/or making it available
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
separation section, in this case a series of four distillation columns: propane (LPG)
polyisopropylbenzenes.
processes based on zeolites. The term zeolitic refers to molecular sieves whose
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
Both the specific three - dimensional structure and the chemical composition,
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
synthesis
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
propylene conversions
As Table 5.6 shows, the selectivities of zeolite - beta and MCM - 22 are similar
0C 7.2. Modified Y - type zeolites were found capable of selectivity over 97%
Recent patents show that the new superactive zeolite catalysts are suitable
heat integration.
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
used, typically less than 10%. Since the reduction of particle size is restricted in
control. In conclusion, the subtle combination of chemical and physical factors leads
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
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
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)
concern from both a physical handling and disposal perspective. This concern has
fueled much development work toward solid acid catalysts, including zeolites, silica
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
catalysts that were introduced for the production of ethylbenzene, cumene and
detergent alkylate .
process industry diagram with standard symbols which shows the interconnection of
process equipment and the instrumentation used to control the process. The P&ID
control installation.
equipment and systems, as well as how these systems connect. During the
design stage, the diagram also provides the basis for the development of
The P and I diagram shows the arrangement of the process equipment, piping,
2. All pipes, identified by a line number. The pipe size and material of construction
should be shown. The material may be included as part of the line identification
number.
3. All valves, control and block valves, with an identification number. The type and
size should be shown. The type may be shown by the symbol used for the valve or
4. Ancillary fittings that are part of the piping system, such as inline sight-glasses,
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 flow-sheet, but the
process information is not shown. The same equipment identification numbers should
The symbols used to show the equipment, valves, instruments and control loops will
depend on the practice of the particular design office. The equipment symbols are
usually more detailed than those used for the process flow-sheet.
Standard symbols for instruments, controllers and valves are given in the
and also shows the American standard symbols (ANSI) and examples of those used by
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
and swagers
Flow directions
Interconnections references
This symbol is used to represent all types of control valve, and both pneumatic an
electric actuators.
The direction of the arrow shows the position of the valve on failure of the power
supply.
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
in the control room. Except on small plants, most controllers would be mounted in the
control room.
The first letter indicates the property measured; for example, F D flow. Subsequent
I = indicating
RC = recorder controller
The suffixes E and A can be added to indicate emergency action and/or alarm
them from the main process lines. Dotted or cross-hatched lines are normally used.
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
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
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,
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,
passageways. Valves are technically pipe fittings, but are usually discussed as a
separate category.
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
commercial, residential, and transport. The industries in which the majority of valves
are used are oil and gas, power generation, mining, water
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
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.
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).
Valves are quite diverse and may be classified into a number of basic types. There are
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
Annular valves are suitable for regulating flow and pressure. They are prepared
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.
Diaphragm valves are used on shut-off and throttling service for liquids, slurries 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.
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
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
Weir: The Weir Diaphragm valve can be used for either off/on and throttling
services
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
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
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.
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
or closed. When fully open, the typical gate valve has no obstruction in the flow path,
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
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,
inspection and cleaning. It also gives the body added strength. Bolted bonnet is used
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,
Gate valves may have flanged ends which are drilled according to pipeline
from cast iron, ductile iron, cast carbon steel, gun metal, stainless steel, alloy steels,
A needle valve is a type of valve having a small port and a threaded, needle-shaped
It is called needle valve due to the shape of the closure member. It consists on
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
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
and seat. A long travel axially (the control input) makes for a very small and precise
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
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
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
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"
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
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
sleeve. The sleeve will contain the flow media and isolate it from the environment
processes with entrained solids, because the flexible rubber sleeve allows the valve to
close droptight around solids—solids 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
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
Generally, the pinch valve is limited to work at low pressures. Pinch valves can
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.
strength properties can be reduced by the attack of the corrosive fluid. Fatigue limit of
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
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.
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
Ball valves are used extensively in industrial applications because they are very
Sizes typically range from 0.2 to 11.81 inches (0.5 cm to 30 cm). They are easy to
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
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
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
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
Types of Body:
Welded: Welded ball valves guarantee the absence of leakages along all the
important requisite especially for ball valves installed onto underground and
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
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
"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,
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
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
As any quarter turn valve, the operative of the butterfly valve is quiet easy. The
closure member is a disc that turns only 90º; to be full opened/closed. This is a quick
operation. Few wear of the shaft, little friction and then less torque needed means a
cheaper actuator. The actuator can be manual, oleo hydraulic or electrical motorized,
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
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
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
1. Concentric butterfly valves - This type of valves has a resilient rubber seat with
a metal disc.
offset butterfly valves) - Different type of materials is used for seat and disc.
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
The wafer style butterfly valve is designed to maintain a seal against bi-
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 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
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
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
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,
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
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
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
plug valves. When fused with the glassware, the valve bodies are made of glass.
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
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
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)
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
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
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
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
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
confused with ball valves, which is a different type of valve in which a ball acts as a
a normally-closed valve. Pressure on the upstream side must be greater than the
differential, for the check valve to open allowing flow. Once positive pressure stops,
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.
then remains open until the tank drains and the flapper falls due to gravity. Another
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
sewage waters. Such risk occurs most often in sanitary drainage systems connected to
A stop-check valve is a check valve with override control to stop flow regardless of
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
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
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.
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
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.
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
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.
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.
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
Safety valve (SV): automatic system that relieves the static pressure on a gas.
Safety relief valve (SRV): automatic system that relieves by static pressure 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
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
RV, SV and SRV are spring-operated (even said spring-loaded). LPSV and VPSV are
spring-operated or weight-loaded.
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.
or monomer?
5. What happens if a line fails, for example, a failure of a high-pressure gas line
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
discharge side.
4. Storage vessels need pressure and vacuum reliefs to protect against pumping
condensation.
5. Vessel steam jackets are often rated for low-pressure steam. Reliefs are
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
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,
1. spring-operated
2. rupture discs)
1. conventional
2. balanced-bellows
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
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,
pressure between the inlet and the outlet of the valve. Therefore the flow is
Rupture discs are specially designed to rupture at a specified relief set pressure.
relief devices. They can be made from a variety of materials, including exotic
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
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
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
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.
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
2) The safety valve is for gas service. Safety valves pop open when the
nozzle that directs high-velocity material toward the valve seat. After
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
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
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.
6.8.3 Justification of the Selection of the Type of Valve and Safety Valve to the Reactor (Major Equipment)
Type of
Location of installation Justification
valve
Ball Installed before and after Ball valves are excellent in chemical applications, including the most challenging services
valve every equipment such as (e.g., dry chlorine, hydrofluoric acid, oxygen). Readily available in a wide variety of
pump, control valve, inlet configurations, 3-piece, end entry and top entry, these valves range from commodity type
purpose is to ease the Advantages of ball valves include ease of operation, standard face-to-face dimensions,
maintenance of each high flow capacity, high pressure/temperature capabilities and ability to handle severe
equipment. For emergency service chemicals. The quarter turn operation is desirable to most operators and fairly
The face-to-face dimensions comply with ASME, making the ball valve easy to retrofit
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.
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
The ability to provide fire safe protection and handle severe service chemicals are two of
Source: http://www.engvalves.com
Relief -installed at discharge A spring operated valve is selected because rupture disk type will cause losing of the
valve point of every pump to entire content. Propylene, benzene and cumemne is an expensive. Besides, it may allow
prevent pressure build up air to enter the process, leading to a possible pump damage, fire or explosion. Propylene,
-installed at jacket benzene and cumemne is highly flammable. Relief valve is selected because of this relief
-installed on top of the is in a liquid service line. A conventional relief device is satisfactory.
reactor to prevent
pressure build up
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
the column as it will affect the reaction rate of the process. Column may not be able
and thus rupture. If the temperature is too low, the reactant may not be able to react
6.9.3 Justification Of The Selection Of The Type Of Valve And Safety Valve To The Cumene Column (Minor)
valve installation
Ball Installed before and Ball valves are excellent in chemical applications, including the most challenging services (e.g.,
valve after every dry chlorine, hydrofluoric acid, oxygen). Readily available in a wide variety of configurations, 3-
equipment such as piece, end entry and top entry, these valves range from commodity type valves to high
valve, inlet to
reactor and so on Advantages of ball valves include ease of operation, standard face-to-face dimensions, high
as shown in the flow capacity, high pressure/temperature capabilities and ability to handle severe service
PID. The purpose is chemicals. The quarter turn operation is desirable to most operators and fairly easy to
maintenance of
each equipment. The face-to-face dimensions comply with ASME, making the ball valve easy to retrofit and
For emergency shut replace in line with most other ball valves and plug valves. Also compliant with ASME is the
down and so on. 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
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
The ability to provide fire safe protection and handle severe service chemicals are two of the
Source: http://www.engvalves.com
Relief -installed at A spring operated valve is selected because rupture disk type will cause losing of the entire
valve discharge point of content. Propylene, benzene and cumemne is an expensive. Besides, it may allow air to enter
every pump to the process, leading to a possible pump damage, fire or explosion. Propylene, benzene and
prevent pressure cumemne is highly flammable. Relief valve is selected because of this relief is in a liquid service
-installed at jacket
-installed on top of
the reactor to
prevent pressure
build up
Line : L-1
Less Flow - Partial blockage - Less feed supply to the - Check maintenance procedure and
of pipeline reactor schedule for valve, pipeline,
- Leaking of - Incomplete reaction in controller and pump
pipeline Reactor R-1 - Install a back-up control valve or
- Control valve 1 - The ratio of propylene to a by-pass across manual valve
fails to respond benzene is not at the right - Install a pump in parallel to the
- Partial failure of ratio existing pump
controller - Install a strainer in the pipeline
- Partial failure of - Install a level indicator on the
pump reactor
- Install a flow indicator on the
pipeline
- Install a low-level alarm on the
reactor to alert the operator
- Check the emergency shutdown
system
More Flow - Failure of - More feed supply to the - Check maintenance procedure and
control valve 1 reactor schedule for valve and controller
- Failure of the - Incomplete reaction in - Install a back-up control valve or
controller Reactor R-1 a by-pass across manual valve
- The ratio of propylene to - Install a level indicator on the
benzene is not at the right reactor
ratio - Install a flow indicator on the
- Flooding of the reactor pipelinE
- Install a high-level alarm on the
reactor to alert the operator
- Check the emergency shutdown
system
Reverse Flow - Failure of - Possible back flow - Check maintenance procedure and
pump schedule for pump
Line : L-2
Line : L-3
Line : L-4
Less Pressure - Failure of the hot - Less steam supply to - Check maintenance procedure and schedule
water tank.Control the reactor for hot water tank, control valve and controller.
valve fails to open - Install backup steam generator
- Failure of the - Install a pressure indicator on the pipeline
controller - Check the emergency shutdown system
- Install a back-up control valve or a by-pass
across manual valve
More Temperature - Failure of the hot - High temperature in the - Check maintenance procedure and schedule
water tank. reactor. for hot water tank.Install backup steam
generator
- Install a temperature indicator on the pipeline
- Check the emergency shutdown system
- Install a high temperature alarm on the reactor
Less Temperature - Failure of the hot - Low temperature in the - Check maintenance procedure and schedule
water tank. reactor. for hot water tank.Install backup steam
generator
- Install a temperature indicator on the pipeline
- Check the emergency shutdown system
- Install a low temperature alarm on the reactor
As well Hot water in - Leak in heating - Dilution of contents - Check maintenance procedure and schedule
as reactor coils, pressure in - Product ruined
reactor is lower - Possible contamination
than pressure in of product
coil
As well Storage - Leak in coils with - Product lost through - Check maintenance procedure and schedule
as product in reactor pressure is coils - Install upstream check valve in hot water
coils greater than coils - Loss of product yield source
pressure - Reduction in heating
function
Reverse Reverse - Back flow due to - Improper heating - Install check valve in hot water source
heating flow back pressure
Line : L-5
Intention: To remove the cool water from the jacket in the reactor and recycle back to the hot water tank
Guide Deviation Possible cause Possible consequences Action recommended
word
No Flow - Blockage of - Cool water cannot be removed and - Check maintenance procedure and
pipeline accumulated in the jacket schedule for pipeline, valve.
- 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
Less Flow - Partial blockage - Cool water hardly be removed and - Check maintenance procedure and
of pipeline accumulated in the jacket schedule for pipeline and steam trap.
- Pressure in the jacket increases - Install a by-pass manual valve across
- Blasting of the jacket the steam trap
- Back flow of the cool water and cause
damage to the control valve
- Low temperature in the 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
27B Less Flow - Partially failure of pump - Insufficient feed to separator - Check maintenance
P303 - Incomplete separation procedure and schedule for
- Control valves CV307 fails - Temperature and pressure pump
to respond increase in separator - Install alarm system for
- Possible of explosion level and temperature
monitor
- Install relief/bypass system
27C More Flow - Overflow in line L22 - Overfeed to the distillation - Select valve to fail close
- Control valves CV307 fails column - Install high temperature
to respond - Incomplete separation and pressure alarm
- Pressure in line L27 increases - Install high flow alarm
- Pressure in distillation column - Fit high-level alarm with
increases automatic pump shut-
- Possible explosion down
- Fit second valve
- Install a bypass valve
27D Reverse Flow - Failure of pump P303 - Back flow of mixture into - Install non-return valve
- Reactor pressure higher distillation column
than delivery
Line : L28
Intention: To transfer the bottom product from cumene Column (C302) to the steam reboiler for burning purpose.
Item Guide Deviation Possible cause Possible consequences Action required
No Word
28A No Flow - Failure in CV308 and - No heat supply in distillation - Install backup control valve
CV309 column - Place controller on critical
- Failure in temperature - Incomplete separation instrument list
recorder and controller - Transfer of the bottom heavy - Maintenance of the control
product could not be done and valve CV308 and CV309
will caused higher mixture need to be done
concentration at cumene
Column
28B Less Flow - Failure in control valve - Incomplete separation - Install backup control valve
CV308 and CV309 - Less bottom product was - Place controller on critical
unable to transfer back to instrument list
column which cause inefficient - Maintenance of the CV308
28F Less Temperature - Failurein boiler - Incomplete separation - Check maintenance and
- Failure in control valve schedule for boiler
CV308 and CV309
28G More Pressure - Controller failure to open - Rupture of C302 - Place controller on critical
valve CV308 and CV309 - Runaway reaction instrument list
- Install relief system
- Install high pressure alarm
28H Reverse Flow - Failure of pump P304 - back flow of the bottom - Install non-return valve
product into cumene Column
Line : L29
Intention: to transfer heavies from distillation column (separator) to heavies collector tank
Item Guide Deviation Possible cause Possible consequences Action required
No Word
29A No Flow - Failure in pump P304 - No flow to heavies collector tank - Check maintenance and
- Control valve fails to - Rupture in distillation column schedule for pump
close - Transfer of the acetone product - Install back-up control valve
- Malfunction in could not be done and will - Select valve to fail open
distillation column caused higher mixture - Place controller on critical
concentration at C302 instrument list
29B Less Flow - Partially failure of - Slow process flow - Install bypass
pumpP304 - Heavies will flow into line L29 - Check maintenance and
- Control valve partially - Less phenol product was unable schedule for pump
open to transfer to the tank which - Install back-up control valve
- Controller fail and causes inefficient separation. - Select valve to fail open
valve fail to respond - Increase of pressure at C302 - Place controller on critical
- Failure of separation process instrument list
29C More Flow - Controller fail to open - Heavies storage tank - Place controller on critical
valve CV310 and - Flood instrument list.
CV311 - Incomplete separated phenol
product was to transfer to the
tank which causes inefficient
separation.
- Increase of pressure at C302
29D Reverse Flow - Failure in pump P304 - Back flow of heavies into - Install non-return valve
- Reactor pressure distillation column
higher than delivery
29E Less Pressure - Partial open valve - Low gas transfer to Fuel gas - Ensure sufficient digestion
CV309 centre occur
- Maintenance on pump, pipe
line and valve
29F More Pressure - Controller fail to open - Rupture of Heavies storage tank - Place controller on critical
valve 310 - Runaway reaction instrument list
- Install relief system
Line : L30
Intention: To transfer the overhead product from cumene Column (C302) to the fuel gas system and reflux stream.
Item Guide Deviation Possible cause Possible consequences Action required
No Word
30A No Flow - Failure in pump P305 - No flow to acetone product - Check maintenance and
- Failure of control column receiver schedule for pump
valve CV 313 - Overhead product was unable to - Install flow indicator at a feed
- Failure in distillation transfer back to column which line
column cause inefficient separation due
to poor reflux of the separation.
- Caused the pressure at cumene
Column to increase
- Failure of separation process
30B Less Flow - Partially failure of - Insufficient flow to acetone - Install bypass
pump P305 product column receiver - Check maintenance and
30C More Flow - Controller fail to open - cumene column receiver flood - Place controller on critical
valve CV313 - Too much overhead product was instrument list.
transferred back to column which - Install level control indicator
cause inefficient separation due
to over reflux of the separation.
- Caused the pressure at cumene
Column to increase
- Failure of separation process
- Increase of pressure along the
pipe will cause explosion.
30D Reverse Flow - Failure inpump P305 - Back flow of Acetone product - Install non-return valve
- Acetone product column condenser
column receiver flood - Flow of mixture back to cumene
pressure higher than Column
delivery
30E More Temperature - Temperature control - Pressure in line L30 increases - Maintenance of the Pump
in distillation column - Possible rupture of line L30 P305 need to be done
failed control - Install high temperature alarm
30F Less Pressure - Partial open valve - Low gas transfer to Fuel gas - Ensure sufficient digestion
CV313 centre occur
- Maintenance on pump, pipe
line and valve
30G More Pressure - Controller fail to open - Rupture of cumene column - Place controller on critical
controller valve receiver instrument list
CV313 - Runaway reaction - Install relief system
- Install high pressure alarm
30H More Temperature - Malfunctioning of - Increase temperature in cumene - Install High temperature alarm
Line : L 31
31D Reverse Flow - Failure in Pump P306 - Back flow of acetone into - Install non-return valve
- Reactor pressure distillation column
higher than delivery
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.
Fire and explosions are the dominant hazards in many industry sectors,
including cumene plant. Accident fires and explosions generally occur when
for determining their cause and assessing life or property loss and for
view points.
One important tool available for the efficient management of fire and
Fire and Explosion Risk Analysis can be carried out at various levels of
particular study can be tailored to the requirements from the main features
outlined as follows:
The major distinction between fires and explosions is the rate of energy
rapidly, typically on the order of microseconds. Fires can also result from
designs.
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
wave.
wind. A shock wave or shock front results if the pressure front has an
materials, such as TNT, but it can also occur from the sudden rupture of a
pressure vessel. The maximum pressure over am- bient pressure is called
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
necessary levels, burning will occur. This means a fire will not occur if:
(3) The ignition source is not energetic enough to initiate the fire.
Anything that can burn is potential fuel for a fire or, in some cases, an
Spirits;
Wood;
Diesel;
A source of ignition is anything that has the potential to get hot enough to
distribution systems;
distribution systems;
surfaces;
Causes Percentages
Smoking 5.7
Friction 5.4
Auto-ignition 3.7
Other 0.7
The main source of oxygen for a fire or explosion is in the general body of air.
storeroom or within pipe work, it is safe to assume that it will always have a
ready supply of oxygen as the mine’s ventilation system will continue to draw
This section covers the first step of a field-level assessment of fire and
The OHS Code in some jurisdictions states that assessments must be written
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.
Points to Remember
1. Anytime all three sides of the fire triangle can co-exist, there is real
2. There are critical risk factors that increase the probability of a fire and
explosion significantly.
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
for the fire and explosion hazard assessment. At a minimum, those identifying
fuel hazards should consider the questions below taking into account the list
operations?
present?
based on?
H. If fuels/hydrocarbons are present, what form are they in? Can they
change? How?
Uncontrolled Releases
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
It is recommended that the steps outlined below be taken before any work
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
questions below taking into account the list of oxygen sources in the
atmosphere?
generated nitrogen?
Step 3: Consider the oxygen-air hazards identified in the fire and explosion
Hazards
It is recommended that the steps outlined below be taken before any work
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).
A. Have all obvious sources such as open flames, sparks, heat sources
been identified?
C. Have all classified areas been identified, as per the Canadian Electrical
requirements?
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.
movements?
may not have enough energy to ignite a dry gas mixture because of
Triangle
The fire triangle in FIGURE 7 shows the three critical components required for
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:
2. There is a wide range of oil and gas operations with an equally wide
closed system.
effect), and/or sudden decompression, are not well understood and are
A fire triangle with expanded parameter lists is therefore provided. 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
Upper and Lower Explosive Limits: The mixture must be within the
(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
The critical risk factors can significantly affect the MIE, frequently
ignition source must also be considered. The ignition source must have
size, wall material, flow velocity and turbulence, and other physical
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
This graph illustrates the impact of the various risk factors on a flammable
2. The Probability of ignition of a mixture may not be zero even below the
4. The introduction of the critical risk factors can significantly expand the
band.
explosive vapors and explosive dusts. However, The most dangerous and
ruptures),
2. Dispersion of the vapor throughout the plant site while mixing with
air
In all chemical plant, the equipment most likely to caught fire and explosion
Piping 20
Vessel 20
Tankage 12
Pump 6
Heater 4
Heat exchanger 4
Compressor 2
Other 32
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
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
explosion to occur too. Continuous of the reactor will cause the reactor
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
The cause of pressure build up and temperature rise was stated in the
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
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
Plant
For the Cumene processing plant, the major flammable inventories are
1. Propylene
2. Benzene
3. Di-isoproply benzene
4. Cumene
5. Propane
thechemical formula C3H6. It has one double bond, and is the second simplest
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).
Propene has the same empirical formula as cyclopropane but their atoms are
Flammable properties:
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.
Flammable properties:
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.
Flammable properties:
Flammable liquid and vapor. Vapor may cause flash fire. Vapors may
ignition and flash back. Runoff to sewer may create fire or explosion hazard.
that has a boiling point of 152 °C. Nearly all the cumene that is produced as a
Flammable properties:
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
Flammable properties:
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.
lives lost, injuries, damage to property and the environment, and to business
in the projection of debris over a wide area. This debris, or missiles, can
equipment.
explosion in one part of the plant projects debris throughout the plant.
missile damage).
The objective of fire and explosion control measures is to avoid any fire
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:
materials such as paper documents ,it should still minimise the potential
ground;
mineral oils;
removed regularly;
alternatives;
below ground.
bitumen-filled couplers;
combustion engines;
motors etc;
fixed objects;
place;
Where diesel vehicles are used, separating electric cables, fuel and
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
ignition risks;
systems;
cleaning;
intervals;
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,
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
analysis (or for having one done by qualified outside persons) prior to the
aware of and support the plant dust and ignition control programs. Their
training should include identifying how they can encourage the reporting of
9.1 Introduction
into the atmosphere from water and dry soil. Cumene is expected to adsorb
soil.
propanol, in both humans and animals. This alcohol and its conjugates are readily
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
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,
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
was applied. Guidance values for the general population of 0.4 mg/m3 and 0.09
mg/m3 were derived for inhalation exposure, based on alternative NOAELs derived
from the same subchronic inhalation study; again, the NOAELs were adjusted to a
because long-term carcinogenicity studies with cumene have not been performed.
(biomagnification).
For sampling and measurement of cumene in air, Method 1501 of the US National
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 0.05µg/litre, and the applicable concentration range for
this method is approximately 0.1-200 µg/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,
weight for soil/sediment samples,0.5 mg/kg wet weight for wastes, and 5 µg/litre for
groundwater.
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
hydrocarbon fuels. Crude oils typically contain approximately 0.1 wt% of cumene,
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%.
Table 9.1 Western European cumene production levels (in tonnes) for the
producer countries.
(in tonnes)
Finland 70 000
emissions from manufacturing and processing plants, and emissions during its
transport (HSDB, 2004). As cumene occurs in crude oil and fuels, the transport,
cumene (HSDB, 2004). It was estimated that the releases of cumene as a result of
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).
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).
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
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
(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
100 (Derwent & Jenkin, 1990). POCP values represent the ability of a substance to
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
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
salt water, Price et al. (1974) observed 70% degradation in fresh water but only
isolated from Atlantic Ocean sediments. On the other hand, cumene was found to be
(1989), who noted that cumene produced only about 2% of theoretical gas
In soil, it appears that cumene might biodegrade fairly rapidly under aerobic
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)
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.
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
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).
chemical plants (1581 µg/litre, Botta et al., 1984; 360 µg/litre, Teply & Dressler,
1980; 11 µg/litre, Pellizzari et al., 1979), around outboard motor operations (700
µg/litre, Montz et al., 1982), near coal gasification facilities (up to 54 µg/litre,
Steurmer et al., 1982), and around petroleum plants and petroleum refineries (5
µg/litre, quantification method not clear; Snider & Manning, 1982). Cumene was
detected in 8 of 135 samples of surface water (detection limit 0.03 µg/litre with gas
µg/litre in several locations near a potential emission source in the 1986 monitoring
levels in sediments and biota in Puget Sound, Washington, USA, ranged from 0.02 to
19 µg/g, with a mean concentration of 2.3 µg/g (Brown et al., 1979). A cumene
level of 140 µg/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
cumene to be about 14.7 µg/m3 (3 ppb) in urban settings and as high as 2.5 µg/m3
(0.5 ppb) in rural settings. Samples taken in Los Angeles, California, in 1966
averaged 14.7µg/m3 (3 ppb) (Lonneman et al., 1968), and samples taken in Houston,
Texas, in 1973-1974 averaged 12.15 µg/m3 (2.48 ppb) (Lonneman et al., 1979). The
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 µg/m3 (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 µg/m3 [<0.01 ppb]), two attempts were positive: Seila (1979)
reported mean levels of 2.5 µg/m3 (0.5 ppb) in samples taken in a rural area near
Houston, Texas, in 1978, and Arnts & Meeks (1980, 1981) reported 0.25 µg/m3
(0.05 ppb) in samples taken near campfires in the Great Smokey Mountains, USA, in
1978.
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 µg/m3 (1.7 ppb) in the urban atmosphere
Ambient air concentrations for the Netherlands in 1980 were reported to average
0.5-1.0 µg/m3 (0.1-0.2 ppb), with maxima ranging up to 34.8 µg/m3 (7.1 ppb)
(Guicherit & Schulting, 1985). An annual average of 1.6 µg/m3 (0.3 ppb) (maximum
3.9 µg/m3 [0.8 ppb]) was reported from the Grenoble area in France in 1987 (Foster
et al., 1991).
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).
samples collected (single breath; range 1-81 µg/m3 [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/m3 (<0.02 ppm) through the work shift. These authors
analysed for but were unable to detect any significant differences in cumene
respiration from each of eight male volunteers (three smokers) were analysed for
the available literature. Coleman et al. (1984) detected cumene in Cincinnati, Ohio,
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 µg/litre
detection limit reported by Westrick et al. (1984), who found no cumene in 945 US
One industrial hygiene survey (US EPA, 1988) reported that approximately
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/m3 (4-30 ppm), 4 in the range of
15-20 mg/m3 (3-4 ppm), and 25 in the range of 5-10 mg/m3 (1-2 ppm), with the
exposure may result from contact with refined petroleum products and ingestion of
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;
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/m3 [49, 98, or 147 ppm]) for 8 h every 10 days. Exhaled breath
samples (10 cm3) 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
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
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
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
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.
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/m3 (100 ppm) to 6.6 h
at 5880 mg/m3 (1200 ppm). The half-life of cumene in the blood in gavage studies
within hepatic and extrahepatic tissues, including lung (Sato & Nakajima, 1987), with
excreted in urine of rats and rabbits include 2-phenyl-2-propanol and its glucuronide
metabolite, possibly the dicarboxylic acid that would result from complete oxidation
Senczuk & Litewka (1976) also conducted excretion studies with human
volunteers exposed to cumene vapours (240, 480, or 720 mg/m3 [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
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/m3 [1200 ppm] for 6 h).
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).
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
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
men and women having no occupational exposure to the chemical (Conkle et al.
Cumene was detected in the urine, blood, and alveolar air of individuals
2001). Ten healthy male and female human volunteers were exposed under
(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
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
blood cumene concentrations, Brugnone et al. (cited in ECB, 2001) reported alveolar
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
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).
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
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).
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
generally for exposures lasting a few days to no greater than one month (Eaton and
Klaasson, 1996).
(Experimental Animals)
Ppm(mg/m3) Period
Systemic:
RD50
(50% reduction in
respiratory rate)
Depressed respiratory
frequency
Neurological:
NOAEL 100 (490) 6 hours Rat
CNS Depression
(behavioural function)
(behavioural function)
(behavioural function)
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,
acutely exposed via inhalation to cumene (also pulmonary edema and hemorrhaging)
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
motor impairment and narcosis was observed in rats exposed to 7,275 mg/m3
Groups of 10 rats were exposed (nose-only) for 6 hours to a dose of cumene vapour
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
were reported 1 hour post-exposure for rats exposed to the highest dose only.
decreased response to toe pinch was reported six hours post-exposure, but only in
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.
days/week, over a 4 week period were observed for neurobehavioural effects ( i.e.,
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
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
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
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
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
Table 9.3 lists the NOAELs and LOAELs reported in the literature from sub-chronic
Animals)
Concentration a
Period
ppm (mg/m3)
Systemic:
Neurological:
effects
effects
Reproductive/Developmental:
5d/wk Rat
effects
of gestation
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
effects on respiratory tract tissue or lung weights were reported in either study (US
EPA, 1997).
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;
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
(males) and kidneys (females) and clinical effects (WHO, 1999; ECB, 2001).
cumene/m3 (Cushman et al. cited in US EPA, 1997). The US EPA (1997) viewed the
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
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
LOAEL of 2,430 mg/m3 and a NOAEL of 490 mg/m3 for sub-chronic exposure to
cumene.
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
US EPA, 1997 or Darmer et al. cited in WHO, 1999). The highest exposure dose
reductions in body weight and food consumption, clinical signs of toxicity, lung
colouration, and increased liver weights. Gestation parameters affected at this dose
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
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
guinea pig, dog, and monkey) following continuous exposure for 90 days to cumene
1997; WHO, 1999; ECB, 2001). Parameters analysed included body weight,
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
cumene.
cumene/m3) reported respiratory effects in mice and rats, including 50% decrease
were reported in rats exposed for 6 hours to cumene vapours at 2,850 mg/m3.
hours to cumene at air concentrations ranging from 2,430 to 5,980 mg/m3 and in
39,200 mg/m3. In all cases, symptoms subsided following withdrawal from exposure;
cumene (a 1948 report by the Dow Chemical Company) reported “no toxic injury”
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
increases in adrenals and kidneys. The NOAEL for these effects was 490 mg/m3.
adverse effects were reported following continuous exposure for 90 days to cumene
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
Little is known about the direct effects of volatile organic compounds (VOCs) on
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
compounds on the photosynthesis of the algal species Chlorella vulgaris (strain 260,
Indiana Culture Collection) and Chlamydmonas angulosa (strain 680, Indiana Culture
Both strains were grown in Bolds Basal Media (pH 6.5) at 19°C, 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.
177 mmol/m3 for Chlorella vulgaris. Galassi et al. (1988) evaluated the effect of
As feedstock costs continue to increase and downstream demand remains flat, the
Production costs for cumene are expected to continue increasing. Global crude
increasing in the US due to the supply tightness and gasoline aklyation values.
to remain stable to slightly higher. This is not enough to support the increases in
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
Pennsylvania, this potential disconnected could lead to volatility in the cumene market.
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
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
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
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
Global cumene demand growth is attributed in year 2011, to a large extent, to 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.
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
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
is used, cumene contracts will vary throughout the month. Spot RGP prices were at
cents/lb in the past four weeks. Moreover, in the past two months the contract price
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
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
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
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 don’t have room to crank up their operating rates until Asian
demand comes back,” a phenol buyer said. “They certainly can’t increase the rates
Cumene supply is snug, but could tighten considerably after the expected
in June. Sources said supply would be tight, but not constrained, as most phenol
However, if operating rates increase to service the Asian market, that added
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.
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.
Table 10.1 shows the details that are needed to build a phenol plant.
http://www.icispricing.com): $ 1210/tonne
http://www.icispricing.com): $ 910/tonne
http://www.icispricing.com): $ 1212.54/tonne
=
$1215.54
×
RM3.04
×
1,015,050 tonne ≈RM3,750,855.00/year
tonne $1 year
≈RM3.76 billion/year
http://themoneyconverter.com/USD/M
YR.aspx)
4. Plant Specifications:
Efficiency = 90 %
= 20 acres ≈ 80,937 m2
10.2.3 Investment
Recent prices paid for similar equipment should be used to estimate the cost of the
made by sizing and costing individual pieces of equipment. (Refer to Appendix for
C1
= C2 (Q1/Q2)0.6
= 26.6 million(3030/400)0.6
= RM70.49million
Thus, Present cost of Plant = (original cost) × (present cost index)/(past cost index)
= RM22 million.
Table 10.2: Typical factors for estimation of total physical plant cost.
Table 10.3: Typical factors for estimation of project fixed capital cost
Salary Per
No. Job No. Pay/Month(RM)
Person
Total - 61 181,600
Considering the inflation rate of 3% per annum, the current fixed capital cost for
Fixed Capital
2012
=PCE(3.4) (Fluids)
≈ RM107 million
Working Capital
Fixed Capital
Purchased
From our plant specifications, we are assuming this plant operates 8040hours/year.
Fixed Cost
Labour
Costs
Variable Cost
material tonne/year
Propylene
5,105,100/year
30,145,500/year
Cost ≈ RM337
million
Production Cost
Cost
Cost Expenses
Production rate)
(For cumene)
APAT(AGP x 0.74)
1400
1200
Cumulative Cash Flow
1000
800
600
400
200
0
0 5 10 15 20
-200
Time /years
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
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
For Year 4:
For Year 9:
flow)
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
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%.
(5×AGP)+[(t−5)×APAT]−IC
= × 100%
t×IC
= 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.
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.
CONTRACT PRICES
Market sources expect to see prices weaken in line with those for feedstocks and
cumene’s primary end-use markets, phenol and acetone but the US cumene contract
Both phenol and acetone prices were experiencing some severe downward
pressure because of weak demand and lengthening supplies but both held steady
The US barge acetone contract price for October fell 15 cents/lb ($331/tonne,
US phenol prices were feeling downward pressure from lower benzene values
Market sources said US cumene values were expected to drop to around 46-48
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,
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
Currently, there are more than 90% of the world’s 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
PROPYLENE
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
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.
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
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.
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 2011–2015 (with most capacity
coming onstream in 2013) to supply its phenol/acetone plants that are slated to come
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
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
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
This freely negotiated environment allows prices to rise with higher demand
and limited supply in classic economics fashion. However, the North American and
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
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
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
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
Mixed
Benzene
Xylenes
Ethylbenzene Paraxylene
(55%) (70%)
Ortho Xylene
Cumene (17%)
(12%)
Cyclohexane
Solvents (14%)
(14%)
Remaining
• Alkylbenzene 3%
• Nitrobenzene 6%
• Others 5%
A feedstock requires
1. Rapid demand growth in Asia
This is perhaps one of the most important differences between the world of olefins
are liquids and are much easier and less expensive to transport than light feedstocks
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
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
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
paraffins) will grow slower at just over 2 percent per year and high N+A naphtha
The rapid increase in ethane and LPG use in the Middle East causing the slow
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
Basically all cumene is used to produce phenol and acetone via the cumene
time with propylene. The use of traditional Friedel-Craft type of alkylation catalysts is
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 acetone’s growth is also
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.
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
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.
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.
Contents
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
10.1.2 Market Survey In Year 2011 (Price Report) ....................................... 372
10.1.3 Market Survey In Year 2012 (Price Report) ....................................... 373
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
sufficiently high to ensure only liquid - phase reaction. To limit the formation of
which in turn implies large benzene recycle and considerable energy consumption.
The energy spent for benzene recycling can be reduced considerably by heat
this raises a number of problems. The reaction rate is considerably reduced with
catalyst is available. This should ensure much higher activity and better selectivity
compared to a liquid - phase process. If these conditions are fulfilled the catalytic
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
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
methods must be made, and the cost of production must decrease, for these
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 km³) of oil per year, and the top oil consumers largely consist of
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
source powering the vast majority of vehicles and as the base of many industrial
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,
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
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
increased risk of corrosion and equipment failures during the production and refining
of heavy crude oil. The most damaging impurities are inorganic salts, organic
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
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
To make matters worse, many of the compounds are unstable during refining
operations and they break into smaller components or combine with other
on alumina was used as the catalyst. Since the mid-1990s, commercial production
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
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
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
reactions, UOP began searching for a new cumene catalyst that would overcome the
limitations of SPA.
UOP’s 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
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
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
the form of both improved catalysts and improved processes. This trend is expected
same catalyst (eg, QZ-2000) is specified for both the alkylation and transalkylation
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%.
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
solution for using the reaction heat inside the process and and/or making it available
A process and instrumentation diagram was drawn for the reactor and
cumene column in the cumene plant. Process and Instrumentation diagrams (P&IDs)
P&IDs for automated analysis, in support of retrofitting, for maintenance, for as-
HAZOP analysis was done on the reactor and cumene column. HAZOP is a
measures.
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
consequences of fires and explosions in pilot plants and plant environments are
even greater.
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
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.
Other effluents will need chemical treatment. The oxygen concentration on water
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.
and general use maybe generated on site, but will more usually be purchased from
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
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
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.
hydrocarbon fuels. Crude oils typically contain approximately 0.1 wt% of 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;
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
1987). Thus, reaction with ozone and direct photolysis are not expected to be
hydroxyl radicals appears to be the primary degradation pathway (t½ l–2 days)
(Lloyd et al., 1976; Ravishankara et al., 1978). Small amounts of cumene may be
value of 35 relative to ethylene at 100 (Derwent & Jenkin, 1990). POCP values
REFERENCES
Agency for Toxic Substances and Disease Registry (ATSDR). 2003. Minimal Risk
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).
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.
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.
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.
Eaton, D.L. and C.D. Klaassen, 1996. Principles of Toxicology. In: Klaasen, C.D.,
M.O. Amdur and J. Doull (eds). Casarett and Doull’s Toxicology. The Basic
Science of Poisons. McGraw-Hill Health Professions Division, Toronto, ON. 5th
ed. pp 13-33.
European Chemicals Bureau (ECB). 2001. European Union Risk Assessment Report:
Cumene, Volume 6. ECB Institute for Health and Consumer Protection.
Luxembourg. ISBN 92-894-0500-7, available at
http://ecb.jrc.it/Documents/Existing-
Chemicals/RISK_ASSESSMENT/REPORT/cumenereport007.pdf
Fire and explosion guidance. (n.d.). Retrieved May 25, 2013, from UK Offshore
Operators Association Limited: http://software-
web.com/download/Part%200.pdf
Fire And Explosion Hazard Management. (n.d.). Retrieved May 25, 2013, from
PistonWell:
http://www.pistonwell.com/irp/irp18_fire_and_explosion_hazard_managemen
t.pdf
Fire and Explosion. (n.d.). Retrieved May 25, 2013, from http://www.cbme.ust.hk:
http://www.cbme.ust.hk/safetycourse/download/06.1FiresandExplosions.pdf
Galassi, S., M. Mingazzini, L. Vigano, D. Cesareo, and M.L. Tosato. 1988. Approaches
to Modeling Toxic Responses of Aquatic Organisms to Aromatic Hydrocarbons.
Ecotoxicol.Environ.Saf. 16(2):158-169.
Gary A. Peterson and Robert J. Schmidt; The UOP Q-Max Cumene Process, in
Meyer ’ s Handbook of Petroleum Refining Processes , McGraw - Hill, New
York, USA , 2nd edn , 1997
Hazardous Substances Data Bank (HSDB). 2004. Hazardous Substances Data Bank.
Toxicology and Environmental Health Information Program, National Library
of Medicine, Bethesda, MD, available on-line at
http://toxnet.nlm.nih.gov/cgibin/ sis/htmlgen?HSDB.
Hutchinson, T.C., J.A. Hellebust, D. Tam, D. Mackay, R.A. Mascarenhas, and W.Y.
Shiu. 1980. The Correlation of the Toxicity to Algae of Hydrocarbons and
Halogenated Hydrocarbons with Their Physical-Chemical Properties,
Environ.Sci.Res. 16:577-586.
Jeanneret, J. J., D. Greer, P. Ho, J. McGeehee, and H. Shakir: “The Q-Max Process:
Setting the Pace
Levin, J.O. and R. Lindahl. 1994. Diffusive Air Sampling of Reactive Compounds – A
Review. Analyst 119: 79-83.
Louisiana Administrative Code (LAC). Title 33 Environmental Quality, Part III Air,
Chapter 51. Comprehensive Toxic Air Pollutant Emission Control Program.
Louisiana Department of Environmental Quality. Baton Rouge, LA.
Lu, C.J., J. Whiting, R.D. Sacks and E.T. Zellers. 2003. Portable Gas Chromatograph
with Tunable Retention and Sensor Array Detection for Determination of
Complex Vapor Mixtures. Anal. Chem. 75: 1400-1409.
Major Hazards : Fires, Explosions and Toxic Release. (n.d.). Retrieved May 25, 2013,
from UTM: http://ocw.utm.my/file.php/98/N8_Fires.pdf
Michigan Administrative Code (MAC). Air Pollution Control Rules. Part 2 Air Use
Approval, R 336.1201 - 336.1299. Air Quality Division, Department of
Environmental Quality. Lansing, MI.
Mukund, R., T.J. Kelly, S.M. Gordan, M.J. Hays and W.A. McClenny. 1995. Status of
Ambient Air Measurement Methods for Hazardous Air Pollutants.
Environmental Science & Technology 29 (4): 183-187.
National Institute for Occupational Safety and Health (NIOSH). 2003. NIOSH Pocket
Guide to Chemical Hazards (NPG) Online. NIOSH, Department of Health and
Human Services, Centers for Disease Control and Prevention, Atlanta, GA.
National Pollutant Release Inventory (NPRI). 2004. 2001 NPRI National Database
(2001 complete database Excel format),
http://www.ec.gc.ca/pdb/npri/npri_preinfo_e.cfm#dbase.
New Hampshire Administrative Rule. Chapter Env-A 1400. Regulated Toxic Air
Pollutants. New Hampshire Department of Environmental Services. Concord,
NH.
New Jersey Administrative Code (NJAC). Title 7, Chapter 27, Subchapter 8. Permits
and Certificates for Minor Facilities (and Major Facilities without an Operating
Permit). New Jersey Department of Environmental Protection. Trenton, NJ.
New Zealand Ministry for the Environment and Ministry of Health (New Zealand).
2000. Proposals for Revised and New Ambient Air Quality Guidelines.
Discussion Document. Air Quality Technical Report No 16. Prepared by the
Ministry for the Environment and the Ministry of Health. December 2000. 79
pp.
NIOSH (National Institute for Occupational Safety and Health). 1994. NIOSH Manual
of Sampling and Analytical Methods – 4th Edition, Method 1501, Issue 2. US
Department of Health, Education, and Welfare, Public Health Service, Centers
for Disease Control, National Institute for Occupational Safety and Health,
Division of Physical Sciences and Engineering, Cincinnati, OH, 1994.
North Carolina Administrative Code (NCAC). North Carolina Air Quality Rules 15A
NCAC 2D.1100 – Air Pollution Control Requirements (Control of Toxic Air
Pollutants). North Carolina Department of Environment and Natural
Resources. Raleigh, NC.
North Carolina Administrative Code (NCAC). North Carolina Air Quality Rules 15A
NCAC 2Q.0700 – Air Quality Permit Procedures (Toxic Air Pollutant
Procedures). North Carolina Department of Environment and Natural
Resources. Raleigh, NC.
Occupational Safety and Health Administration (OSHA). 2003. TABLE Z-1 Limits for
Air Contaminants. - 1910.1000 TABLE Z-1. US Department of Labor, OSHA,
Washington, DC. Available at:
www.oshaslc.gov/pls/oshaweb/owadisp.show_document?p_table=STANDARD
S&p_id=9992 (accessed 5 December 2003).
Ohio Environmental Protection Agency (EPA). 2003. Review of New Sources of Toxic
Emissions. Air Toxics Unit, Division of Air Pollution Control, Ohio EPA.
Columbus, OH. 11 pp. Available at:
http://www.epa.state.oh.us/dapc/atu/atu.html (accessed 5 December 2003).
Ohio Environmental Protection Agency (Ohio EPA). 1994. Review of New Sources of
Air Toxic Emissions. Proposed for Public Comment. Division of Air Pollution
Control, Ohio EPA. Columbus, OH. January 1994. 31 pp.
Oklahoma Administrative Code (OAC). Title 252. Chapter 100. Air Pollution Control.
100:252- 41 - Control of Emission of Hazardous and Toxic Air Contaminants.
Oklahoma Department of Environmental Quality. Oklahoma City, OK.
Ontario Ministry of the Environment. 2001. Ontario Air Standards for Isopropyl
Benzene. Standards Development Branch, Ontario Ministry of the
Environment, Toronto, ON. March 2001. 55 pp.
OSHA (Occupational Safety and Health Administration). 2000. OSHA Sampling and
Analytical Methods, Organic Vapors Method 7. Organic Methods Evaluation
Branch, Occupational Safety and Health Administration, US Department of
Labor, OSHA Salt Lake Technical Center, Salt Lake City, UT. May 2000.
Peng, C.Y. and S. Batterman. 2000. Short Path Thermal Desorption for Volatile
Organic Compounds. J. Environ. Monit. 2: 313-324.
Plog, B.A., J. Niland, P.J. Quinlan. (eds.) 1996. Fundamentals of Industrial Hygiene
4th Ed. National Safety Council. Itasca, Il. pp1011.
Royal Society of Chemistry (RSC). 1999. Dictionary of Substances and Their Effects
Database. Royal Society of Chemistry, Cambridge, UK, on-line database,
accessed on January 14, 2004.
Sanchez, J.M. and R.D. Sacks. 2003. On-Line Multibed Sorption Trap and Injector for
the GC Analysis of Organic Vapors in Large-Volume Air Samples. Anal. Chem.
75: 978-985.
SKC Inc. 2004. SKC Passive Sampling Guide - Cumene. SKC Inc, Eighty Four, PA,
accessed January 2004. (available on-line at
http://www.skcinc.com/diffusive/LIST_C.asp).
Spicer , C.W., Gordon, S.M., Holdren, M.W., Kelly, T.J. and Mukund, R. 2002.
Hazardous Air Pollutants Handbook: Measurements, Properties, and Fate in
Ambient Air, Lewis Publishers, a CRC Press Company, Boca Raton, FL,
Texas Natural Resource Conservation Commission (TNRCC). 2003. Toxicology & Risk
Assessment (TARA) Section Effects Screening Levels. Available at:
http://www.tnrcc.state.tx.us/permitting/tox/index.html (accessed 5 December
2003).
The Netherlands National Institute of Public Health and the Environment (RIVM).
2001. Reevaluation of human-toxicological maximum permissible risk levels.
RIVN Report 11701 025. RIVN, Bilthoven, The Netherlands. March 2001. 297
pp.
Vermont Air Pollution Control Regulations. 2001. Appendix C - Rule 5-261 - Control
of Hazardous Air Contaminants, Vermont Air Pollution Control Regulations.
State of Vermont Agency of Natural Resources. Air Pollution Control Division.
Waterbury, VT. 29 November 2001. 187 pp.
Wallace , J.W. , Gimpel , H.E. ; The Dow - Kellogg Cumene Process, in Meyer ’ s
Handbook of Petroleum Refining Processes , McGraw - Hill, New York, USA ,
2nd edn , 1997
Washington Administrative Code (WAC). Chapter 173-460 WAC. Controls For New
Sources Of Toxic Air Pollutants. Washington State Department of Ecology.
Olympia, WA.
Wisconsin Administrative Code (WAC). Air Pollution Control Rules. Chapter NR 445.
Control of Hazardous Pollutants. Wisconsin Department of Natural Resources.
Madison WI
World Health Organization (WHO). 2000. Air Quality Guidelines for Europe, 2nd
Edition. WHO Regional Publications, European Series, No. 91. WHO Regional
Office for Europe, Copenhagen. 273 pp.