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1
Introduction
1.1
Chapter 1
Introduction
Percent range
Carbon
83 to 85%
Hydrogen
10 to 14%
Nitrogen
0.1 to 2%
Oxygen
0.05 to 1.5%
Sulfur
0.05 to 6.0%
Metals
< 0.1%
Four different types of hydrocarbon molecules appear in crude oil. The relative
percentage of each varies from oil to oil, determining the properties of oil.[3]
Composition by weight
Hydrocarbon
Average
Range
15 to 60%
Naphthenes
49%
30 to 60%
Aromatics
15%
3 to 30%
Asphaltics
6%
remainder
Chapter 1
1.3
Introduction
Crude oil is of three main classes named according to the nature of the residue left
when the more volatile components are removed by distillation.
1: Paraffin based crudes consist mainly of paraffin hydrocarbons and leave a distillation
residue of paraffin wax. They give good yields of high grade lubricating oils. These crudes
contain little or no asphaltic (naphthenic) matter.
2: Asphaltic based crudes are mainly hydrocarbons of the naphthenic series and contain little
or no paraffin mix. On distillation, they leave a residue of black, lustrous material of complex
character known as bitumen or asphalt. Asphaltic based crudes are dark, very viscous, and
difficult to separate mechanically from dirt and water and generally contain more sulfur than
paraffin based crudes.
3: Mixed based crudes contain substantial proportions of both paraffin wax and asphaltic
matter. Both paraffinic and naphthenic hydrocarbons are present over a wide range of
molecular weights together with some aromatic species. On distillation, a residue of mixed
paraffin wax and bitumen is left. The bulk of the crude oil at present produced is of this
mixed type. [4]
1.4
1.4.1
Hydrocarbons:
Chapter 1
Introduction
The lighter, straight chain paraffin molecules are found in gases, and paraffin
waxes. Examples of straight chain molecules are methane, ethane, propane and butane (gases
containing from 1-4 Carbon atoms), Pentane and Hexane (Liquids with 5-6 Carbon atoms).
The branched chain Paraffins are usually found in heavier fractions of crude oil and have
higher octane numbers than normal Paraffins.
1.4.1.2 Aromatics:
Aromatics are unsaturated ring type (cyclic) compounds which react readily
because they have carbon atoms that are deficient in hydrogen. All aromatics have at least
one benzene ring (a single ring compound characterized by three double bonds alternating
with three single bonds between six carbon atoms) as part of their molecular structure.
Naphthalenes are fused double ring aromatic compounds. The most complex aromatics, polynuclear (three or more fused aromatic rings), are found in heavier fractions of crude oil.
1.4.1.3 Naphthenes:
Naphthenes are saturated hydrocarbons grouping with the general formula CnH2n
arranged in the form of closed rings (cyclic) are found in all fractions of crude oil except the
very lightest. Single ring Naphthenes (mono-cycloparaffins) with 5 and 6 carbon atoms
predominate, with two-ring Naphthenes (Di-cycloparaffins) found in the heavier ends of
Naphtha.
1.4.2
Non-hydrocarbons
Non Hydrocarbons in crude oil may include all or the combinations of the following
types of substance; [5]
1.4.2.1 Sulfur compounds:
Sulfur may be present in crude oil as hydrogen sulfide (H2S), as compounds (e.g.,
mercaptans, sulfides, disulfides, thiophenes, etc.), or as elemental sulfur. Each crude oil has
different amounts and types of sulfur compounds but as a rule the proportion, stability and
complexity of the compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a
primary contributor to corrosion in refinery processing units. Other corrosive substances are
elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an
obnoxious odor.
1.4.2.1.1 Impacts:
Pyrophoric iron sulfide results from the corrosive action and sulfur compounds on
the iron and steel used in refinery process equipments, piping and tanks.
The combustion of petroleum products containing sulfur compounds produces undesirables
such as sulfuric acid and sulfur dioxide.
4
Chapter 1
Introduction
1.4.2.1.2 Treatment:
Catalytic hydro treating processes such as hydrodesulphurization remove sulfur
compounds from refinery products streams. Sweetening processes either remove the
obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of
mercaptans.
1.4.2.2 Oxygen Compounds
Oxygen compounds such as phenols, ketones and carboxylic acids occur in crude
oils in varying amounts.
1.4.2.3 Nitrogen Compounds
Nitrogen is found in lighter fractions of crude oil as basic compounds, and more
often in heavier fractions of crude oil as monobasic compounds that may also include trace
metals such as copper, vanadium and/or nickel. Nitrogen oxides can form in process furnaces.
The decomposition of nitrogen compounds in catalytic cracking and hydro cracking
processes forms ammonia and cyanides that can cause corrosion.
1.4.2.5 Salts
Crude oils often contain inorganic salts such as sodium chloride, magnesium
chloride and calcium chloride, in suspension or dissolved in entrained water (brine). These
salts must be removed or neutralized before processing to prevent catalyst poisoning,
equipment corrosion and fouling.
1.4.2.5.1 Impact:
Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen
chloride (HCl) and the subsequent formation of hydrochloric acid when crude is heated.
Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH4OH),
which causes fouling and corrosion.
5
Chapter 1
1.4.2.6
Introduction
Carbon Dioxide
Naphthenic Acids
Some crude oils contain naphthenic (organic) acids, which may become corrosive at
temperatures above 450 F when the acid value of the crude is above a certain level.
1.5
The first refineries used horizontal, elevated tanks to heat the crude oil and vaporize volatile
components. The hot vapor would rise, cool and condense in a batch operation. The process
was repeated at different temperatures to separate the various fractions. The technology was
simple, refineries was easy to set up and before long, refining capacity exceeded crude
supply. The need for improved product separation led to the use of fractionating column,
which allowed the different boiling point cuts to be separated out in a continuous process.
John D. Rockefeller sought to consolidate the US refining business and in 1870 he
established the Standard Oil Co. with his partners. By 1879, Standard Oil control 90 % of the
US refining capacity. Developments continued, but the first widely recognized continuous
distillation plants were those of M. J. Trumble (1912). [6]
The number of automobiles and the demand for gasoline greatly increased following the
advent of mass production. Distillation processes, however, could only produce a certain
amount of gasoline depending upon the composition of the crude oil and so scientist and
engineers searched for new ways to increase the yield and performance of gasoline. Thermal
cracking processes were first discovered in 1913, when heat and pressure was used to break
down, rearrange and combine hydrogen molecules.
The introduction of catalytic cracking and polymerization processes in the mid to late
1930s met the demand for higher octane gasoline. Eugene Haudry developed the first
commercial process of cracking in the presence of clay mineral catalysts which resulted in the
large hydrocarbon molecule break apart ; the product were converted to branched Paraffins,
Naphthenes and aromatics with desirable properties. Visbreaking, another form of thermal
cracking, was developed in the late 1930s to produce a more desirable and valuable product
slate. In the 1940s alkylation processes were developed to create high quality aviation fuels
for the war effects, which later were used extensively to produce gasoline blending stocks.
Chapter 1
1.6
Introduction
Refinery products
Volatile products
Liquefied gases and natural gasoline
1.6.2
Light oils
Gasoline, rocket and jet fuels, solvents, tractor fuels and kerosene
1.6.3
Distillates
Range oil, furnace distillates, diesel fuel and gas oil.
1.6.4
Lubricating oil
Motor, engine, machines, cylinder, spindle, gear, etc, oils
1.6.5
1.6.6
Residues
Fuel oil, coke, asphalt carbon black etc
1.6.7
Specialties
Medicinal products, hydrocarbons, chemicals, insecticides, etc
1.7
Gas Oil
Any oily liquid obtained in the fractional distillation of petroleum, boiling between
the kerosene lubricating oil fractions: used esp. as a diesel fuel and heating oil. Gas oil is a
heavier product than kerosene. It may be produced from atmospheric distillation units.
Atmospheric gas oil (AGO), with a boiling range of approximately190-225oC or from
vacuum distillation (VGO) having boiling point range of 299-500oC. Atmospheric gas oil has
relatively lower density and lower S content than VGO produced from same origin. The
aromatic content of gas oil ranges from about 48% for VGO. It is general rule that VGO
contain about three times as much as S as AGO.
Gas oils are used as heating oils, fuels for metallurgical other manufacturing purposes.
Gas oils containing crack products are unstable and produced more smoke and more deposit
than AGO.
Chapter 1
Introduction
Specific gravity of gas oil is usually falls within wide range of approximately 0.810.89. Substantial amounts of gas oils are used as feeds to catalytic cracking units and to steam
cracking for olefin production. Gas oils are used for ethylene production normally require a
pretreatment step to remove the sulpher compounds.
Desulphurization of heavier oil such as AGO or VGO and deasphalted oil, is widely
used in order to meet the environmental residue.
1.8
Hydrodesulphurization
1.8.1
Mercaptans,
Sulfides,
Disulfides,
Thiophenes (T),
Benzothiophenes (BT),
Dibenzothiophenes (DBT), and their alkyl and hydrogenated derivatives.
Chapter 1
Introduction
1.8.2
History
Chapter No.2
LITERATURE REVIEW
2.1
Hydrotreatment Process
Hydrotreatment has been part of refinery processing since the 1930s (Topsoe et al.,1996).
Typical Hydrotreatment reactions refer to the catalytic hydrodesulphurization (HDS),
hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodearomatization
(HDA) in presence of hydrogen. These reactions are typicallycarried out over a
sulfidedCoMo or NiMo catalyst at 350-450C and 35-250 atm of hydrogen partial
pressure.
A summary of the hydrotreating process conditions for different feed stocks are shown in
Table 2.1. [10]
Feedstock
Naphtha
Kerosene
Atmospheric gas oil
Vacuum gas oil
Atmospheric residue
Vacuum heavy gas oil
Vacuum residue
Temperature
(oC)
320
330
340
360
370-410
380-410
400-440
Hydrogen partial
pressure (atm)
10-20
20-30
25-40
50-90
80-130
90-140
100-150
LHSV
(h-1)
3-8
2-5
1.5-4
1-2
0.2-0.5
1-2
0.2-0.5
In the last two decades petroleum refining technology has significantly changed andthe
reactions of hydrotreatment, in particular, have risen to a level of economic
importance (Gates et al., 1979; Ma et al., 1994). Hydrotreaters now have a central
position in modern refineries as shown in Figure 2.1.
Figure 2.1 Schematic of typical hydrotreatment (HDT). (Adapted from Castaneda et al.,
1999)
10
Chapter 2
2.2
Literature Review
Hydrodesulphurization
Nearly all literature for HDS dynamic models (listed in Table 2.2) is based on validation with
pilot plant data. This approach does not transfer well to industrial applications for the
following reasons:
1. Dynamic models only run from approximately forty minutes to 3 months in length
2. Multiple variable disturbances and operator responses are not considered
3. Low conversion occurs since pilot plant reactor is 10-20 times shorter
Table 2.2: Summary on literature found and cited for modeling catalytic reactors [11]
Reference
Model
Steady
Dynamic
state
Catalyst
Deact.
Levenspiel et al
(1968)
Kodama et al (1980)
Tamm Et al (1981)
Baiker and
Bergougnan (1985)
Dhler and Rupp
(1987)
Chao et al. (1990)
Barto et al (1990)
Chao et al. (1991)
Barto et al (1991)
Miyauchi and deWind (1994)
Lucien et al (1993)
Froment et al (1994)
X
X
X
X
X
Residue
desulfurization
Industrial
Desulfurization,
metals deposition
Fixed Bed 1-d vs
2-d modeling
P/I
VGO-treatment
X
X
X
X
X
I/P
P
X
Trickle Bed
Fixed bed reactor
HDS
Pellet Dynamics
Residue
Hydrotreating
Shell HDS process
HDS, 1-d
heterogeneous
Four stages reactor
Kulkarni and
Dudukovic (1996)
Application
Fixed bed reactor
Experiment
P=Pilot
I= Industrial
Vacuum Residue
HDS
Gas and solid phase
fixed bed reactor
3-phase trickle bed
reactor
hydrogenation of
toluene
11
Chapter 2
Korsten and
Hoffmann (1996)
Literature Review
Recke and
Jrgensen (1997)
Iliuta et al. (1998)
X
X
HDS, 3-phase,
Trickle Bed
Catalytic oxidation
of hydrogen to form
water
Residence time
distribution
Lababidi et al.
(1998)
Juarez et al (1999)
Kokayeff (1999)
Ho (1999)
Oballa (1999)
Julcour et al (1999)
Matos and
Guirardello (2000)
X
X
P
P
Hu et al (2001)
HDS on Industrial
data
Chowdury et al
(2002)
Lababidi et al.
(2004)
Mederos et al (2006)
X
X
Desulfurization
X
X
P
P
Advanced control
HDS, Trickle Bed
All the dynamic models developed are run over such a short time, that the accuracy of any
catalyst deactivation factors, if included, cannot be ascertained. In addition, the robustness of
these models cannot be verified since the interaction of various variables (crude, temperature
and hydrogen changes) is not demonstrated. Finally, non-validated correlations have been
developed to factor in the incomplete catalyst wetting through contacting effectiveness that
creates lower sulfur conversion in pilot plants. As a result, there is little or no confidence in
scaling up a pilot plant validated dynamic model to industrial scale conditions. Any one of
these factors show that there is a need to create a VGO HDS dynamically based model that is
valid over an entire run length (at least 1.5 years).
There are a few papers (Table 3.2) that try to show compatibility with industrial data by
adding 1 or 2 commercial reactor data points from other literature to show how well the
model could be applied to industry. Any model can match up with one or two data points.
Also, they exhibit one of the three noted deficiencies when trying to extend applicability to
actual industrial conditions.
The literature review of dynamic modelling is still important for this body of work, since
there are definitely valuable findings from pilot-plant validated dynamic model development
12
Chapter 2
Literature Review
that can be used for creating a novel industrial validated dynamically based Vacuum gas-oil
hydro-treater model.
2.2.1 Thermodynamics
The HDS of sulfur compounds is exothermic and fundamentally irreversible under the
reaction conditions employed industrially (Gates et al., 1979; Speight, 1981; Vrinat,1983).
Actually, there is very little thermodynamics data available for sulfur compounds present in
high boiling fractions. Vrinat (1983) shows data for dibenzothiophene HDS. According to
these results the conversion of dibenzothiophene into biphenyl is favoredat
temperatures of industrial practice and is exothermic (Ho = -11 kcal/mol). Those
results also suggest that the HDS of higher molecular weight sulfur compounds (e.g.,
benzo naphtha thiophenes) are also favored.
Sulfur removal occurs along two parallel pathways, hydrogenolysis and hydrogenation
(Froment, 2004). Since hydrogenation of the rings of sulfur compounds is equilibriumlimited at industrial HDS temperatures, the pathways concerning previous
hydrogenation of the ring can be affected by thermodynamics (Girgis and Gates,
1991). Vrinat (1983) found that the equilibrium constant for hydrogenation of
thiophene into tetra hydrothiophene is less than unity at temperatures above 350C.
Thus, sulfur-removal pathways via hydrogenated sulfur intermediates may be inhibited at
low pressures and high temperatures because of the low equilibrium concentrations of
the latter species.
2.2.2 first-order Kinetics
The most important hydroprocessing application in a refinery is hydrodesulphurization
(HDS), which comprises reactions leading to removal of sulfur from petroleum
fractions by their conversion into hydrocarbon products and hydrogen sulfide (H2S).
The literature on hydrodesulphurization of oil fractions and sulfurcontaining model
compounds has been reviewed by Gates et al. (1979), Vrinat (1983), Vanrysselberghe
and Froment (2003) and Froment (2004) The kinetics for the decomposition of substituted
benzothiophene and dibenzothiophenes in complex mixtures has been published by Kabe
et al. (1992) in the study of hydrodesulphurization of a light oil on a CoMo/Al2O3
catalyst, and Ma et al. (1994) in the study on hydrodesulphurization in a diesel fuel, a gas
oil, and a vacuum gas oil, on CoMo/Al2O3
The numbering of the carbon atoms in benzothiophene and dibenzothiophene is as follows:
13
Chapter 2
Literature Review
Reactant
Structure
Thiophene (T)
1.38 x 10-3
Benzothiophene (BT)
8.11 x 10-4
Dibenzothiophene (DBT)
6.11 x 10-5
Benzo[b]naphtho-[2,3-d]
thiophene
1.61 x 10-4
7,8,9,10-Tetrahydrobenzo[b]naphtho-[2,3-d]
thiophene
7.78 x 10-4
14
Chapter 2
Literature Review
Structure
Dibenzothiophene (DBT)
6.11 x 10-5
2,8-dimethyldibenzothiophene
(2,8-DMDBT)
6.72 x 10-5
3,7-dimethyldibenzothiophene
(3,7-DMDBT)
3.53 x 10-5
4-methyldibenzothiophene
(4-MDBT)
6.64 x 10-6
4,6-dimethyldibenzothiophene
(4,6-DMDBT)
4.92 x 10-6
15
Chapter No 3
Process of hydrodesulphurization
3.1
Processing considerations
The operating conditions in the distillate hydrodesulphurization are dependent on the stock to
be charged as well as the desired desulphurization or quality improvement. Kerosene and
light gas oils are generally processed at mild severity and high throughput.
The principal variables affecting the required severity in the distillate desulphurizer are:
i.
ii.
iii.
iv.
i.
The important effect of hydrogen partial pressure is the minimization of coking reactions. If
hydrogen pressure is too low for the required duty at any position within the reaction system,
premature aging of the remaining portion of the catalyst will be encountered. The effect of
hydrogen partial pressure on desulphurization varies with feed boiling range. For a given feed
there exists a threshold level above with hydrogen pressure is beneficial to the desired
desulphurization reaction. Below this level desulphurization drops off rapidly as hydrogen
pressure is reduced.
ii.
Space velocity
iii.
Reaction temperature
Higher temperature increases the rate of desulphurization. The start-of -run temperature is set
by the design desulphurization level, space velocity and hydrogen partial pressure. Capability
to increase temperature as catalyst deactivates is built into the unit design. Temperature of
780 oF and above will result in excessive coking reaction and higher than normal catalyst
aging rates. Therefore units are designed to avoid use of such temperatures for any significant
part of the cycle life.
iv.
The feed boiling range has the greatest effect on the ultimate design of the unit. The reaction
rate constant in the kinetic relationships decreases rapidly with the increasing average boiling
16
Chapter 3
Process of hydrodesulphurization
point in the kerosene and light gas oil range but much more slowly in the heavy oil range.
This is attributed to the difficulty in removing sulphur from ripping present in the entire
heavy gas oil boiling range. [1]
3.2
Process description
Hydro processing has largely replaced acid base sweetening processes. Modern reactors
generally use sulfide CoMo4 catalyst. Careful control of operating conditions results in
conversion of mercaptans, alkyl sulfides and thiophenes to hydrogen sulfide without
significant Hydro cracking or hydrogenation of aromatics. Olefins, however, are converted to
paraffin. Hydrogen sulfide is scrubbed out of the gas stream with an alkaline or amine
absorbent and is eventually recovered as sulfuric acid, or with the Claus process, as elemental
sulfur.
Modified process is becoming popular for the heavier feed stocks. Its used for catalytic
reforming and hydro cracking feeds is widespread. A development effort has been under the
way for many years on residuum HDS. It is difficult task because of sulfur content, 2 to 5
wt% and the high level of, V and Ni which deposit in the catalyst pores, reducing catalyst
activity.
Table 3.1 Distillate feed stock for hydrodesulphurization
Petroleum feed stock
Light
Light gasoline
Naphtha (Reformer feed)
Kerosene (Jet fuel)
Gas oil (Diesel and heating oil)
Heavy
Residual oil (fuel oil)
Chapter 3
Process of hydrodesulphurization
18
Chapter 3
Process of hydrodesulphurization
removed. With feed stock low in metals, catalyst deactivation occurs primarily through coke
deposition and catalyst life without regeneration may be a year or more.
The catalyst may be regenerated when necessary, without removing it from the reactor, by
passing over it a mixture of steam and air to burn out the coke deposits. The trickle bed is
flexible and can be used for treating a variety of refinery streams.
Operating practice calls for gradually increasing the temperature of feed to the reactor to
compensate for coking of the catalyst. Periodically, the reactor is shut down and the
accumulated coke is burnt off as mentioned above. A catalyst charge may endure several of
these run-regeneration cycles and remain in the reactor for as long as 10 years. Catalyst life is
reduced sharply with heavier feeds, reflecting their higher metal content and propensity to
form coke.
Table 3.2 hydrodesulphurization operating conditions as function of feed stock
Processing conditioning
Temperature oC
Pressure range (atm)
LHSV ( vol., fed/vol.,
catalyst/hr)
H2 recycle rate (std.
ft3/bbls)
Catalyst life (years)
Heavy petroleum
(Feedstock)
340-425
55-170
2-10
0.2-1
300-2000
2000-10,000
10
-1
A possible alternative to trickle beds for residuum, bitumen and coal processing is a three
phase fluidized or emulating bed Reactor. Catalyst particles are held in suspension by the
upward velocity of the liquid reactants, through which hydrogen flows concurrently.
There are several advantages to this Reactor design:
I.
II.
III.
The deactivating catalyst can be removed and replaced continuously (as in catalytic
cracking).
Small catalyst particles can be used, and they are more effective than larger particles
because intra particles mass-transport interface is insignificant (particles with
dimensions less than few mm are avoided in fixed bed because the pressure drop is
unacceptably high), and
The fluidized bed Reactor contents are expected to be very well mixed, which
suggests that uniform temperatures can be maintained.
19
Chapter 3
3.3
Process of hydrodesulphurization
Hydrodesulphurization catalysis
Catalyst developed for hydrotreating includes cobalt and molybdenum oxides on alumina,
nickel oxide, nickel thiolybdate, tungsten and nickel sulphides, and vanadium (II) oxide. The
cobalt and molybdenum oxides on alumina catalysts are in most general use today because
they have proven to be highly selective at the same operating conditions, easy to regenerate
and resistant to poisons. They must be activated by converted the hydrogenation metals from
the oxides to the sulphide form.
Cobalt-molybdenum catalysts are selective for sulphur removal and nickel molybdenum
catalysts are selective for nitrogen removal although both catalysts have a higher
hydrogenation activity than Cobalt-molybdenum catalyst which results, at the same operating
conditions, in a greater saturation of aromatic rings. Simply stated if sulphur reduction is
primary objective, then a Cobalt-molybdenum catalyst will rescue the sulphur a given amount
at less severe operating conditions with low hydrogen consumption than nickel-molybdenum
catalyst. If nitrogen reduction or aromatic ring saturation is desired, nickel-molybdenum
catalyst is the preferred catalyst.
Catalysts commonly used for distillates are alumina-supported mixed oxide of Co and Mo
whose surfaces are usually sulphides before use. Industrial catalyst may contain as high as 10
to 20 percent Co and Mo. Molybdates predominates in the mixture and usually the Mo/Co
ratio is much greater than one. One widely used catalyst contains 3 weight% CoO and 12
weight% MoO. A number of related compositions have also been employed as HDS
catalysts, for example, Ni and W instead of Co and Mo. In contrast to the supported Pt and Pt
alloy catalyst used in reforming, HDS catalyst have hydrogenation activity in the presence of
high concentration of sulphur compounds; their activities, however, are characteristically less
than Pt by several orders of magnitude.
Catalyst structure and details of the desulphurization mechanism are still far from understood.
Sulphiding clearly converts the surface layers to the metal sulphide (MoO3+MoS2:
CoO+Co9S8). The sulphide ion S-2 is much larger than O-2 so Sulphiding disrupts the surface
structure. Since MoS2 is much more active than Co9S8, but quite a bit less active then mixture
of sulphides, and intercalculation explanation for the activity had been proposed. Al2O3 is
used exclusively as a support apparently because the surface structure inhibits then formation
CoMoO4. On sulphiding, CoMoO4 forms a sulphide which is catalytically inactive. Schultz
and Gates have purposed a radix mechanism for the sulphides catalysts involving electron
transfer from MO+3 to the sulphur containing hydrocarbon for form Co and Mo+4. HDS
catalyst is furnished as porous particles or extradites with diameter of 1.5 to 3mm. The
particles size and pore geometry significantly influence catalyst performance, especially for
the heaviest feeds.
20
Chapter 3
3.4
Process of hydrodesulphurization
Hydrodesulphurization Reactions
Petroleum crudes contain many different sulphur compounds. More are created in cracking
operations which may precede HDS units. Figure 2 identifies a few of these compounds and
illustrates their structure. Note the first four members of the list represent different kinds of
C-S bonding. The list is ordered to show reactivity of each class in hydrodesulphurization.
The thiols are very reactive, while S bond into an aromatic ring is refractory. Reactions which
take place are cleavage of the C-S and S-S bonds;
Thiols:
RSH + H2
Disulphides:
RSSR + 3H2
Sulphides:
RSR + 2H2
RH + H2S
RH + RH + 2H2S
RS + RH + H2S
All of the above reactions are essential irreversible at 350-450 oC and 100-200 atm H2
pressure, although at very low sulphur levels the equilibrium system must be considered.
+ 2
21
Chapter 3
Process of hydrodesulphurization
Reaction of this type may be beneficial. Removing nitrogen from feed stocks is often
necessary before refining by hydro cracking, since basic nitrogen containing compounds are
poisons for the acidic sites of bifunctional hydro cracking catalysts.
Hydrogenation of unsaturated compounds also occurs during HDS and reaction rates are
significant compared with those of hydrodesulphurization. For example, naphthalenes
hydrogenated readily:
The last three classes of reactions take on economic importance in the processes by
consuming expensive hydrogen without removing sulphur.
HDS reactions are exothermic with heats of reaction of the order of 10 to 20 Kcal/mole of
hydrogen consumed or roughly 50 to 100 Btu/standard cubic foot of hydrogen consumed.
Compounds Class
Structure
Thiols (Mercaptans)
Disulphides
Sulphides
RSH
RSSR
RSR
Thiophenes
Benzothiophenes
Dibenzothiophenes
Benzonaphthothiophenes
BenzoDibenzothiophenes
Figure 3.2: Classes of sulphur containing compounds in petroleum
22
Chapter 3
3.5
Process of hydrodesulphurization
Hydrodesulphurization Kinetics
A thiophenes compound are the least reactive sulphur compounds in petroleum, is the
simplest compound in this class. Thiophenes have frequently been chosen for the study as a
model reactant. Thiophenes hydrodesulphurization is examined in series kinetics. The
catalysts are a commercial Co-Mo/Al2O3 (1.3 percent Co and 6.1 percent Mo), Chromia, and
several molybdenum disulphides. Hydrodesulphurization apparently proceeds through
rupture of the -S- bonds to form butadiene.
23
Chapter 3
Process of hydrodesulphurization
Temperature
Kr/
KH2S/
KB/
(oC)
(mole/gatm.sec)
atm-1
atm-1
mole/gtam.sec
atm-1
235
1.5 x 10-5
43
31
2.0 x 10-8
980
91
251
1.6 x 10-5
23
13
12.2 x 10-8
120
19
265
1.8 x 10-5
25
56
--------------
-------
13
3.6
3.6.1
Introduction
A trickle-bed reactor (TBR) is a chemical reactor that uses the downward movement of a
liquid and gas over a packed bed of catalyst particles. It is considered to be the simplest
reactor type for performing catalytic reactions where a gas and liquid (normally both
reagents) are present in the reactor and accordingly it is extensively used in processing plants.
Typical examples are liquid phase hydrogenation in refineries (three phase hydro treater) and
oxidation of harmful chemical compounds in wastewater streams. [12]
At high liquid and/or gas flow rates, TBRs are operated in the pulsating flow regime, where
the gas/liquids distributions vary and liquid rich pulses move down the bed. The conductance
method had been used extensively to characterize this liquid pulses [13] with two or more
pairs of conductance rings place at different heights down the bed. Each pairs measures the
electrical impedance of the liquid, hence the liquid holdup, in the bed cross section between
the ring electrodes at a sampling rate of up to thousands of Hz. This technique is in situ and
very robust for studying transient behavior in TBRs. However, an intrinsic drawback is that
all measurements made are averaged between pairs of conductance rings and no spatial
information is given.
24
Chapter 3
3.6.2
Process of hydrodesulphurization
Summary of the typical H2 and oil phase mass flow rates for HDS are reproduced. Bearing in
mind that the transition between trickling and pulsing is downward concurrent operation is
2<L<10kg/m2/s and 0.1<G<1.0kg/m2/s, pilot plant HDS beds operate in the trickling regime,
while full scale units may sometimes function in the pulsating regime.
The gas and liquid loading in HDS trickle beds make it unlikely that mass transfer from the
liquid phase to the catalyst particles is rate controlling. On the other hand, transport within
the catalyst reduces the apparent HDS activity. Effectiveness factors, are about 0.4 to 5mm
diameter CoMoO4/Al2O3 extradites (55 atm, 370oC), whereas they are about 0.6 for 3.2mm
particles at 34 atm and 416oC. Internal diffusion may not be the only source of the particle
size dependence.
Advantages of a trickle bed are ease of installation, low liquid holdup(and therefore less
undesirable homogeneous reactions), minimal catalyst handling issues, low catalyst attrition,
and catalyst life of 1 to 4 years.
The liquid and gas flow in trickle beds approaches plug flow (leading to higher conversion
than slurry reactors for the same reactor volume).
Downsides of trickle beds include flow maldistribution (bypassing),sensitivity to packing
uniformity and prewetting (leading to hot spots),incomplete contacting/wetting, intra particle
diffusion resistance, potential for fouling and bed plugging due to particulate matter in the
feed, and high pressure drop. A significant fraction of the flow is gas that has to be
compressed and recycled (i.e., increased compressor costs).
3.6.3
Figure shows a vertical cross section of a trickle bed designed to hydro treat 25,000 bbl/day
of gas oil. Nominal feed rates of the 30oAPI oil and gas (75%H2) are 323,078 lb/hr and
weight hourly space velocity for this reactor is about 3.5. Oil and hydrogen are mixed prior to
the fired heater. They enter the reactor at about 700-800oF and 800-1000 psi. Somewhat over
the half i=oil is vaporized in the heater.
The liquid phase entering the top of the reactor drops into a perforated catch plate which
distributes the phase across the upper catalyst bed. Gas enter the bed through the chimneys a
six inch deep layer of inert ball protect the catalysts and probably further distributed the
liquid and gas phase, depending on the bed depth. Primarily, flow distributer will be used as
may be seen in PFD. Their design is much like the top distributor. Gas descends to the lower
bed in chimneys and most of the liquid phase is redistributed by the catch plane. The design
shows also permits a gas quench for temperature controls. [14]
25
Chapter 3
Process of hydrodesulphurization
A bed of coarse, inert spheres supports the catalyst (beds are connected through the
chimneys), while a bed of finer spheres prevents catalyst from mixing with the supports. A
nozzle in the bottom of head may be opened to withdraw spent catalyst. Fresh catalyst would
be loaded from the top of the reactor.
Chapter 3
Process of hydrodesulphurization
The need to limit pressure drop is driven by the capital and operating costs associated with
the hydrogen recycle compressor. Catalyst granules are 1.5 to 3.0 mm (0.06 to 0.12 in),
sometimes a little more. Catalysts are 10 to 20 percent Co and Mo (or Ni and W) on alumina.
The adiabatic temperature rise in each bed usually is limited to 30C (86F) by injection of
cold hydrogen between beds. Since the liquid trickles over the catalyst, the wetting efficiency
of the catalyst is important in determining the volumetric reaction rate. As expected, wetting
efficiency increases with increasing liquid rate. Catalyst effectiveness of particles 3 to 5 mm
(0.12 to 0.20 in) in diameter has been found to be about 40 to 60 percent. [15]
27
Chapter No. 4
PLANT LOCATION & LAYOUT
4.1
Plant Location
The geographical location of the final plant can have strong influence on the success of an
industrial venture. Considerable care must be exercised in selecting the plant site, and many
different factors must be considered. Primarily, the plant should be located where the
minimum cost of production and distribution can be obtained, but other factors, such as room
for expansion and safe living conditions for plant operation as well as the surrounding
community, are also important.
A general consensus as to the plant location should be obtained before a design project
reaches the detailed estimate stage, and a firm location should be established upon
completion of the detailed-estimate design. The choice of the final site should first be based
on a complete survey of the advantages and disadvantages of various geographical areas and,
ultimately, on the advantages and disadvantages of available real estate. The following
factors should be considered in selecting a plant site:
1. Raw materials availability
2. Markets
3. Energy availability
4. Climate
5. Transportation facilities
6. Water supply
7. Waste disposal
8. Labor supply
9. Taxation and legal restrictions
10. Site characteristics
11. Flood and fire protection
12. Community factors
The factors that must be evaluated in a plant-location study indicate the need for a vast
amount of information, both quantitative (statistical) and qualitative. Fortunately, a large
number of agencies, public and private, publish useful information of this type greatly
reducing the actual original gathering of the data. [16]
4.1.1
The source of raw materials is one of the most important factors influencing the selection of a
plant site. This is particularly true if large volumes of raw materials are consumed, because
location near the raw-materials source permits considerable reduction in transportation and
storage charges. Attention should be given to the purchased price of the raw materials,
distance from the source of supply, freight or transportation expenses, availability and
reliability of supply, purity of the raw materials, and storage requirements.
28
Chapter 4
4.1.2
Markets
The location of markets or intermediate distribution centers affects the cost of product
distribution and the time required for shipping. Proximity to the major markets is an
important consideration in the selection of a plant site, because the buyer usually finds it
advantageous to purchase from nearby sources. It should be noted that markets are needed for
by-products as well as for major final products.
4.1.3
Energy availability
Power and steam requirements are high in most industrial plants, and fuel is ordinarily
required to supply these utilities. Consequently, power and fuel can be combined as one
major factor in the choice of a plant site. Electrolytic processes require a cheap source of
electricity, and plants using electrolytic processes are often located near large hydroelectric
installations. If the plant requires large quantities of coal or oil, location near a source of fuel
supply may be essential for economic operation. The local cost of power can help determine
whether power should be purchased or self-generated.
4.1.4
Climate
If the plant is located in a cold climate, costs may be increased by the necessity for
construction of protective shelters around the process equipment, and special cooling towers
or air-conditioning equipment may be required if the prevailing temperatures are high.
Excessive humidity or extremes of hot or cold weather can have a serious effect on the
economic operation of a plant, and these factors should be examined when selecting a plant
site.
4.1.5
Transportation facilities
Water, railroads, and highways are the common means of transportation used by major
industrial concerns. The kind and amount of products and raw materials determine the most
suitable type of transportation facilities. In any case, careful attention should be given to local
freight rates and existing railroad lines. The proximity to railroad centers and the possibility
of canal, river, lake, or ocean transport must be considered: Motor trucking facilities are
widely used and can serve as a useful supplement to rail and water facilities. If possible, the
plant site should have access to all three types of transportation, and, certainly, at least two
types should be available. There is usually need for convenient air and rail transportation
facilities between the plant and the main company headquarters, and effective transportation
facilities for the plant personnel are necessary.
4.1.6
Water supply
The process industries use large quantities of water for cooling, washing, steam generation,
and as a raw material. The plant, therefore, must be located where a dependable supply of
29
Chapter 4
water is available. A large river or lake is preferable, although deep wells or artesian wells
may be satisfactory if the amount of water required is not too great. The level of the existing
water table can be checked by consulting the state geological survey, and information on the
constancy of the water table and the year-round capacity of local rivers or lakes should be
obtained. If the water supply shows seasonal fluctuations, it may be desirable to construct a
reservoir or to drill several standby wells. The temperature, mineral content, silt or sand
content, bacteriological content, and cost for supply and purification treatment must also be
considered when choosing a water supply.
4.1.7
Waste disposal
In recent years, many legal restrictions have been placed on the methods for disposing of
waste materials from the process industries. The site selected for a plant should have
adequate capacity and facilities for correct waste disposal. Even though a given area has
minimal restrictions on pollution, it should not be assumed that this condition will continue to
exist. In choosing a plant site, the permissible tolerance levels for various methods of waste
disposal should be considered carefully, and attention should be given to potential
requirements for additional waste-treatment facilities.
4.1.8
Labor supply
The type and supply of labor available in the vicinity of a proposed plant site must be
examined. Consideration should be given to prevailing pay scales, restrictions on number of
hours worked per week, competing industries that can cause dissatisfaction or high turnover
rates among the workers, and variations in the skill and productivity of the workers.
4.1.9
State and local tax rates on property income, unemployment insurance and similar items vary
from one location to another. Similarly, local regulations on zoning, building codes, nuisance
aspects, and transportation facilities can have a major influence on the final choice of a plant
site. In fact, zoning difficulties and obtaining the many required permits can often be much
more important in terms of cost and time delays than many of the factors discussed in the
preceding sections.
4.1.10
Site characteristics
The characteristics of the land at a proposed plant site should be examined carefully. The
topography of the tract of land and the soil structure must be considered, since either or both
may have a pronounced effect on construction costs. The cost of the land is important, as well
as local building costs and living conditions. Future changes may make it desirable or
necessary to expand the plant facilities. Therefore, even though no immediate expansion is
planned, a new plant should be constructed at a location where additional space is available.
30
Chapter 4
4.1.11
Many industrial plants are located along rivers or near large bodies of water, and there are
risks of flood or hurricane damage. Before selecting a plant site, the regional history of
natural events of this type should be examined and the consequences of such occurrences
considered. Protection from losses by fire is another important factor in selecting a plant
location. In case of a major fire, assistance from outside fire departments should be available.
Fire hazards in the immediate area surrounding the plant site must not be overlooked.
4.1.12
Community factors
The character and facilities of a community can have quite an effect on the location of the
plant. If a certain minimum number of facilities for satisfactory living of plant personnel do
not exist, it often becomes a burden for the plant to subsidize such facilities. Cultural
facilities of the community are important to sound growth. Churches, libraries, schools, civic
theaters, concert associations, and other similar groups, if active and dynamic, do much to
make a community progressive. The problem of recreation deserves special consideration.
The efficiency, character, and history of both state and local government should be evaluated.
The existence of low taxes is not in itself a favorable situation unless the community is
already well developed and relatively free of debt.
4.2
The major factors in the selection of most plant sites are (1) raw materials, (2) markets, (3)
energy supply, (4) climate, (5) transportation facilities, and (6) water supply. For a
preliminary survey, the first four factors should be considered. Thus, on the basis of raw
materials, markets, energy supply, and climate, acceptable locations can usually be reduced to
one or two general geographical regions. For example, a preliminary survey might indicate
that the best location for a particular plant would be in the south-central or south-eastern part
of the United States. In the next step, the effects of transportation facilities and water supply
are taken into account. This permits reduction of the possible plant location to several general
target areas. These areas can then be reduced further by considering all the factors that have
an influence on plant location.
As a final step, a detailed analysis of the remaining sites can be made. Exact data on items
such as freight rates, labor conditions, tax rates, price of land, and general local conditions
can be obtained. The various sites can be inspected and appraised on the basis of all the
factors influencing the final decision. Many times, the advantages of locating a new plant on
land or near other facilities already owned by the concern that is building the new plant
outweigh the disadvantages of the particular location. In any case, however, the final decision
on selecting the plant site should take into consideration all the factors that can affect the
ultimate success of the overall operation.
31
Chapter 4
We have selected our site near pak-arab refinery limited (PARCO) Qasba Gujrat District
Muzaffargarh Pakistan.
4.3
Plant Layout
After the process flow diagrams are completed and before detailed piping, structural, and
electrical design can begin, the layout of process units in a plant and the equipment within
these process units must be planned. This layout can play an important part in determining
construction and manufacturing costs, and thus must be planned carefully with attention
being given to future problems that may arise. Since each plant differs in many ways and no
two plant sites are exactly alike, there is no one ideal plant layout. However, proper layout in
each case will include arrangement of processing areas, storage areas, and handling areas in
efficient coordination and with regard to such factors as: [16]
1. New site development or addition to previously developed site
2. Type and quantity of products to be produced
3. Type of process and product control
4. Operational convenience and accessibility
5. Economic distribution of utilities and services
6. Type of buildings and building-code requirements
7. Health and safety considerations
8. Waste-disposal requirements
9. Auxiliary equipment
10. Space available and space required
11. Roads and railroads
12. Possible future expansion
32
Chapter No. 5
Material Balance
5.1
Material balance
Material balance is defined as the mass conserved; the mass entering in a process is equal to
mass exiting from the process. It is based on the law of conservation of mass which states that
mass is neither be created nor be destroyed.
5.1.1
It states that:
[Rate of mass going into the system]-[Rate of mass going out of the system] +[Rate of mass
generation within the system]-[Rate of mass consumption within the
system]=[Rate of mass accumulation in the system]
5.2
0.8767 [18]
APIo
30
1.81% (wt)
25,000bbl/day
0.05%
33
Chapter 5
5.3
Material Balance
Gas Oil
We want to know the mass of gas oil used.
=
.. 1
water
=
1kg/litre
.
= 0.8767 * 1
=0.8767 kg/litre
(as 1kg = 2.2lbm)
= 0.8767
= 1.9287
2.2
1
Quantity of oil
25,000 bbl/day
25,000
V oil
3974565 litre/day
3.7853
34
Chapter 5
Material Balance
1.9287
3974565 litre/day
M oil
7665744 lbm/day
319406 lbm/hr
5.4
Hydrogen gas
H2 * VH2
H2
0.0056 lbm/ft3
= 315 ft3
0.0055954
M hydrogen
44064 lbm/day
M hydrogen
1836 lbm/hr
7875000
35
Chapter 5
Material Balance
1836*2
M hydrogen
3672 lbm/hr
5.5
M hydrogen
3672 lbm/hr
= 319406 lbm/hr
Oil = ?
= 1.81% of oil
H2= ?
= 5781.25 lbm/hr
H2S = ?
Reaction occurring is
+
Theoretical H2 required
H2S produced
5781.25*2/32
361.33 lbm of H2
5781.25*34/32
36
Chapter 5
Material Balance
Gas oil contains different sulphur compounds such as sulphides, cyclic sulphide,
Benzothiophenes,
.. (A)
1 mole of C4H4S
34 lbm of H2S
84 lbm of C4H4S
84/34*6142.58
15175.8 5781.25
Total C4H4
From the equation A it is clearly indicate that 1 mole of H2 react with C4H4S to form one
mole of H2S and two moles of H2 reacts with C4H4 to form C4H8.
1 mole of C4H4 require
2 moles of H2
4 lbm of H2
4/52*9394.55
722.66 lbm of H2
Unreacted H2
37
Chapter 5
Material Balance
Unreacted H2
M3
MH2 + Moil
oil + H2 + H2S
3672 + 319406
M hydrogen
3672 lbm/hr
M1
Trickle Bed Reactor
M2
M3
M oil
= 319406 lbm/hr
= 1.81% of oil
= 5781.25 lbm/hr
38
Chapter 5
5.6
Material Balance
Separator
5.7
M3
Scrubber
M4
Rich DEA
Moles of H2S
6142.58
180.66 lbmol/hr
39
Chapter 5
Material Balance
1 mol of H2S
180.66*1.3
Moles
weight/ mol. wt
Weight
moles * mol.wt
234.66 * (105*.25)
6165.1 lbm/hr
M3
M4
2588
M4
M4
12307.68 lbm/hr
Total balance
M1
M2
Scrubber
M3
H2= 2588 lbm/hr
M4
Rich DEA = 12307.68 lbm/hr
40
Chapter 5
Material Balance
Stripper
Oil = = 314347.42 lbm/hr
Gas oil = ?
(Desulphurized)
From the reactor mass balance
+2
722.66 lbm of H2
9394.55 + 722.66
10117.21 lbm/hr
Total oil
314347.42 lbm/hr
10117.21 lbm/hr
Gas oil
Gas oil
314347.21 10117.21
304230.21 lbm/hr
41
Chapter 5
Material Balance
Fuel gas = 10117.21 lbm/hr
Stripper
Oil = = 314347.42 lbm/hr
Gas oil = 304230.21 lbm/hr
(Desulphurized)
42
Chapter 5
Material Balance
43
Chapter No. 6
Energy Balance
6.1.
Energy balance
Energy balance is defined as the energy conserved; the energy entering in a process is equal
to energy exiting from the process. It is based on the law of conservation of energy that
energy is neither being created nor be destroyed but it changes from one form to another.
6.1.1
It states that
[Rate of energy going into the system]- [Rate of energy going out of the system] +[Rate of
energy generation within the system]-[Rate of energy consumption within the system]=[Rate
of energy accumulation in the system]
6.1.2
Reference conditions
6.2.
= 101.325 kPa
78,75,000 ft3/day
7875000
Hydrogen consumed
328125 ft3/hr
50 BTU [21]
50*328125
16406250 BTU/hr
Hydrogen consumed
(1day = 24hr)
44
Chapter 6
Energy Balance
Heat produced, Q
1.641*107 BTU/hr
M oil
319406 lbm/hr
Cp at 750 oF
MoilCpT
1.641*107
T2
813 0F
1.641*107 BTU/hr
813 0F
6.3.
Cold stream
Heat Exchanger
t1 = 77 0F
t2 = 250 0F
T2= ?
319406 lbm/hr
Average temperature
(t1 + t2)/2
(77 + 250)/2
163.5 0F
45
Chapter 6
Energy Balance
Cp at 163.5 oF
Qcold Stream
MoilCp(t2 - t1)
27628619 BTU/hr
Qcold Stream
Cp at 813 oF
Qhot stream
27628619
314347.42*0.845*(T2 813)
T2
729 0F
729 0F
27628619 BTU/hr
46
Chapter 6
6.4.
Energy Balance
Cooler
T1 = 7290F
t1 = 77 0F
T2 = 100 0F
t2 = 130 0F
Heat in cooler
Qin
MCpT1
Cp at 729 0F
Qin
314347.42*0.81*729
185619008.0358 BTU/hr
T2
100 0F
Cp at 100 0F
Qout
MCpT2
314347.42*0.465*100
14617155.03 BTU/hr
Qin - Qout
47
Chapter 6
Heat removed in cooler
Energy Balance
=
171001853 BTU/hr
t1
77 0F
t2
130 0F
t2 - t1
130 77
53 0F
(t2 + t1)/2
(130 + 77) / 2
103.5 0F
Cp of water at Tavg
mCpt
Q/Cpt
171001853/(1*53)
3226450.06 lbm/hr
Tavg
Mass of coolant, m
?
48
Chapter 6
Energy Balance
m/
62.4 lbm/ft3
6.5.
.
.
51705.93 ft3/hr
6.5.1 Heat in
For oil
M oil
319406 lbm/hr
250 0F
Cp at 100 0F
Qoil
MoilCp T
43918325 BTU/hr
M hydrogen
3672 lbm/hr
77 0F
Cp of Hydrogen at 77 0F
Qoil
For Hydrogen
49
Chapter 6
Qhydrogen
Qhydrogen
Energy Balance
=
MhydrogenCp T
3672 * 3.5 * 77
989604 BTU/hr
(MoilCp T) + (MhydrogenCp T)
Qin
Qin
44907929 BTU/hr
Reference temperature, TR
32 0F
{319406 * 0.55 * (250 32)} + {3672 * 3.5 * (77 32)} = {(319406 * 0.55) + (3672 * 3.5)}
* {T 32}
38296779.4 + 578340 = (175673.3 + 12852) * (T 32)
38875119.4 = 188525.3 T - 6032809.6
=
238.2 0F
238.2 0F
750 0F
50
Chapter 6
Energy Balance
Cp at 750 oF
M oil
319406 lbm/hr
Qoil
MoilCp T
196434690 BTU/hr
750 0F
Cp at 750 oF
M hydrogen
3672 lbm/hr
Qhydrogen
MhydrogenCp T
Qhydrogen
9639000 BTU/hr
Qoil + Qhydrogen
196434690 + 9639000
Qout
206073690 BTU/hr
Qout Qin
206073690 44907929
161165761 BTU/hr
For Hydrogen
51
Chapter 6
Energy Balance
28 lbm/lbmol
1540 BTU/ft3
1407 BTU/ft3
1 ft3
1/1407
1/1407 * 161165761
114545.67 ft3
Air needed
1 ft3 of fuel (Refinery gas) needed air
15.7 * 114545.67
1798367.019 ft3/hr
1.35 * 1798367.019
2427795.5 ft3/hr
52
Chapter 6
6.6.
Energy Balance
314347.42 lbm/hr
100 0F
Cp of oil at 100 0F
M Cp T
14617155 BTU/hr
300 0F (Assume)
Cp at 300 0F
Qout
M Cp T
54224930 BTU/hr
Heat in
Qin
Heat out
Qout Qin
54224930 14617155
53
Chapter 6
Energy Balance
39607775BTU/hr
Source of heating
Steam enter at 214.7 Psia or 200 Psig
T
388 0F
Latent heat,
m*
Q/
39607775/837
47321 lbm/hr
Mass of Steam, M
54
Chapter 6
Energy Balance
55
Chapter No. 7
Equipment Design
7.1
Design of furnace
The furnace is designed to heat the feed form 238.2 0F to 750 0F.
The fuel used in heater is the refinery gas. Furnace is handling the flow rate of feed
238.2 0F
750 0F
(750 238.2)
511.8 0F
(T1 + T2)/2
(238.2 + 750)/2
494.10F
Cp at Tavg
323078 lbm/hr
Heat absorbed
mCpT
113265654.5 BTU/hr
Tavg
56
Chapter 7
Equipment Design
0.004
1/ (1/hi + Ro)
1/ (1/180 + 0.004)
104.65 BTU/hr-ft2-0F
UAT
Q/UT
2114.75 ft2
2 inch
0.622 ft2/ft
1 ft
1/0.622
1/0.622 * 2114.75
57
Chapter 7
Equipment Design
=
3399.92 ft
3399.92/30
114 pipes
Stainless steel
Number of 30 ft pipes
58
Chapter 7
Equipment Design
Units
Duty
BPD
25,000
Flow rate
lbm/hr
323078
Gravity
API
30
Inlet Temperature
238.2
Outlet Temperature
750
106 BTU/hr
113.27
BTU/hr-ft2-0F
180
Fouling factor
hr-ft2-0F/BTU
0.004
Area
ft2
2114.75
Pipe size
Inch
ft
3399.92
No. of pipes
114
Material of construction
Stainless steel
59
Chapter 7
7.2
Equipment Design
Reactor Design
The function of reactor is to react 319406 lbm/hr of gas oil containing 1.81% (wt) of
sulphur with 3672 lbm/hr of Hydrogen. Feed passed through fixed bed reactor and sulphur is
converted into H2S in the presence of catalyst. We are using Trickle bed reactor. In this
reactor flow rate of liquid is very slow as compared to gas flow rate. Thats why the process
of Trickling occurs.
Calculations
Inlet temperature of the stream
750 0F
813 0F
1200 psia
3.5 hr-1
Space velocity, S
3.5 hr-1
Space Time, T
1/S
1/3.5
0.29 hr
V/Vo
Volume of reactor
Space Time, T
We know the equation
T
Where,
V
60
Chapter 7
Equipment Design
Vo
319406 lbm/hr
3672 lbm/hr
323078 lbm/hr
0.8767
water
62.4 lbm/ft3
oil
0.8767 * 62.4
oil
54.71 lbm/ft3
hydrogen
0.0056 lbm/ft3
323078/54.71
Vo
5905.3 ft3/hr
T * Vo
0.29 * 5905.3
1712.5 ft3
Since reactor is packed with catalyst. So, we will have to consider fraction voids
which is . suppose
61
Chapter 7
Equipment Design
=
0.4
V/
Vf
Vf
1712.5/0.4
Vf
4281.3 ft3
We have formula
Vf
Where,
4281.3 * 1.3
Vf
5565.69 ft3
15 ft
Vf
A*L
A*L
5565.69 ft3
/4 * d2 * L
5565.69 ft3
31.5 ft
2568.8 ft3
62
Chapter 7
Empty Space
Equipment Design
=
1275.39 ft3
637.695 ft3
637.695 ft3
Stainless steel
63
Chapter 7
Equipment Design
Units
Duty
Flow rate
lbm/hr
323078
Pressure range
Psia
900-1200
Inlet Temperature
750
Outlet Temperature
813
LHSV
hr-1
3.5
Volume of reactor
ft3
5565.69
Fraction Voids
0.4
%age
30
Dia of reactor
ft
15
Length of reactor
ft
31.5
ft3
2568.8
Material of construction
Stainless steel
64
Chapter 7
7.3
Equipment Design
that on the load on the furnace can be reduced by preheating second. We want to lower down
the temp. of stream from the reactor. Feed stream is heated from 77F to 250F while
temperature of stream from the reactor is lower down from 813F to 729F.
Hot Stream T1=8130F
Cold stream
Heat Exchanger
t1 = 77 0F
t2 = 250 0F
T2= ?
319406 lbm/hr
Average temperature
(t1 + t2)/2
(77 + 250)/2
163.5
Cp at t Avg
MoilCp (t2-t1)
319406*0.5*(250-77)
27628619 Btu / hr
65
Chapter 7
Equipment Design
Cp at 813 oF
Qhot stream
27628619
314347.42*0.845*(T2 813)
T2
729 0F
729 0F
Calculation of LMTD
Flow is countercurrent. So,
1
lm
T1 t2
813 250
563 0F
T2 t1
729 -77
652 0F
(652-563) /ln(652/563)
606.41 0F
66
Chapter 7
Equipment Design
Ud is given in literature =
So, Ud
38 Btu / hr ft2-0F
Ud A lm
Q/ Udlm
27628619/ (38*606.41)
1199ft3
3.14DoNtL
Now, A
We should have to select shell dia, no. of tubes length heat exchange and dia of tube
Let,
Outer dia of tubes, Do
1.5 in [22]
Square pitch
1.875 in
Shell ID
31 in
No. of tubes, Nt
151
20ft
3.14 DoNtL
1185.35 ft2
Q/ A lm
27628619/ (1185.35*606.41)
67
Chapter 7
U
Equipment Design
=
T1 T2
813-729
84 0F
Kc
t2 t1
250-77
173 0F
T1 t2
729-77
652 0F
T1 t2
813- 250
563 0F
652/563
1.16
0.3
tc
th
tc/th
As Kc
and
tc/th
= 1.16
68
Chapter 7
Equipment Design
Fc
0.48 [22]
Tc
729 +0.48(813-729)
769.32 0F
770 0F
tc
t1 + Fc(t2 t1)
tc
77 +0.48(250-77)
160 0F
Allocation of Fluids
Hot oil passes through tube side while cold oil will flow through shell side
Properties of Oil
Properties of cold Fluid (shell side)
Tc
160Fo
Cp
4.5 c.p.
4.5*2.42
10.9 lb / hr ft
69
Chapter 7
S.G
Equipment Design
=
0.84
As
I D * C B / 144 pt
Pt
1.875 in [22]
Dia of tubes
1.5 in
pt - Do
0875-1.5
0.345 in
ID
31 in
31 in
As
(31*0.375*31) /(144*1.875)
As
1.335 ft3
Moil/As
319406/1.335
Flow Area
Mass Velocity
Gs
70
Chapter 7
Equipment Design
DeGs/
De
1.48 in [22]
De
1.48/12
0.123 ft
(0.123)*(239255)/10.9
2700
28 [22]
(Cp/K)1/3
(0.5*10.9/0.0743)1/3
4.13
ho
Jh(k/De)(Cp/k)0.33s
ho/ s
28*(0.0743/0.123)*4.13
ho/ s
Res
JhFactor
Jh
Prandtl no.
Pt
71
Chapter 7
Equipment Design
770 0F
Cp
0.53 c.p.
0.53*2.42
1.283 lb / hr ft
0.615
ID
1.23 in or 0.1025 ft
3.14*(ID)2/4
1.19 in2
A*Nt/(144*n)
1.19*15.1/(144*1)
1.25ft2
Area of tube
Area Calculations
At
Where,
A
72
Chapter 7
At
Equipment Design
=
Moil/At
319406/1.25
Ret
IDtGt/
Ret
(0.123)*(255525)/1.283
244970
20/0.1025
195
520 [22]
(Cp/K)1/3
(0.85*1.283)/(0.06)1/3
2.627
Mass Velocity
Gt
JhFACTOR
L/D
Jh
Prandtl no.
Pt
73
Chapter 7
Equipment Design
hi/t
hi
Jh(k/De)(Cp/k)1/3t
hi/t
520*(0.06/0.1025)*2.627
hi/t
hio/t
(hi/t)(I D / OD)
800*(1.23/1.5)
hio/t
218.7 0F
219 0F
tw
219 0F
2.5 cp
2.5*2.42
6.05lb / (ft-hr)
(/w) 0.14
(10.9/6.05)
1.082
tw
TUBE SIDE
74
Chapter 7
Equipment Design
ho/ s
ho
69.85*1.082
ho
hio/t
hio
656 * 1.082
hio
(hio*ho)/(hio+ho)
(709.8*75.6)/ (709.8+75.6)
(1/UC) +RD
1/(68.32)+0.003
and
Calculation of UC
UC
UC
Calculation of UD
1/UD
UD
244970
75
Chapter 7
Equipment Design
0.00012 ft2/in2
Pt
(fG2tLn)/(5.22*1010*D*S* t)
=
Pt
{0.00012*(255525)2*20*1}/ (5.22*1010*0.1025*0.8767*0.805)
=
0.041 psi
Gt
255525 lb / (hr-ft2)
V2/2g
Pr
(4n/S)(v2/2g)
(4*1/0.8767*0.0084)
0.038 psi
Pt+Pr
0.041+0.038
0.079 psi
10psi
2700
0.0027 ft2/in2
12*L/B
When
Pt
Allowable PT
SHELL SIDE
Res
[22, fig-29]
76
Chapter 7
Equipment Design
N+1
Ps
=
12*20/31
7.74
{f*Gs2*D*(N+1)}/(5.22*1010*Ds*S*s)
{0.0027*(239255)2*(31/12)*7.74}/(5.22*1010*0.123*0.8767*1.086)
=
0.5 psi
Allowable Ps
10 psi
Material of construction
stainless steel
77
Chapter 7
Equipment Design
Units
ALLOCATION OF FLUID
Shell side
in
Shell side
out
lbm/hr
TEMPERATURE
SP.GRAVITY
Tube side
in
Tube side
Out
319406
319406
319406
319406
77
250
813
729
0.84
0.615
10.9
1.283
0.5
0.85
0.0743
0.06
0.05
0.079
FOULDING RESISTANCE
hr-ft2-OF/Btu
0.003
0.003
68.32
VISCOSITY
lb/ft-hr
O
SP. HEAT
Btu/lb- F
THERMAL CONDUCTIVITY
ft2-OF
PRESSURE DROP ALLOW
Btu/hrPsi
Btu/hr-ft2-OF
56.7
LMTD
606.41
CALORIC TEMP
160
HEAT EXCHANGE
AREA REQUIRED
DIAMETER
Btu/hr
Ft
Inch
NO. OF PASSES
BAFFLE SPACING
Inch
27628619
1186
31(inner)
1.5(outer)
31 segment
NO. OF TUBES
H.E TYPE
MATERIAL OF CONSTRUCTION
Stainless steel
78
Chapter 7
7.4
Equipment Design
Separator Design
The function of Separator is to separate the oil from the gas. We are using horizontal
314347.42 lbm/hr
oil
314347.42 /54.71
5745.70 ft3/hr
GH2S
6142.58 lbm/hr
H2S
QH2S
63985.21 ft3/hr
GH2
2588 lbm/hr
H2
2588/8730.58
WH2
0.3
WH2s
1 - 0.3
Qoil
79
Chapter 7
Equipment Design
WH2s
0.7
gas
gas
QH2
462142.86 ft3/hr
Qgas
Qgas+ QH2
Qgas
63985.21 + 462142.86
Qgas
526128.07 ft3/hr
Settling velocity, Ut
Where Ut
0.07{(54.71+0.069)}/0.069}1/2
1.97 m/sec
6.46 ft/sec
Ut
If a demister pad is not used, the value of Ut obtained should be multiplied by a factor
of 0.15 to provide a margin of safety and to allow for flow surges. [23] pg-461
Try a separator without a demister pad.
80
Chapter 7
Equipment Design
So,
Ut
0.15 * 6.46
0.97 ft/sec
35.15 ft3/sec
Taking hv
0.5 Dv and
Lv
5 Dv
fv
Where
hv
fv
Dv
Vessel diameter
Lv
Length of vessel
Av
Vapour velocity, Uv
( Dv2/4)*0.5
0.393 Dv2
Q/A
35.15 / (0.393Dv2)
89.44 Dv-2
81
Chapter 7
Equipment Design
Vapour residence time required for the droplets to settle to liquid surface
Residence time required
hv/Ua
Trequired
0.5 Dv/0.97
0.52 Dv
Lv/Uv
0.0056 Dv3
So,
0.0056 Dv3
Dv2
92.86
Dv
9.64 ft say 10 ft
1.6 ft3/sec
Tactual
For satisfactory separation
0.52 Dv
Chapter 7
Length, Lv
Equipment Design
=
5* Dv
5* 10
Lv
50 ft
Hold up volume
Lv * AL
50 * 39.25
1962.5 ft3
1226.56 sec
20.5 min
Stainless Steel
Hold up time
Material of construction
83
Chapter 7
Equipment Design
Units
Duty
lbm/hr
323078
lbm/hr
8730.58
lbm/hr
314347.42
Operating Temperature
100
Settling Velocity
ft/sec
6.46
Dia of separator
ft
10
Length of separator
ft
50
Hold up time
min
20.5
Material of construction
Stainless steel
84
Chapter 7
7.5
Equipment Design
Scrubber Design
Lean DEA
M2
M1
Scrubber
M3
H2= 2588 lbm/hr
M4
Rich DEA
180.66 lbmol / hr
0.002 * 180.66
H2S to be Scrubbed
(180.66-0.36)/180.66
Eal
0.998
(Lo/Vn+1) min
KI* EaI
11.5 * 0.998
11.48
Moles of H2S in H2
85
Chapter 7
Equipment Design
Value of Kl is taken from equilibrium charts for avg. Tower condition i.e.
T = 90 F0
Operating (Lo/Vn+1)
and p = 60 psig
11.48 x 1.25
14.35
14.35x1/ 11.5
1.25
n+1
Eai
(Aio
- Aio)/ (Aio
- 1) [24]
21
Absorption efficiency,
55-60%
Actual plates, N
n/
21/0.6
86
Chapter 7
Equipment Design
35
6165.1 lbm/ hr
Density of DEA
67.8 lbm/ft3
6142.58 + 2588
8730.58 lb /hr
Density of gas
=
P1V1/T1
359/492
?
P2V2/T2
(As P1=P2)
V2/560
V2
gas
M.Wavg/ volume
M.Wavg
0.7 * 34 + 0.3*2
M.Wavg
24.4 lbm/lbmol
gas
24.4 / 408.62
0.06 lbm/ft3
L/G (P V/PL)1/2
FLV
Chapter 7
FLV
Equipment Design
=
0.021
Csb(/20)0.2
Uvf
13.1 ft/sec
Uvf
Uvf * (% flooding)/100
13.1 * (85)/100
11.14 ft/sec
Chapter 7
Equipment Design
At
Qv/Uv
Qv
G/v
8730.58 / 0.06
Qv
40.42 ft3/sec
Then, At
40.42 / 11.14
At
3.63 ft2
3.63 * 1.2
At
4.4 ft2
(4*At/) 0.5
(4*4.4/) 0.5
2.4 ft
2.5 ft
Area of column
*2.52/4
4.91 ft2
89
Chapter 7
Equipment Design
Units
Duty
lbm/hr
8730.58
H2S to be Scrubbed
lbm/hr
6130.34
lbm/hr
6165.1
Absorption factor
1.25
Absorption Efficiency
60 %
Tray Spacing
Inch
24
Velocity
ft/sec
13.1
Dia of Column
ft
2.5
Area of column
ft
4.91
Operating Temperature
100
Material of construction
Stainless steel
90
Chapter 7
7.6
Equipment Design
Stripper Design
Fuel gas = 10117.21 lbm/hr
Stripper
Oil = = 314347.42 lbm/hr
Gas oil = 304230.21 lbm/hr
(Desulphurized)
Stripper is designed to separate 10117.21 lbm/hr of fuel gas from 314347.42 lbm/hr of oil.
Assumption:
L
5d
Oil out, G
304230.21 lbm/hr
oil
54.71 lbm/ft3
G/oil
304230.21/54.71
5560.8 ft3/hr
(5560.8*2)/60
91
Chapter 7
Equipment Design
=
185.4 ft3
Volume of tower, VT
1.5 * 185.4
VT
278.1 ft3
VT
(*d2*L)/4
VT
(*5d3)/4
d3
4/5*(VT/)
4/5*(278.1/)
d3
70.82 ft3
4.14 ft
5*d
5*4.14
20.7 ft
Stainless steel
(assume, L=5d)
92
Chapter 7
Equipment Design
Units
Duty
lbm/hr
314347.42
lbm/hr
10117.21
lbm/hr
304230.21
Operating Temperature
300
ft3/hr
5560.8
Volume of tower
ft3
278.1
Dia of tower
ft
4.14
Length of tower
ft
20.7
Operating time
min
Material of construction
Stainless steel
93
Chapter No. 8
Instrumentation & Process Control
8.1
Instrumentation
Instruments are provided to monitor the key process variables during plant operation.
They may be incorporated in automatic control loops or used for the manual monitoring of
the process operation. They may also be part of an automatic computer data logging system.
Instruments monitoring critical process variables will be fitted with automatic alarms to alert
the operators to critical and hazardous situations.
It is desirable that the process variable to be monitored be measured directly.
However, this is often impractical and some dependent variable that is easier to measure,
monitored in its place. For example, in the control of distillation columns the continuous online, analysis of the over-head product is desirable but it is difficult and expensive to achieve
reliably, so temperature is often monitored as an indication of composition. [26]
8.2
There might be lot of control objectives depending upon the situation, condition and
equipment. Some of common and major objectives of instrumentation and control schemes
are given following:
8.2.1
8.2.2
Production Rate
a) To achieve the design product output.
b) To increase production rate by fast and accurate control action
8.2.3
Product Quality
To maintain the product composition within the specified quality standards
94
Chapter 8
8.2.4 Cost
To operate at the lowest production cost, commensurate with the other objectives.
These are not separate objectives and must be considered together. The order in which they
are listed is not meant to imply the precedence of any objective over another, other than that
of putting safety first. In a typical chemical processing plant these objectives are achieved by
a combination of automatic control, manual monitoring and laboratory analysis.
8.3
8.3.1
Process
Any operation or series of operations that produces a desired final result is a process.
In this discussion the process is the CO2 recovery from reformed natural gas.
8.3.2
Measuring Means
Of all the parts of the control system the measuring element is perhaps the most
important. If measurements are not made properly the remainder of the system cannot operate
satisfactorily. The measured available is dozen to represent the desired condition in the
process.
8.3.2.1
Measured
a) Pressure measurements
b) Temperature measurements
c) Flow Rate measurements
d) Level measurements
Variables to be recorded
Indicated temperature, composition, pressure, etc
8.3.3
Controller
The controller is the mechanism that responds to any error indicated by the error
detecting mechanism. The output of the controller is some predetermined function of the
error. In the controller there is also an error-detecting mechanism which compares the
measured variables with the desired value of the measured variable, the difference being the
error.
95
Chapter 8
8.3.4
The final control element receives the signal from the controller and by some
predetermined relationships changes the energy input to the process.
8.4
Classification of Controller
Pneumatic controllers
Electronic controllers
Hydraulic controllers
In the H2S recovery from H2 gas the controller and the final control element may be
pneumatically operated due to the following reasons:
i) The pneumatic controller is very rugged and almost free of maintenance.
ii) The pneumatic controller appears to be safer in a potentially explosive atmosphere
which is often present in the petro-chemical industry.
iii) Transmission distances are short. Pneumatic and electronic transmission systems are
generally equal up to about 250 to 300 feet. Above this distance, electronic systems
begin to offer savings.
8.5
Modes of control
The various types of controls are called "modes" and they determine the type of
response obtained. In other words these describe the action of the controller that is the
relationship of output signal to the input or error signal. It must be noted that it is error that
actuates the controller. The four basic modes of control are:
a.
b.
c.
d.
On-off Control
Integral Control
Proportional Control
Rate or Derivative Control
96
Chapter 8
Advantage
Disadvantage
On-off
Simple, inexpensive
Constant cycling
Proportional
Integral
Eliminates offset
Derivative
Responds to noise
8.6
Alarms are used to alert operators of serious and potentially hazardous, deviations in
process conditions. Key instruments are fitted with switches and relays to operate audible and
visual alarms on the control panels.
The basic components of an automatic trip system are:
A sensor to monitor the control variable and provide an output signal when a
preset valve is exceeded (the instrument).
An actuator to carry out the required action; close or open a valve, switch off a
motor.
A safety trip can be incorporated in control loop. In this system the high-temperature
alarm operates a solenoid valve, releasing the air on the pneumatic activator closing the valve
on high temperature.
97
Chapter 8
Interlocks
Where it is necessary to follow the fixed sequence of operations for example, during a plant
start-up and shut-down, or in batch operations-inter-locks are included to prevent operators
departed from the required sequence. They may be incorporated in the control system design,
as pneumatic and electric relays or may be mechanical interlocks.
8.7
Types of Controllers
8.7.4
Flow Controllers
Flow-indicator-controllers are used to control the amount of liquid. Also all manually
set streams require some flow indication or some easy means for occasional sample
measurement. They are also used to control feed rate into a process unit. Orifice plates are by
far the most common type of flow rate sensor. Normally, orifice plates are designed to give
pressure drops in the range of 20 to 200inch of water. Venture tubes and turbine meters are
also used.
8.7.5
Temperature Controller
Thermocouples are the most commonly used temperature sensing devices. The two
dissimilar wires produce a millivolt emf that varies with the "hot-junction" temperature. Iron
constrictant thermocouples are commonly used over the 0 to 1300F temperature range.
8.7.6
Pressure Controller
Bourdon tubes, bellows and diaphragms are used to sense pressure and differential
pressure. For example, in a mechanical system the process pressure force is balanced by the
movement of a spring. The spring position can be related to process pressure.
8.7.7
Level Controller
Liquid levels are detected in a variety of ways. The three most common are:
1. Following the position of a float, that is lighter them the fluid.
2. Measuring the apparent weight of a heavy cylinder as it buoyed up more or less by
the liquid (these are called displacement meters).
3. Measuring the difference between static pressure of two fixed elevation, one on
the vapor which is above the liquid and the other under the liquid surface. The
differential pressure between the two level taps is directly related to the liquid
level in the vessel.
98
Chapter 8
8.8
Transmitter
The transmitter is the interface between the process and its control system. The job of
the transmitter is to convert the sensor signal (milli volts, mechanical movement, pressure
differential, etc.) into a control signal 3 to 15 psig air-pressure signal, 1 to 5 or 10 to 50 milli
ampere electrical signal, etc.
8.9
Control Valves
The interface with the process at the other end of the control loop is made by the final
control element is an automatic control valve which throttles the flow of a stem that opens or
closes an orifice opening as the stem is raised or lowered. The stem is attached to a
diaphragm that is driven by changing air-pressure above the diaphragm. The force of the air
pressure is opposed by a spring.[25]
99
Chapter 8
8.13
The thermocouple is one of the most common temperature measuring devices. Chromelalomel thermocouple is suggested for the process.
8.13.1 Temperature Indicator Controller (T.LC)
The normal method for controlling a heat exchanger to measure the exit temperature
of the fluid being processed and adjust the input of the cooling or heating medium to hold the
desired temperature. Therefore, the temperatures are recorder-controller are installed to
control the heat exchangers.
8.13.2 Pressure Indicator Controllers (P.I.C)
This instrument is used to pressure of the separator.
8.13.3 Level Controller
This is used to control the level of liquid in separator.
8.13.4 Gate Valve
This is used for in-off services requiring infrequent throttling.
100
Chapter 8
101
Chapter 8
102
Chapter No. 9
The HAZOP (hazard and operability) Method
9.1
Introduction:
9.1.1
The HAZOP process is based on the principle that a team approach to hazard analysis will
identify more problems than when individuals working separately combine results. The
HAZOP team is made up of individuals with varying backgrounds and expertise. The
expertise is brought together during HAZOP sessions and through a collective brainstorming
effort that stimulates creativity and new ideas, a thorough review of the process under
consideration is made.
9.1.2
The HAZOP team focuses on specific portions of the process called nodes. Generally
these are identified from the P&ID of the process before the study begins. A process
parameter is identified, say flow, and an intention is created for the node under consideration.
Then a series of guideword is combined with the parameters flow to create a deviation. For
example, the guideword no is combined with the parameter flow to give the deviation no
flow. The team then focuses on listing all the credible causes of a no flow deviation
beginning with the cause that can result in the worst possible consequence the team can think
of at the time. Once the causes are recorded the team lists of consequences, safeguards and
ant recommendations demand appropriate. The process is repeated for the next deviation and
so on until the completion of the node. The team moves on to the next node and repeats the
process.
9.1.3
HAZOP Objectives:
103
Chapter 9
9.1.4
HAZOP Method
1. Design review is normally a check, where the contributors work alone, so interaction
is not possible.
2. HAZOP is a design review, but is structured, systematic and complete.
3. It involves a skilled team working together and interacting to identify and solve the
problems.
9.1.5
1. What if studies are similar to HAZOP, but are normally less systematic and
complete.
They require less time, but provide less comfort!
2. FMEA is sometimes carried out as a team exercise, when it can be similar to
HAZOP. However, it concentrates on single components rather than the systems.
3. A very power full combination is possible, using HAZOP first to identify issues and
consequences, then using FMEA to review the controls, alarms and interlock,
component by component.
9.1.6
Application of HAZOP
104
Chapter 9
HAZOP Method
9.1.7
Advantages of HAZOP
i.
ii.
Team work.
iii.
Everyone is responsible for his or her work, so no one can blame can blame the
others.
iv.
v.
9.1.8
Limitations of HAZOP
a. Qualitative technique
b. Very time consuming and laborious for complex systems.
c. Required detailed drawings design.
HAZOPs concentrate on identifying both hazards as well as operability problems. While the
HAZOP study is designed to identify hazards through a systematic approach, more than
80%of study recommendations are operability problems and are not, of themselves, hazards.
Although hazard identification is the main focus, operability problems should be identified to
the extent that they have the potential to lead to process hazard, results in an environmental
violation or have a negative impact on profitability. A definition of hazard and operability is
given below:
9.2.1
Definition:
Hazard
Any operation that could possibly cause a catastrophic release of toxic, flammable or
explosive chemicals or any action that could result in injury to personal.
Operability
Any operation inside the design envelope that would cause a shutdown that could possibly
lead to a violation of environmental, health or safety regulations or negatively impact
profitability.
105
Chapter 9
9.3
HAZOP Method
9.3.1
The HAZOP process creates deviations from the process design intent by combining guide
words (No, more, less, etc.) with process parameters resulting in a possible deviation from
design intent, for example, when the guide word No is combined with the parameter flow
the deviation no flow results. The team should then list all credible causes that will in a no
flow condition for the node. A sample list of guide words is given below. It should be pointed
out that not all guideword/parameters combination will be meaningful.
9.3.2
Guidewords:
No or not-no part of the intent is achieved and nothing else occurs (e.g., no flow)
More-quantitative increase (e.g., higher temperature)
Less-quantitative decrease (e.g., lower pressure),
Part of-qualitative decrease (e.g., only one of two components in mixture)
Reverse-opposite (e.g., backflow)
Other than-no part of the intent is achieved and something completely different occurs (e.g.,
flow of wrong material) [16]
As well as-qualitative increase (e.g., an impurity) The application of parameters will depend
on the type of process being considered , the equipment in the process and the process intent,
the HAZOP-PC software include two pop-up menus that lists both specific parameters and
general parameters, The most common specific parameters that should be considered are
flow, temperature, pressure, and where appropriate, level. In almost all instances, these
parameters should be evaluated for every node. The scribe shall document, without
exception, the teams comments concerning these parameters.
Additionally, the node should be screened for application of the remaining specific
parameters (see list below) and for the list of applicable general parameters (see PHApro3TMsoftware). These should be recorded Only if there is a hazard or operability problem
associated with the parameter. A sample set of parameters includes the following:
9.3.3
Specific Parameters
Flow
Temperature
Pressure
Composition
Phase
Level
106
Chapter 9
HAZOP Method
Instrumentation.
Relief
9.4
Sampling
Corrosion/Erosion
Services/Utilities
Maintenance
Addition
Safety
Reaction
Inserting/Purging
Contamination
Requirements; Specific parameters should be considered by team when evaluating each node.
If a particular parameter does not change from one node to the next then it is not necessary to
repeat all of the deviation that were considered in the previous node.
Merely refer to the case in the deviations column of the node presently being considered.
9.5
The team should use care when listing safeguard, Hazard analysis require an evaluation of the
consequences of failure of engineering and administrative controls, so a careful determination
of whether or not these items can actually be considered safeguard must be made. in addition
, the team should consider realistic multiple failures simultaneous events when considering
whether or not any of the above safeguards will actually function as such in the event of an
occurrence.
107
Chapter 9
9.6
HAZOP Method
General:
Synonyms: sulfur, brimstone, flour sulfur, flower of sulfur, precipitated sulfur,
sublimed sulfur, bensulfoid, flower of sulfur, , precipitated sulfur, agri-sul, asulfasupra,
collokit, colsul, cosan, crystex, devisulfur, elosal, gofrativ, hexasul, kolofog, kolospray,
kristex, kulumus, microwetulf, sofril, sperlox-s, spersul, sufran, sulfex, sukfidal, sulforon,
sulkolsulsol, tesuloid, thiolux, thiovit, thiozol, wettasul.
Use: added to soil to increase acidity, chemical reagent
Molecular formula: S
Physical data:
Appearance: yellow powder or fused solid, or amber to yellow crystals
Melting point: 116 0C (depending upon form)
Boiling point: 445 0C
Vapour density (air=1): 8.8
Density (g/cm3): 2.01
Flash point: 188 0C
Flammable Limits: LEL: 3.3 UEL: 46.0
Water solubility: negligible.
Stability:
Stable, Dust may form a flammable or explosive mixture with air. Incompatible with
strong oxidizing agents, most common metals, hydrogen, chlorine, fluorine.
Toxicology:
Eye, skin and respiratory irritant.
Personal protection:
Safety glasses. [27]
108
Chapter 9
9.7
HAZOP Method
General:
Synonyms : hydrogen sulphide , hepatic acid, sewer gas, sulfur hydride,
dihydrogenmonosulfide, dihydrogenmonosulfide, sulfur hydride, stinkdamp, sulfureted
hydrogen.
Physical data:
Appearance: colorless gas with strong odour of rotten eggs(odour threshold ca.0.2 ppt)
Melting point: -85 0C
Boiling point: -60 0C
Vapour density: 1.19
Vapour pressure: [typical cylinder pressure ca.17 bar]
Critical pressure: 88 atm
Specific gravity: 0.993 g/ml (liquid at BP), 1.539 g/l at 0C, 760 mm Hg (gas)
Flash point: -82 0C
Explosion limit: 4.3%-46%
Autoignition temperature: 260 0C
Stability:
Stable high flammable, may form explosive mixture with air. Note wide explosive limits.
Incompatible with strong oxidizing agents, many metals. Many react violently with metal
oxides, copper, fluorine, sodium, ethanol.
Toxicology:
Highly toxic-may be fatal if inhaled. Inhalation of a single breath at a concentration of 1000
ppm (0.1%) may cause coma. Corrosive when moist. Skin contact may cause burns, There is
a rapid loss of sense of smell on exposure to gas concentrations above 150 ppm, and this
means that the extent of exposure may be underestimated.
Perception threshold ranges from 0.5 ppt to 0.1 ppm. Irritant, Asphyxiant.
Personal protection:
Safety glasses, rubber gloves, good ventilation. Remove all sources of ignition from the
working area. [28]
109
Chapter 9
9.8
HAZOP Method
Many of the problems which may arise during the storage of Gas Oil can easily be prevented
by good housekeeping which should include:
Regular draining of tanks to remove water, so helping to prevent the possibility of
microbiological contamination.
Periodic inspection of tanks for evidence of corrosion.
Periodic internal cleaning of tanks to remove any accumulated sludge.
Avoidance of translucent plastic tanks for storage purposes.[29]
110
Chapter No.10
Cost Estimation
10.1 Why estimation?
Before the plant to be operated, specified money must be supplied to purchase and
install the equipment. The capital needed to supply the necessary plant facilities is called
fixed capital investment while that for the operation of the plant is called the working
principal and sum of two capitals is called total capital investment.
An acceptable plant design must present a process that is capable of operating under
conditions which will yield a profit. Since, Net profit total income-all expenses. It is essential
that chemical engineer be aware of the many different types of cost involved in
manufacturing processes. Capital must be allocated for direct plant expenses; such as those
for raw materials, labor, and equipment. Besides direct expenses, many other indirect
expenses are incurred, and these must be included if a complete analysis of the total cost is to
be obtained. Some examples of these indirect expenses are administrative salaries, product
distribution costs and cost for interplant communication. [16,23]
CE
CB * (Q/QB)M [30] 1
Where CE
CB
Ce
C*Sn [23]
Ce
cost constant
.. 2
Where,
111
Chapter 10
Cost Estimation
=
CE Index 2013 (average)
577.4
CE index 2006(average)
500
444
435.8
$ 540 *2 [23]
$ 1080
0.77
3.3*104 kW
$ 1080 * (3.3*104)0.77
$ 3.26*106
$ 3.26*106 (577.4/444)
$ 4.24 *106
QB
80 m2
CB
$ 3.28 * 104
0.68 [30]
Ce
Heat Exchanger
Capacity of exchanger, Q
110.183 m2
112
Chapter 10
Cost Estimation
CE
$ 4.08 * 104
CE
CE
$ 5.40 * 104
Reactor
Material of construction = Stainless steel
Ce
a + bSn
Ce
a,b
Cost constants
Size parameter
157.6 m3
$ 1656995
Putting values
$ 1656995
1656995 * (1.025)7
$ 1969646.35
113
Chapter 10
Cost Estimation
Pump
Material of construction = Carbon steel
Ce
a + bSn
$ 13361.74
$13361.74 * (1.025)7
$ 15882.91
Scrubber
QB
0.1 m3
CB
$ 4.92 * 103
0.53 [30]
Capacity of Scrubber, Q
1.74 m3
CE
$ 2.24 * 104
CE
CE
$ 2.97 * 104
0.1 m3
Stripper
QB
114
Chapter 10
Cost Estimation
CB
$ 4.92 * 103
0.53 [30]
Capacity of Stripper, Q
7.87 m3
CE
$ 4.98 * 104
CE
CE
$ 6.6 * 104
QB
70.88ft2
CB
$ 60781.22
0.49 [16]
Separator
Capacity of exchanger, Q
78.50 m2
$ 60781.22* (78.50/70.88)0.49
CE
$ 63899.72
CE
$ 63899.72 * (577.4/500)
CE
$ 73791.5
$ 1.70/kg [23]
$ 1.70 * (577.4/390)
$ 2.52/kg
115
Chapter 10
Cost Estimation
Cost of hydrogen
Cost
$ 4240000
Fired heater
$ 54000
Heat exchanger
Reactor
$ 1970000
Separator
$ 73791.5
Scrubber
$ 29700
Stripper
$ 66000
Centrifugal Pump
$ 15883
$ 6449374.5
Total
Cost million $
6.449
0.645
7.094
40
2.838
Instrumentation&Controls(installed)
11
0.780
Piping (installed)
90
6.385
60
4.256
10
0.709
Yard improvements
03
0.213
20
1.419
23.694
116
Chapter 10
10.3.2
Cost Estimation
Indirect cost
Component
Engineering and supervision
Cost million $
0.709
Construction expenses
09
0.638
Legal expenses
04
0.284
Contractor's fee
04
0.284
Contingency
07
0.497
2.412
F.C.I
D.C
23.694 + 2.412
$ 26.106 *106
F.C.I
I.C
Working capital
Allowing 5% of fix capital investment to cover the cost of initial charge
Working capital
Working capital
$ 1.305*106
$ 27.411*106
117
Chapter 10
Cost Estimation
Variable cost
Name of Material
Raw Materials
Price, $/liter
Annual Amount,
million liter/y
Annual raw
materials cost,
million $/y
Gas Oil
0.50
1450.700
Hydrogen
0.01
47965.000
Diethanolamine
2.74
0.062
Total annual cost of raw materials =
Item
Factor
Raw materials
Operating labor
Operating supervision
Utilities
Maintenance and repairs
Operating supplies
Laboratory charges
Royalties (if not on lump-sum
basis)
10.5.2
Basis
725.35
306.98
0.17
1032.50
Basis cost,
million $/y
Cost,
million $/y
0.15
of operating labor
0.885
0.05
of FCI
of maintenance &
repair
of operating labor
26.816
1032.496
0.885
0.133
2.025
1.341
1.341
0.885
0.201
0.133
1172.281
11.723
1048.768
0.15
0.15
0.01 of co
Variable cost =
Fixed cost
Item
Taxes (property)
Financing
(interest)
Insurance
Rent
Factor
Basis
0.02
of FCI
0
0.01
0
of FCI
26.816
of FCI
26.816
of FCI
26.816
Fixed Charges =
Cost, million
$/y
0.536
0.000
0.268
0.000
0.804
118
Chapter 10
10.5.3
Cost Estimation
Plant overhead
Item
Factor
Plant overhead,
general
10.5.4
0.6
Basis cost,
million $/y
Basis
Cost,
million $/y
1.415
1.415
General expenses
Basis cost,
million $/y
Cost,
million $/y
2.358
0.472
of co
1155.449
57.772
of co
1155.449
46.218
104.462
Item
Factor
Administration
Distribution &
selling
Research &
Development
General Expense =
0.2
0.05
0.04
Basis
$1155.449*106/year
Manufacturing cost =
Manufacturing cost =
$1050.987*106/year
$ 1173 *106
Assume that the Fixed Capital Investment depreciate by straight line method for 10 years.
Gross income
Depreciation, D
(V-Vs)/N
F.C.I
$ 26.106 *106
Vs
No. of years, N
10
($ 26.106 *106)/ 10
$ 2.6106*106
119
Chapter 10
Cost Estimation
=
Gross income
$ 14.94 *106
Net profit
Tax
$ 5.98 *106
Net Profit
Net Profit
$ 8.96 *106
$ 11.57 *106
Rate of return
32.68 %
2.26 year
120
References
References
1.
2.
3.
http://en.wikipedia.org/wiki/petroleum
4.
5.
6.
7.
8.
http://en.wikipedia.org/wiki/hydrodesulfurization
9.
10. http://organica1.org/ops_85/desulfurization.pdf.
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13. Ludwig E Allied process design for chemical & Petroleum plant Gulf Publication
corp (1964)
14. Ramchnadran, P.A & Chaudhari, R.V Three Phase Catalytic Reactor Gordon &
Beach science Publishers
15. Perry, R.H & Green, D. Perrys chemical Engineering Handbook 7th edition
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4th Edition, McGraw-Hill Company Inc. (1991)
17. Kenneth Denbigh F.R.S Chemical Reactor Theory Cambridge University Press
(1966)
18. http://www.gulfoilphilippines.com/msds_2000data/msds.gasoil%20-%20diesel.html
121
References
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Ancheyta, CRC press Taylor & Francis group, 2013
20. Kohl, A.Riesenfeld Gas Purification 3rd Edition, Gulf Publication Company
21. Gianetto, A & Silverstone, P. Multi phase chemical reactors hemisphere
publishing corp.(1986)
22. Kern, D.C Process Heat Transfer McGraw-Hill Company Inc.(1963)
23. Coulson & Richardsons Chemical Engineering Vol 6, 4th edition, R. K. Sinnott
24. RULES OF THUMB FOR CHEMICAL ENGINEERS A manual of quick, accurate
solutions to everyday process engineering problems Fourth Edition Carl R. Branan,
Editor
25. Perry, Robert H., and Chilton, Cecil H., 1973, Chemical Engineers Handbook, Fifth
Edition, Mc Graw-Hill, New York.
26. Stephanopoulos, G. (1984) "Chemical process control, an introduction to theory and
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27. http://msds.chem.ox.ac.uk/SU/sulfur.html
28. http://msds.chem.ox.ac.uk/HY/hydrogen_sulfide.html
29. https://www.gdjones.co.uk/Content/UserFiles/files/TDS_GasOil.pdf
30. Chemical Process: Design and Integration by Robin Smith ISBN: 978-0-471-486817 712 pages January 2005,
31. http://www.itm-power.com/news-item/hydrogen-cost-structure-update
122