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Table of Contents
1Chapter 1
1O-Hydroxy benzoic acid and related compounds
1Introduction
15Chapter 2
15Process selection and description of flow sheet
15 Flow Sheet Selection
19Flow Sheet Description
21Chapter 3
21Material balance
24Chapter 4
24Energy Balance
30Chapter 5
30Design of Equipments
30 Design of CFSTR
42Flash Tank Design
52Design of Distillation Column
72Design of autoclave
96Design of Centrifuge
102Design of dryer
119Sublimation
127Chapter 6
127Instrumentation and process control
128Control scheme of distiallation column
131Chapter 7
131Basic principles of Hazop study
135Chapter 8
Potential Health Effect 121140Chapter 9
140Cost Estimation
141REFERENCES
Chapter No.1
O-HYDROXY BENZOIC ACID AND RELATED COMPOUNDSChapter 1O-HYDROXY
BENZOIC ACID AND RELATED COMPOUNDSIntroduction
Compounds of the general structure
Where the hydroxy is ortho [69-72- 7], meta [99-06.9], or para
[99-96-7] are commonly known as the monohydroxybenzoic acids. Of
the three acids, the ortho isomer, salicylic acid, is by far the
most important. The main importance of salicylic acid and its
derivatives lies in their antipyretic and analgesic actions (see
Analgesics, antipyretics, and anti-inflammatory agents). Natural
salicylic acid, which exists mainly as the glucosides of methyl
salicylate [119-38-6] and salicyl alcohol [90-01-7], is widely
distributed in the roots, bark, leaves, and fruits of various
plants and trees. As such, their use as preparations for ancient
remedies is probably as old as herbal therapy. Hippocrates
recommended the juice of poplar trees as treatment for eye
diseases. Salicyl alcohol glycosides (salicin) [138-52-3) occur in
Populous halsamifera (poplar) and Snlix helix (willow) trees.
Methyl salicylate glucosides occur in Betula (birch) and Togas
(beech) trees. A more familiar source of methyl salicylate is the
leaves of Gaultheria procumbens (wintergreen) (see also hydroxy
carboxylic acids).Free salicylic acid occurs in nature only in very
small amounts. It has been isolated from the roots, plants,
blossoms, and fruit of Spirctea ulmaria, from which its original
name, acidium spiricum, was derived. Salicylic acid as well as
salicyfiltes occur in tulips, hyacinths, and violets, and in common
fruits, eg, oranges, apples, plums, and grapes, which explains the
presence of salicylic acid in most wines (1 2).
Physical Properties. Salicylic acid is obtained as white
crystals, fine needles, or fluffy white crystalline powder. It is
stable in air and may discolor gradually in sunlight. The synthetic
form is white and odorless. When prepared from natural methyl
salicylate, it may have a lightly yellow or pink tint and a faint,
wintergreenlike odor. Hydroxybenzoic acid crystallizes from water
in the form of white needles and from alcohol as platelets or
rhombic prisms. p-Hydroxybenzoic acid crystallizes in the form of
monoclinic prisms. Various physical properties of hydroxybenzoic
acids are listed in Tables 14.
Table 1Physical Properties of Hydroxybenzoic Acids
PropertyValue (Isomer)
OrthoMetaPara
Molecular weight138.12138.12138.12
Melting point, oC15920L5-203214.5 215.6
Boiling point, oC211 swub
Density
1.497
Refractive Index1.565
Flash point (Tag closed-cup), oC1.57
Ka (acid dissociation) at 25oC1.05 8.3(10-52.6(10-5
Heat of combustion, mJ/molo3.0263.0383.035
Heat of sublimation, kJ/molo95.14116.1
To convert J to cal, divide by 4.184.
Table 2Solubilities of the Hydroxybenzoic Acids in Water, Wt
%
Temperature, oCIsomer
OrthoMetaPara
00.120.350.25
100.140.550.50
200.200.850.81
300.301.350.81
400.422.01.23
500.643.02.3
600.904.34.2
701.377.07.0
802.2111.012.0
Figure 1. Reactions of the carboxyl group of salicylic acid.
Reactions. The hydroxybenzoic acids have both the hydroxyl and
the carboxyl moieties and, as such, participate in chemical
reactions characteristic of each. In addition, they can undergo
electrophilic ring substitution. Reactions characteristic of the
carboxyl group include decarboxylation; reduction to alcohols; and
the formation of salts, acyl halides, amides, and esters. Reactions
characteristic of the phenolic hydroxyl group include the formation
of salts, esters, and ethers. Reactions involving form sodium
salicylate. However, if salicylic acid dissolves in the presence of
alkali metals or caustic alkalies, e.g., excess sodium hydroxide,
the disodium salt forms.
Salicylic acid can be converted to salicyloyl chloride by
reaction with thionyl chloride in boiling benzene. However, the
formation of acyl halides can be complicated by the presence of the
phenolic hydroxyl. For example, the reaction with phosphorus to
arid pentachlorides is not restricted to the formation of the acid
chloride. Further interaction of the phosphorus halide and the
phenolic hydroxyl results in the formation of the phosphoric or
phosphorous esters.
The formation of amides can be accomplished by the dehydration
of the ammonium salt of salicylic acid. The more common method for
amides is the reaction of the ester, acylhalide, or anhydride with
an amine or ammonia. Each step is fast and essentially
irreversible.
Esterification is frequently carried out by direct reaction of
the carboxylic acid with an alcohol in the presence of a small
amount of mineral acid, usually concentrated sulfuric or
hydrochloric acid. The ester of commercial importance is methyl
salicylate. Direct esterification has the advantage of being a
single-step synthesis; its disadvantage is the reversibility of the
reaction. The equilibrium can be shifted to the right if either raw
material is used in large excess, or by selective removal of one of
the products. One less frequently employed technique is the
transformation of the acid to the acid chloride followed by
alcoholysis; each step is essentially irreversible. Another method
is the reaction of the alkali salt, eg, sodium salicylate, with an
alkyl or an aryl alkyl halide.
Hydroxyl. The hydroxyl group is alkylated readily by the sodium
salt and an alkyl halide (Williamson ether synthesis) (see Fig. 2).
Normally, only O-alkylation is ob ring substitution includes
nitration, sulfonation, halogenation, alkylation, and acylation.
The following reactions are illustrated only with salicylic acid;
however, these reactions are characteristic of all the
bydroxybenzoic acids.
Table 3 Solubilities of the Hydroxybenzoic Acids in Non aqueous
Solvents, Wt %
SolventIsomer
OrthoMetaPara
Acetone at 23oC396327285
Benzene at 25 oC0.7750.0100.0035
1-butanol
Ethanol (99 wt %)
n-heptane
Methanol at 15 oC39.8740.3836.22
Carbon tetrachloride at 25 oC0.262
Chloroform (satd in H2O) at 25 oC1.84
Ethanol (abs) at 21 oC34.87
I-propanol at 21 oC27.36
Table 4 Saturated Vapor Pressure (p) of o- and p-Hydroxybenzoic
Acids
Temperature,oCo-Hydroxybenzoic acidp, Pabp-Hydroxybenzoic acidp,
Pab
9530.9
10048.7
10570.1
110104
115153
120220
1253223.03
1304.59
1356496.94
14010.6
14516.1
15023.9
15534.6
15947.3
B. To convert Pa to mm Hg, divide by 133.3.
Salicylic Acid
Reactions: Carboxyl. Typical decarboxylation by simple heating
of a free acid occurs with only a few types of acids. However,
decarboxylation of salicylic acid takes place readily because of
the presence of the hydroxyl group, which is electron donating (see
Fig. 1). Upon slow heating, salicylic acid decomposes to phenol and
carbon dioxide; when heated rapidly, it sublimes.
Generally, the carboxyl group is not readily reduced. Lithium
aluminum hydride is one of the few reagents that can reduce an acid
to an alcohol. The scheme involves the formation of an alkoxide,
which is hydrolyzed to the alcohol. Commercially, the alternative
to direct reduction involves esterification of the acid followed by
reduction of the ester.
Salicylic acid dissolves in aqueous sodium carbonate or ~odium
bicarbonate to serve. However, phenolate ions are ambident
nucl~ophiles and, as such and under certain conditions, as with the
use of alkyl halides, the problem of C- versus O-alkylation can
occur. Either reaction can be made essentially exclusive by the
proper choice of reaction conditions. For example, polar solvents
favor formation of the ether, whereas nonpolar solvents favor ring
substitution (see Alkylation).
Figure 2. Reactions of the hydroxyl group of salicylic acid.
Esters of the phenolic hydroxyl are obtained easily by the
Schotten-Baumann reaction. The reaction in many cases involves an
acid chloride as the acylating agent. However, acylation can also
be achieved by reaction with an acid anhydride. The single most
important commercial reaction of this type is the acetylation of
salicylic acid with acetic anhydride to yield acetylsalicylic acid
[50-78-2] (aspirin).
Ring Substitution. In the introduction of a third group into a
disnbstituted benzene, the position the group takes depends on the
groups present (see Fig. 3). In the case of salicylic acid the
hvdroxyl directs ortho and pan and the carboxyl directs meta
substitution. It is generally accepted that if both an ortho-para
and a meta director are competing for the orientation of a third
group, the ortho-para director prevails since, unlike the meta
director, it activates the ring. Specifically, the hydroxyl group
is electron-donating which, on the basis of resonance
considerations, increases the
Figure 3 Ring-substitution reactions of salicylic acid. X =
halogen.
Electron density in the S and 5 positions. The
electron-withdrawal nature of the car-boxyl group decreases the
electron density around the 4 and C positions, which further
enhances the electron density of the 3 and 5 positions. As a rule,
direct substitution occurs more easily in the less sterically
hindered 5 position, but most often small amounts of the 3
substituted and 3,5-disubstituted product also form. High yields of
the 3-substituted salicylic acid usually can only be prepared
indirectly.
Direct halogenation of salicylic acid is generally carried out
in glacial acetic acid. As expected, the main product is the
5-halo-salicylic acid with small quantities of the 3-halo- and 3,
5-dihalosalicylic acids.
Reaction with cold nitric acid results primarily in the
formation of 5-nitrosalicylic acid [96-97-9]. However, reaction
with fuming nitric acid results in decarboxylation as well as the
formation of 2, 4, C-trinitrophenol [88-89-1] (picric acid).
Sulfonation with chlorosulfonic acid at 16OoC yields
5-sulfosalicylic acid [56507-30-3]. At higher temperatures (1800 C)
and with an excess of chlorosulfonic acid, 3,5-disulfosalicylic
acid forms. Sulfonation with liquid sulfur trioxide in
tetrachloroethylene leads to a nearly quantitative yield of
5-sulfosalicylic acid (5).
Because salicylic acid contains the deactivating meta-directing
carboxyl group, Friedel-Crafts reactions (qv) are generally
inhibited. This effect is somewhat offset by the presence of the
activating hydroxyl group. Salicylic acid also reacts with isobutyl
or t-butyl alcohol in 80 wt % sulfuric acid at 750C to yield
5-t-butylsalicylic acid [16094-31-8]. In the case of isobutyl
alcohol, the intermediate carbonium ion rearranges to (CH3)3C+.
Miscellaneous. The Reimer-Tiemann reaction of salicylic acid
with chloroform and alkali results in the 3- and 5-formyl
derivatives.
If the reaction is carried out with carbon tetrachloride, the
corresponding dicarboxylic acids form.
Alkylation involving formaldehyde in the presence of hydrogen
chloride is known as chloromethylation. The reagent may be a
mixture of formalin and hydrochloric acid, paraformaldehyde and
hydrochloric acid, a chloromethyl ether, or a formal. Zinc chloride
is commonly employed as a catalyst, although many others can be
used. Chloromethylation of salicylic acid yields primarily the
5-ubstituted product.
The reaction of salicylic acid with formaldehyde with catalytic
amounts of acid results in the condensation product methylene-5,
5-disalicylic acid [122-25-8].
Salicylic acid, upon reaction with amyl alcohol and sodium,
reduces to a ring-opened aliphatic dicarboxylic acid, ie, pimelic
acid. The reaction proceeds through the intermediate
cyclohexanone-2-carboxylic acid.
During certain substitution reactions, the carboxyl group is
often replaced by the entering group. Au example is fuming nitric
acid, which results in the formation of trinitrophenol. Another is
the bromination of salicylic acid in aqueous solution to yield the
tribromophenol derivative.
Salicylic acid couples with diazonium salts in the expected
manner. With diazotized aniline, i.e, benzenediazonium chloride,
the primary product is 5-phenylazosalicylic acid [314 7-53-3].
The close proximity of the carboxyl and the hydroxyl groups can
be used for beterocyclic synthesis, as in the preparation of
hydroxyxanthones (6).
USES
Approximately 60% of the salicylic acid produced in the United
States is consumed in the manufacture of aspirin: this statistic
has remained relatively constant for at least the last ten years.
Approximately 10% of the salicylic acid produced is consumed in
various applications, eg, foundry and phenolic resins, rubber
retarders, dyestuffs, and other miscellaneous uses. The remaining
30% is used in the manufacture of its salts and esters for a
variety of applications.
There are many foundry-resin systems in use. Salicylic acid is a
small component only in the Shell process. It is used as a
cross-linking agent in the phenolfornrnldehyde resin used as a sand
core and mold binder and imparts higher tensile strength. More
recent developments have demonstrated that higher concentrations of
salicylic acid than previously used further improve cold and hot
tensile strength and reduce cure and machine processing time (18).
The continuing interest in energy and environmental considerations
has led to the low energy processes, which typically do not use
salicylic acid. Their growth has been somewhat limited because of
the large capital expenditures required; however, the economics is
expected to shift as the cost of energy increases. Therefore, a
zero or small negative growth for salicylic acid is predicted in
foundry-resin applications. Salicylic acid has also been used in
other phenolic resin applications, ie, binders for grinding wheels,
fiber glass, and brake linings (qv) (see Phenolic resins).
Chapter No. 2
Process Selection and Description
Of Flow Sheet
Chapter 2 Process Selection and Description of Flow SheetFIRST
SYNTHESIS
Salicylic acid was first prepared by R.Piria by the fusion of
salicyaldehide with the potassium hydroxide. In 1859, a synthesis
method of preparing salicylic acid was discovered by treating the
phenol with carbon dioxide in presence of metallic sodium. However
the only commercial method of manufacturing salicylic acid until
1874 was the sponification of the methyl salicylate obtained from
the leaves of the winter green or Bark of the birch.
KOLB PROCESS The first technically suitable process was
introduced in 1874 by Kolb. It involves the reaction of the dry
sodium phenolate with carbon dioxide under pressure and high
temperature (180-200) 0C. The drawback of the process was that the
yield was not more than 50% and the separation of byproducts which
were in large quantity was difficult. Salicylic acid is
manufactured by the reaction of phenol with caustic soda and the
subsequent treatment of the sodium phenolate formed with carbon
dioxide and acidifying the resultant product with the sulfuric acid
.Phenol and caustic soda are charged in equomolar proportions to a
mixer. The resulting solution is heated to a temperature of 1300C
and further evaporated to dryness in a stirred autoclave or a
heated ball mill. Dry carbon dioxide gas is absorbed and the crude
product from the autoclave is dissolved in the equal amount of
water and filtered. The filtrate is precipitated and dried.To
obtain pure product, the crude sodium salicylate solution
decolorized with the activated carbon containing the zinc dust and
filtered. The clarified filtrate is acidified with the excess of
sulfuric acid to precipitate the salicylic acid which is
centrifuged and dried to give the high grade salicylic
acid.SCHMITT
Schmitt introduced the new lower temperature ranges from
120-1400C which significantly increased the yield of the process.
The reaction of the carbon dioxide on the phenol forms an
intermediate phenyl carbonate which rearranges itself to give
o-sodium salicylate. The Kolb-Schmitt synthesis method is still the
only industrial process in use in different modifications.
More, et al
More introduced a new step process for the carbonation of dry
sodium phenolate. The reaction is carried out in a stirred reactor.
Carbon dioxide is passed at a temperature of 1300C until 25% of the
stiochiometeric amount of the carbon dioxide is absorbed. In step
11 the temperature of the raised to 2100Cand the remaining carbon
dioxide is introduced into the reactor for 5 hr. the yield of the
process was 80 to 82% and for time duration the yield was 76%.
Stopp,et al
The carbonation of the sodium salicylate is carried out in a
fluidized bed reactor at 1400C and pressure of 6bar until half of
the phenolate is converted to salicylate. The resulting reaction
mixture can be further carbonated in a subsequent stage at a
temperature of 2100Cand a pressure of 10 bars. The subsequent stage
may be fluidized bed reactor or stirred vessel. The yield was
85%.
Barkley et al
The sodium phenolate was cooled to 900C. The carbon dioxide was
passed into the autoclave; the temperature was maintained at 1200C
until the carbon dioxide adsorption was come to an end. The
temperature was raised to induced rearrangement of the intermediate
product. The temperature was kept 160-1700Cunder a carbon dioxide
pressure 5 bar.
Jenson, et at
An improved method for the production of salicylic acid from
phenol with high degree of conversion and with a significant
reduction in the by products was modified by Jenson and his
colleagues. The process comprises of reaction of sodium phenolate
with the carbon dioxide indirect single step at a temperature above
1650C.In the Kolb carboxylation, the reaction between sodium
phenolate with carbon dioxide could advantageously takes place in
single step well the temperature at which sodium phenyl carbonate
is ordinarily converted to sodium salicylate. More particularly
instead of introducing carbon dioxide below 1500C to produce sodium
phenyl carbonate which is then in second step is converted to
sodium salicylate being held above 1650C.
Our contributions
The reaction of sodium phenolate and carbon dioxide is slowest
reaction in whole plant so every scientist focused his attention
for finding the set of thermodynamics properties that would give
maximum conversion and minimum byproduct as well as cost factor
would remain under considerations along with the safe
operation.
I was personally interested in finding such data to improve the
performance of the plant used for manufacturing of salicylic acid.
The autoclave present in our department was quite unsuitable for
the reaction of carbon dioxide with sodium phenolate at different
temperature and pressure. But fortunately the circumstances for
carrying the experiments in determination the kinetic data I was
given opportunity in the chemistry department lab. I performed
number of experiment at different temperature and different speed
of agitation in simple conical flask.
After the result of experiment I decided batch reaction was not
economical.
So I made changes in the flow diagram available in
literature.
FLOW SHEET DESCRIPTION
Preparation of Sodium Phenolate
Phenol is approximately 54% is reacted with 50%caustic soda in a
CFSTR. The reaction temperature is 95-990C. The reaction is
exothermic; heat evolved from the reaction is utilized raising the
temperature of the product to 990C. Slightly excess amount of
phenol is fed into the reactor instead of caustic soda because of
material of construction is greatly influenced by the strong
alkali. The reaction temperature is so high that lump formation of
sodium phenolate is out of question. Preparation of Sodium
salicylate The product of the first reactor is fed into the flash
tank where separation of water is carries out and then for any
batch valve is opened and autoclave is charged and valve of the
carbon dioxide is opened at the pressure of 8bars for the time of
5-6hrs. The reaction temperature is raised to about 1250C.
Almost 70% conversion is achieved; carbon dioxide released is
recycled back and then utilized. Now 600Kg of phenol is added so
that some sort of azeotrope is formed and when steam is provided,
this mixture is vaporized leaving the thick slurry of sodium
salicylate. The evaporated material is condensed and sent into the
continuous distillation column where separation of phenol and
sodium phenate is carried out.
Acidification tank
The product of the autoclave is thick slurry and it is diluted
with the water in the dilution tank. The solution, so obtained is
charged into the acidification tank where 40% sulfuric acid is
reacted that comes from the storage tank of sulfuric acid. Almost
two hr along with agitation gives 100 app. Conversion. In the
acidification tank solid salicylic acid as well as sodium sulfate
is formed
Purification from water (removal of water)
Removal of water is carried in two steps: in first step
centrifuge removes the large amount of water i.e. from 66 to 16
%water content. The waste water is sent to the waste water
treatment plant. The solid product that contains salicylic acid and
sodium sulfate is sent to the dryer where app. All water content is
removed.
Sublimation and crystallization The solid product is charged
into the sublimation tank where steam is used as heating medium and
vacuum is created with the help of vacuum pump. At reduced pressure
the sublimation of salicylic acid is carried out at 760C. The
vapors coming from the sublimation tank are injected into
crystallizer where condensation of vapors takes place resulting
more than 99% pure product.
Chapter No. 3
Material Balance
Chapter 3
Material Balance
Reactor-1
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH10.65625426.2515.643750.1566.240.22902697
H2O66.480561196.6543.9181176.980561385.6550.8575665
phenol11.72161101.8340.438141.22114.684.20910456
Na-Ph00010.5121844.704302
total88.85842724.7310088.856562724.57100
FLASH TANK
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH0.1566.240.2290270.1566.240.45868862
H2O76.980561385.6550.857571.944444352.57277271side stream
Phenol1.22114.684.2091051.07617101.167.43604822
Na-Ph10.5121844.704310.5121889.5324904water-out1350.65
88.856562724.5710013.676611360.4100total2711.05
phenol13.52
Autoclave reactor-2
Addition of CO2 and reaction
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH0.1566.240.3259510.1566.240.36897969
H2O1.944444351.8282491.9444352.06959761
Phenol1.07617101.165.2841621.07617101.165.98172841side
stream
Na-Ph10.5121863.623073.15365.421.6065991CO2231
CO212.655428.9385700
Na-Sal007.351183.3569.9730952
1914.41001691.15100
Addition of phenol and separation of azeotrope
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH0.1566.240.2847820.1566.240.50849529
H2O1.9444351.5973351.9444352.85213707
Phenol6.395319601.1627.435820.012341.160.09452797side stream
Na-Ph3.15365.416.676170.0120691.40.11408548phenol600
CO200000Na-Ph364
Na-Sal7.351183.3554.005897.351183.3596.4307542
2191.151001227.15100
Dilution tank
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH0.1566.240.5084950.1566.240.16949843
H2O1.9444352.852137138.29442489.367.617379
Phenol0.012341.160.0945280.012341.160.03150932
Na-Ph0.0120691.40.1140850.0120691.40.03802849side input
CO2000000water2454.3
Na-Sal7.351183.3596.430757.351183.3532.1435847
1227.151003681.45100
Acidification tank
inputoutput
component(Kgmol)Kg%WtKgmolKg%Wt
NaOH0.1566.240.169498000
H2O138.29442489.367.61738168.53063033.5566.0226652
Phenol0.012341.160.0315090.012341.160.02524642
Na-Ph0.0120691.40.0380280.0120691.40.03046982
salicylic acid0007.351014.322.0753867
Na-Sal7.351183.3532.14358000
Na2SO40003.815845541.8511.7929097
side input0
sulfuric acid362.62.450.05332219
water543.94594.71100
4587.95
Centrifuge
inputoutputside stream
component(Kgmol)Kg%WtKgmolKg%WtKgmolKg%Wt
NaOH000000000
H2O168.53063033.5566.0226716.46667296.416.0044493152.06392737.1599.79673
Phenol0.012341.160.0252460.0017020.160.008639380.0106310.03646
Na-Ph0.0120691.40.030470.0034480.40.021598450.00862110.03646
salicylic acid7.351014.322.075397.351014.354.7682622000
Na-Sal000000000
Na2SO43.815845541.8511.792913.799296539.529.13090552.35/1422.350.085681
sulfuric
acid2.450.0533220.01251.2250.066145240.01251.2250.044664
4594.711001851.9851002742.725100
Drying unit
inputoutputside stream
component(Kgmol)Kg%WtKgmolKg%WtKgmolKg%Wt
NaOH000000000
H2O16.46667296.416.004450.1644442.960.1900896516.30222293.4499.53023
Phenol0.0017020.160.0086390000.0017020.160.054269
Na-Ph0.0034480.40.0215980.0034480.40.02568779000
salicylic acid7.351014.354.768267.351014.365.137815000
Na-Sal000000000
Na2SO43.8539.529.130913.8539.534.6464076000
sulfuric acid0.01251.2250.0661450000.01251.2250.415501
1851.9851001557.16100294.825100
Sublimation unit and Crystallization
inputoutputside stream
component(Kgmol)Kg%WtKgmolKg%WtKgmolKg%Wt
NaOH000000000
H2O0.1644442.960.190090.0694441.250.123365410.0951.710.345829
Phenol00000000
Na-Ph0.0034480.40.0256880000.40.080896
salicylic
acid7.351014.365.137817.333333101299.87663462.30.46515
Na-Sal00000000
Na2SO43.8539.534.64641000539.5109.1081
sulfuric acid00000000
1557.161001013.25100543.91110
Chapter No.4
ENERGY BALANCE
Chapter 4
ENERGY BALANCE FOR THE PROJECT
REACTOR 1 ENERGY BALANE :
HR = Hfp - H fr
= { 10.656*(-326.6) + 10.656(-258.84)}{10.656(-165) +
10.656(-426.99)}
HR= 59.247 KJ
TOTAL HEAT RQUIRED = mCp dT + HR= (1.22*220.53KJ/Kgmol.K *
5)phenol+ (76.98*75*5)water+(10.5*243.17*5) + 0.156*78.62*5 +
59.247 KJ
H= 43099 KJ
ENERGY BALANCE OF AUTOCLAVE:
1 ST STEP : SEPARATION OF WATER
TOTAL HEAT RQUIRED = sensible heat + latent heat
= { 0.156*78*7}NaOH + { 76.98*75*7}water +{1.22*298*17}phenol+{
10.5*243*7}Na-ph + {1350.65*2551.6}water+ { 13.52/94 *45700
KJ/Kgmol}phenol= 3513130.53 KJ
2nd STEP: ADDITION OF CO2 AND REACTIONHEAT OF REACTION = HR =
HFP + HFR
LATENT HEAT REQUIRED = (12.6* 38.65*95)CO2+ 0.156*78*78)NaoH +
(1.944*75*18)H2O + (1.07117*220*18)phenol
+(10.5*243.17*18)Na-ph
= 99310 KJ
TOTAL HEAT RQUIRED = H = Hl + HR = 0
Hl = HR
Hl = nHfp - nHfr,
nHfr + Hl = nHfp7.35(-393.51* 1000) +7.35(-453*1000) = -7.35*
X
X = 859.511 KJ/gmol
5% loss so,
X= 904.74 KJ/gmol
3rd step: addition of phenol and separation of azeotropeSIMPLE
VACUUM SEPARATING THE COTENTSENERGY BALANCE OF DILLUTION TANKHeat
balance:
137*75*(T-25)= {( 0.156*78*(125-T))NaOH +(1.944*75*(125-T))H2O
+(0.01234*220*(125-T))phenol+(7.35*257.76*(125-T))sod.sal
+(0.012069*243*(125-T))Na-phenTherefore,
1521+18228.75+339.35+236817+3665.96+256875=T{1027512.168+145.8+2.7148+1894.536+2.93)}
T =62.97 C
ACIDIFICATION TANKHR = nHfp - nHfr{-96909+(9703*44)}*1000=
{3.81158*(-1384.5*1000)KJ+
7.35*(-589.5*1000)}-
{(-904*7.35)+(-811*3.69)+0.156*(-426)}*1000
HR = 93480 KJ
This much amount of heat is contained after the reaction in the
system.
Now reaction temp. is 20 C
Heat balance: Heat input = Heat out put
{3.69*137.777*5}H2SO4 +{ 30.22*75*5}water+ {
0.156*78*(63-20)}NaOH +{138.2944*75*(63-20)}water + {
0.01234*220*43}phen + {0.0120*69*243.17*(63-20)}Na-phen +
{7.35*257.76*43}Na-sal
= 542097.75 KJ
This much amount is contained in the system before reaction
occurs.
Now the total amount of heat that must be rejected to keep the
system at 20C
= 542097.75 + 93480 = 635575.73
Chapter No. 5
Design of Equipments
Chapter 5 Design of Equipments
REACTOR DESIGN
Reactor selection
I selected the CSTR
Reactor selection criteria
1- Conversion
2- selectivity
3- productivity
4- safety 5- economics
6- availability
7- flexibility
8- compatibility with processing
9- energy utilization
10- feasibility
11- investment operating cost
12- heat exchange and mixing
Kinds of impellers
A rotating impeller in a fluid imparts flow and shear to it, the
shear resulting from the flow of one portion of the fluid past
another. Limiting cases of flow are in the axial or radial
directions so that impellers are classified conveniently according
to which of these flows is dominant. By reason of reflections from
vessel surfaces and
obstruction by affles and other intemals, however, flow patterns
in most cases are mixed. When a close approach to axial flow is
particularly desirable, as for suspension of the solids of a
slurry, the impeller may be housed in a draft tube; and when radial
flow is needed, a shrouded turbine consisting of a rotor and a
stator may be employed. Because the performance of a particular
shape of impeller
usually cannot be predicted quantitatively, impeller design is
largely an exercise of judgment so a considerable variety has been
put forth by various manufacturers. A few common types are
illustrated on Figure 10.2 and are described as follows:
a. The three-bladed mixing propeller is modelled on the marine
propeller but has a pitch selected for maximum turbulence. They are
used at relatively high speeds (up to 1800rpm) with low viscosity
fluids, up to about 4000cP. Many versions are available: with
cutout or perforated blades for shredding and breaking
up lumps, with sawtooth edges as on Figure 10.2(g) for cutting
and tearing action, and with other than three blades. The
stabilizing ring shown in the illustration sometimes is included to
minimize shaft flutter and vibration particularly at low liquid
levels.b. The turbine with flat vertical blades extending to the
shaft is
suited to the vast majority of mixing duties up to 100,000 CP or
so at high pumping capacity. The simple geometry of this design and
of the turbines of Figures 10.2(c) and (d) has inspired extensive
testing so that prediction of their performance is on a more
rational basis than that of any other kind of impeller. c. The
horizontal plate to which the impeller blades of this turbine are
attached has a stabilizing effect. Backward curved blades may be
used for the same reason as for type e.
d. Turbine with blades are inclined 45" (usually). Constructions
with two to eight blades are used, six being most common. Combined
axial and radial flow are achieved. Especially effective for heat
exchange with vessel walls or internal coils.
e. Curved blade turbines effectively disperse fibrous materials
without fouling. The swept back blades have a lower starting torque
than straight ones, which is important when starting up settled
slurries. f. Shrouded turbines consisting of a rotor and a stator
ensure a high degree of radial flow and shearing action, and are
well adapted to emulsification and dispersion. g. Flat plate
impellers with sawtooth edges are suited to emulsification and
dispersion. Since the shearing action is localized, baffles are not
required. Propellers and turbines also are sometimes
provided with sawtooth edges to improve shear. b. Cage beaters
impart a cutting and beating action. Usually they are mounted on
the same shaft with a standard propeller. More violent action may
be obtained with spined blades. SHAFT
The shaft is vital component of the agitator and frequently
limits its mechanical performance. In addition to transmitting
torque, the shaft undergoes bending, and if not stiff enough or
rigidly supported, it may vibrate badly and cause discomfort to
personnel or damage to the equipment. Therefore it must be analyzed
for combined torsional and bending stresses, deflection, and
critical speed and must be selected to meet the limiting criteria
for each. Inadequately in these respects can result in failure of
the shaft by overstress, failure of the seal due to excessive shaft
bending, or failure of bearings due to wear or impact Torsional and
bending stresses calculation
COUPLINGS
Most agitators with long overhung shaft have rigid couplings to
connect the agitator shaft and the gear reducer output shaft. The
coupling facilities shipment, installation, removal and servicing
of the agitators. Although it is an innocuous appearance block of
metal, care in its design and fabrication can contribute
significantly towards the satisfactory performance of the agitator.
The reasons for this become manifest from the requirement that the
rigid coupling must meet
1- the coupling must be capable of transmitting the agitator
torque
2- the coupling must provide at least as much rigidity as the
shaft if the critical speed of the agitator is not to be reduced
.
3- the coupling must strong enough to withstand the bending
moments imposed upon it by the unbalanced hydraulic and centrifugal
force.
4- The coupling must provide good alignment between the shafts
being connected
5- Because it must be assembled and disassembled in the field,
frequently under inconvenient working condition, the coupling
should be relatively easy to take apart and reassembled, and should
preferably be self-aligning.
6- The coupling must be capable of taking the thrust due to
weight of the agitator.
DRAFT TUBES
A draft tube is a cylindrical housing around and slightly larger
in diameter than the impeller. Its height may be little more than
the diameter of the impeller or it may extend the full depth of the
liquid, depending on the flow pattern that is required. Usually
draft tubes are used with axial impellers to direct suction and
discharge
Streams. An impeller-draft tube system behaves as an axial flow
pump of somewhat low efficiency. Its top to bottom circulation
behavior is of particular value in deep tanks for suspension of
solids.calculationsSodium hydroxide concentration calculation
NaOH added = 10.656 Kgmol = 426.25 Kg
Water added = 66.48 Kgmol = 1196.65 Kg
Density of NaOH = 1023.7 Kg/M3
Density of water = 997Kg/M3
Total volume of the mixture = V1+V2+dV
whereV1 is partial volume of NaOH
V2 is partial volume of water
dV is change in volume due to solubility
426.25 1196.65
V = ---------- + -----------
1023.7 997
= 1.617 M3
Reactor volume and dimensions calculations 10.656
= -----------
1.617
= 6.59 Kgmol/M3
CA0 = 6.59 gmol/lit
V Xa
-------- = --------- = 342 (from graph)
Fa0 - Ra
V = 0.12233*25*342
= 1.055 M3
V = 2.1 (50% reactor is filled) prove it
:
Basic equation used for calculating reactor volume =
(XA
Vf = FA0 (------------)
- rA
Vf = 1.35 m3 Vf = volume of fluid
V = 2.1 m3 (73% fill) V = volume of vessel
D = 1.2 m D = diameter of vessel
H = 1.2 m H = height of fluid
L= 1.87 m L = length of vessel
Selection and geometry of Impeller
I selected the 300 curved, square pitched turbine blade with
the
Following specifications:
S-1 = Da/Dt = 0.33
S-2 = E/Dt = 0.33
S-3 = L/Da = 0.25
S-4 = W/Da = 0.20
S-5 = J/Dt = 0.0833
S-6 = H/Dt = 1.00
No. of baffles = 4 (no clearance, not twisted but adjacent
with
wall of the vessel )
Power calculation:
P =Np0(Nr3)(Da)5( = Kt (Nr3)(Da)5( = 0.34 Kw =0.45 hp
= 0.55 (82 % efficiency of the motor)
SHELL THICKNESS
X=
P=Pressure of system
=Radius of shell
S=Stress of material
Ej=Efficiency of joint
Cs=Corrosion rateik
X=
=5.502 mm
HEAD THICKNESS
Pressure at the lease=(gh
=1080.46 9.8 4.43
= 46.907 KPa
Total pressure at base=827.697 KPa
t=
=
=5.84 mm
Power number, N, = Pg,/N3D5p, against Reynolds number, NRe =
NDzp/p, for several kinds of impellers: (a) helical shape (Oldshue,
1983); (b) anchor shape (Oldshue, 1983); (c) several shapes: (1)
propeller, pitch equalling diameter, without
baffles; (2) propeller, s = d, four baffles; (3) propeller, s =
2d, without baffles; (4) propeller, s =2d, four baffles; (5)
turbine impeller, six straight blades, without baffles; (6) turbine
impeller, six blades, four baffles; (7) turbine impeller, six
curved blades, four baffles; (8) arrowhead turbine, four baffles;
(9) turbine impeller,inclined curved blades, four baffles; (10)
two-blade paddle, four baffles; (11) turbine impeller, six blades,
four baffles; (12) turbine impeller with stator ring; (13) paddle
without baffles (data of Miller and Mann); (14) paddle without
baffles (data of White and Summerford). All baffles are of width
0.1D [after Rushton, Costich,
and Everett, Chem. Eng. Prog. 46(9), 467 (1950)l.
Specification Sheet
Identification:Item :
CFSTR ( Continuous Flow Stirred Tank Reactor)
Item no:
R-01
No.required:
01
Function:
Formation of sodium phenate from carbolic acid and caustic
soda
Operation:
Continuous
Type:
Agitator cylindrical vessel
Design Data:Vessel:
Working Volume1.35 m3
Design Volume1.86 m3
Temperature (Process temperature)99C
Design Temperature109C
Working Pressure1 atm
Design Pressure1.5 atm
Dia of Vessel1.2 m
Height of vessel1.56 m
Working height1.2 m
Height to dia ratio1.3
Type of headTorispherical
Thickness of cylindrical protion
Thickness of bottom head
No. of baffle
Width of Baffle
Height of baffle
Agitator:
Following specifications:
S-1 = Da/Dt = 0.33 S-2 = E/Dt = 0.33 S-3 = L/Da = 0.25 S-4 =
W/Da = 0.20 S-5 = J/Dt = 0.0833
S-6 = H/Dt = 1.00
No. of baffles = 4 (no clearance, not twisted but adjacent with
wall of the vessel )
Flash tank design
The name originate from the fact that a liquid at a pressure
equal to or greater than its bubble point pressure flashes or
vaporizes, when the pressure is reduced below its bubble point
pressure producing two phase system of liquid and vapor in
equilibrium. Basic equations used in flash calculation are
L + V = 1 (material balance equation)
Ki =Yi/Xi
Where Ki equilibrium constant
Yi vapor phase composition
Xi liquid phase composition
From Raults and Henry Law
Yi(iP = XiiPisat
(I = 1 for low to moderate pressure
i = 1 assumption as no data is available in literature
Zi Ki
Yi = ----------------------
1+V(Ki 1)
Zi
Xi = -----------------------
1+V (Ki 1)
for flash calculation necessary condition
P dew < P< Pbubble
Very important equation used in flash calculation
i - idew (i - (idew P P dew
---------------- = ---------------- = --------------------
i bubble -idew (I bubble - (idew Pbubble - Pdew
V - 1
= ---------------
0 - 1
P P dew
= -----------
Pbubble - Pdew
P - P dew
V = ---------------------
P bubble P dew
P bubble = X1P1sat +X2P2sat ..
1
P dew = ------------------ Y1/P1sat+Y2/Psat Throttling Valves
Globe Valve is an economical throttling valve. Its heavy duty
design provides for long service life. The in-line globe design
causes relatively high pressure drops, however this is a desirable
valve due to its economy and reliability.
Features 1- Slow closing
2- Prevents water hammer in PVC piping
3- Heavy Duty Construction
4- Long service life
5-efficient throttling with minimum wire drawing or disk or seat
erosion
6-available in multiports- short disk travel and fewer turn to
operate, saving time and wear on stem and bonnet
Jet Ejector
The two most common ejectors are operated by water or steam. The
liquid ejectors are used for creating a modest vacuum or for mixing
liquids. The steam ejectors is important in creating and holding a
vacuum in a system. Ejectors have no moving parts and operated by
the action of one high pressure steam entraining and other vapors
(or liquids) at low pressure into a moving stream and thereby a
removing them from the process system at an intermediate
pressure
Feature
Ejectors have the following features which make them good choice
for continuously producing economical vacuum condition.
1- They handle wet, dry or corrosive vapor mixtures
2- They develop any reasonable vacuum needed for industrial
operation.
3- All sizes are available to match any small or large capacity
requirement.
4- Their efficiencies are reasonable to good.
5- Have no moving parts, hence maintenance low, operation fairly
constants when corrosion is not a factor.
6- Quiet operation.
7- Stable operation within design range
8- Installation cost relatively low when compare to mechanical
vacuum pumps.
9- Space requirement is small
10- Simple operation.
Types
Ejectors may be single or multi-stage. The extra stages, with or
without inter stage condensing of steam; allow the system to
operate at lower absolute pressure than a single stage unit.
Various combinations of series of jets with no inter-condensing can
be connected to jets with inter-condensers or after condensers to
obtain various types of the operation and steam economy.
Material of construction
Since the ejector is basically simple in construction, it is
available in many material suitable for handling corrosive vapors.
Standard materials include cast iron, meehanite, cast steel, and
bronze for the body and diffusers depending upon the pressure and
temperature rating. The nozzle is usually stainless steel or monel.
Other material of construction include porcelain, carbon graphite,
impregnated graphite, synthetic resins, glass and special metal of
all types
DEMISTERS OR IMPINGENT SEPARATOR
As the descriptive name suggests, the impingement separator
allows the particles to be removed to strike some type of surface.
This action is better accomplished in pressure system where
pressure drop can be taken as a result of turbulence which
necessarily accompanies the removal action. Particles removed in
stream line flow is less efficient than for turbulent flow and not
be effective if the path of travel is not properly well
baffled.
There is basically three construction type for impingement
separators.
1-wire mesh
2- Plates (curved, flat or special shaped)
3-packed impingement beds
A demister pad resembles a giant brillo pad with the soap. Many
process plants have discarded demister pads lying around their
scrape heaps. The theory of operation of demister is simple. Vapors
and droplets of liquids strike the demister pad with a sustainable
velocity. The force of this impingement velocity causes the tiny
droplets. The heavier droplets of liquid to coalesce into large
droplets.
For knockout drum with a demister pad it apparently must have
K-value of at least
0.15 to 0.20 When a demister plugs it increases the pressure
drop of the vapor, but pressure drop cannot increase a lot because
the demister will break. Demister failure creates two problems.
1- The dislodged section of the demister pad are blown into down
stream equipment as into suction of the centrifugal wet gas
compressor
2-the failed demister promotes high localized velocities. Vapors
blows through the open areas of the vessel. The remaining section
of the demister pad impedes vapor flow. The resulting high
localized velocities of vapors creates more entrainment than we
could have without any demister
Steam trap
A steam trap is self actuating automatic drain valve in a steam
distribution system that performs the following functions.
1- Removal of condensate
2-Remove air or other noncondensible gases
3- Prevents or limits the loss of steam
Condensate (water) is formed when steam condenses to release
latent heat. Some heat is released in the distribution system in
the form of unavoidable losses. Most of the heat is utilized in the
process equipment. Once steam has condensed, the hot condensate
must be removed immediately as it hinders effective heat transfer
from the incoming steam. By selectively purging a steam system of
its condensate and noncondensible, steam trap helps maintain high
heat transfer coefficient in equipment without losing live
steam
In the recent years user interest in steam trap has closely
paralleled the increase in energy cost. High fuel cost associated
with the malfunctioning trap cannot be ignored. Spiraling cost have
highlighted the need for optimum steam trap selection and
application. Experience indicates that improper selection and
application are the most frequent cause of the trap failure and
steam loss. The installation or the replacement of steam trap has a
pay back period of as little as three to six months.
Classification of steam trap
There are three basic type of steam traps using different
physical principle to distinguish between steam and condensate.
Thermostatic steam trap
These traps are actuated by the temperature sensitive which
operate on the basis that the steam is hotter than condensate, air,
and other noncondesibles. There are three types of thermostatic
traps.
1- Liquid expansion
2- Balanced pressure
3- Bimetallic
Mechanical steam trap
These traps operate on the difference of density between steam
and condensate. The two important type of mechanical steam traps
are
1- ball float
2- bucket
Thermodynamic steam trap
These traps are operates on the facts that flash steam is
produced when pressure is reduced on the hot condensate. The
release of flash steam causes the discharge to close. There are the
following further types.
1- Disk type
2- Piston type
3- Lever type FLASH CALCULATION
datafluid composision
temperature 100namecomposition
v.p.of waterKPa101.33water0.87
v.p.of phenol Kpa3.51phenol0.0137
v.p.of Na-PheKPa2.07Na-Phe0.1182
Pbubble Kpa88.45
Pdew Kpa14.36
vaporliquid
0.8563910.143609
PRESURE KpacomponentK-valuescompositioncomp. Yi Xi
25water4.0530.9755290.02206930.97860.028531
phenol0.14040.007290.0519240.0070890.061549
Na-Phe0.08280.01396880.8710020.0143610.9099
1.0284420.94511
Total mole for 25-ton per day = 88.85656*25 = 2221.4 Kgmol
Total moles in tank = 318.995 Kgmol
Total weight = 318.995(0.9*116+0.061*94+0.02818)
= 35293.41 Kg
Weight required for 1.5-batch of autoclave = 35293.41/4 =
8823.35 Kg
Average density = 0.90*1258+0.061*1023+0.028*994
= 1222.25 Kg/m3
Filled volume = 7.2174 m3 % fill = 45 %
total volume = 16 m3
L = 5m , D = 2mSome more specifications
Height of liquid =
Height of inlet pipe =
Height of demister pad =
Thickness of demister pad =
Material of demister pod =
Height of outlet =
Steam pressure =
DESIGN OF DISTILLATION COLUMNThe detailed process design of the
carbolic acid column is given below. The pictorial Representation
of the column is given in fig. The feed to the column is a mixture
of carbolic acid and sodium phenolate. The compositions of the
components are given below. The top and bottom product, both are
the required products used in reactor one and in autoclave (second
reactor).
I. Thermodynamics: The primary requirement while designing mass
transfer contact equipment is the
Thermodynamic equilibrium data. The data required is in the
Vapor-Liquid Equilibrium
(VLE) data for the carbolic acid and sodium phenolate system.
The X-Y curve is shown in the fig. To
Develop the VLE data, a model was used.
yi pt = i xi Pi sat --------------------------(1)
Where,
yi = mole fraction of component i in vapor.
pt = total system pressure.
i = activity coefficient of component i in liquid.
xi = mole fraction of component i in liquid.
Pi sat = saturation vapor pressure of component i.
The equilibrium vapor pressure was evaluated using correlations
given in literature. The correlation was based on the critical
properties of the components. The two components carbolic acid and
sodium phenolate form a highly non-ideal system. To accommodate
this nonideality, an activity coefficient term was used for the
liquid phase. The activity coefficient was evaluated using the
UNIFAC model. Since the evaluation of the VLEdata is highly
iterative, an algorithm was developed which was solved using a
computer program. The gas phase was assumed to be ideal. This is a
valid assumption since the column is at 1 atmosphere pressure (760
mm Hg. abs.). The boiling points of the two components require the
column to be operated at 1 atmosphere. The operating pressure was
chosen to be 760 mm Hg (abs).
The following questions must be answered before going into
detailed design of the distillation column
1- what column is selected packed or tray column ?
Answer
Tray column would be better choice in situation facing due to
the following reasons
1- stage efficiency can be determined experimentally in packed
column because
=f(type and sizing of packing, fluid rates, fluid properties,
column diameter, operating temperature and pressure, extent of
liquid dispersion)
Where as a number of correlations are available for tray column
efficiency discussed by the famous authors. Coulson and Richardson,
Ludwig, Perry, Peter and Timmerhaus, conceptual design of
distillation column and more..
2-tray column can be designed over a wide range without
flooding
3-total dry weight of the tray column is less than the packed
column
4-design information for tray column id readily available as
compared to packed column. This made path of working easy for me
when I decided tray column
5-if chances of foam formation are more then packed column would
be given preference, but in situation facing me no foam formation
(surface tension at different temperature and pressure would
dictate foam formation criteria)
6- Thermal expansion chances can be easily handled with tray
column instead of packed column.
7- Equilibrium Data for large compounds as well as my compound
are available in literature and this data is more reliable for tray
column instead of packed column
What type of tray is selected sieve tray, bubble cap, or valve
tray ?
Answer
I decided sieve tray because of the following reasons
1- Manufacturing cost is low
2-operating cost is low
3-simple to construct
4-minmum entrainment as compare to bubble cap and valve tray
5-less pressure drop as compare to other
6-most commonly used
Glossary of notations used:
F = molar flow rate of Feed, gm
D = molar flow rate of Distillate, gmol/hr.
W = molar flow rate of Residue, gmol/hr.
xF = mole fraction of phenol in liquid/Feed.
yD = mole fraction of phenol in Distillate.
xW = mole fraction of phenol in Residue.
MF = Average Molecular weight of Feed, g/gmol
MD = Average Molecular weight of Distillate, g/gmol
MW = Average Molecular weight of Residue, g/mol
RRm = Minimum Reflux ratio
RR = Actual Reflux ratio
LR = Molar flow rate of Liquid in the Enriching Section,
gmol/hr.
VR = Molar flow rate of Vapor in the Enriching Section,
gmol/hr.LS = Molar flow rate of Liquid in Stripping Section,
gmol/hr.
Vs = Molar flow rate of Vapor in Stripping Section, gmol/hr. q =
Thermal condition of Feed l = Density of Liquid, kg/m3.
g = Density of Vapor, kg/m3.
ql = Volumetric flow rate of Liquid, m3/s
qv = Volumetric flow rate of Vapor, m3/s
(l = Viscosity of Liquid, cP.
Tl = Temperature of Liquid, 0K.
Tv = Temperature of Vapor, 0K.
II. Preliminary calculations:
Feed = 9915 gmol/h
xF = 0.67, MF = 101.16g/gmol.
D = 6783.89gmol/hr, xD = 0.97, MD = 94.66g/gmol.
W=3131.1gmol/hr, xW = 0.02, MW =115.56g/mol.
Basis: 1 Hour Operation.
From the graph
Rm = 1.5
Let, R= 2.1 *Rm (from trial this value is estimated )
RR= 1.52.0= 3.2
Number of Ideal trays = 17
Number of Ideal trays in Enriching Section = 8
Number of Ideal trays in Stripping Section = 9
Now, we know that,
RR = R/ D => R =RRD
i.e., R= 3.2*6783.89 = 21705gmol/h
L= Liquid flow rate on the Top tray = 21705gmol/h
VR= L + D
= (R+1)*D = 4.2*6783.89mol/hr = 28488.6gmol/h
VR = Gas flow rate in the Enriching Section = 28488.6gmol/h
Since feed is Liquid, entering at bubble point,
q= (HV-HF) / (HV-HL) = 1
Now,
Slope of q-line = q/ (q-1) = 1/ (1-1) = 1/0 = .
Now we know that,
LS = F + LR
LS = 9915+21705.6=31619.6 gmol/h
Therefore, liquid flow rate in the Stripping Section = 31619.6
gmol/h
Also, we know that,
VS = [(q-1) F] + VR
VS = [(1-1) F] + VR
VS = VR = = 28488.6gmol/h
Therefore, the flow rate of Vapor in the Stripping Section = =
28488.6gmol/h
IV. Design Specification:
Tray Hydraulics
The design of a sieve plate tower is described below. The
equations and correlations are borrowed from the 6th and 7th
editions of Perrys Chemical Engineers Handbook, plant design and
economics by Peter and Timmerhaurse, ludwick, unit operation of
chemical engineering by McCabe and Smith, Coulson and Richardsons
book, separation techniques by C.G. King The procedure for the
evaluation of the tray parameters is iterative in nature. Several
iterations were performed to optimize the design.
The final iteration is presented here.
1. Tray Spacing, (ts):
Let ts = 457mm (18in).
2. Hole Diameter, (dh): Let dh = 5 mm.
3. Hole Pitch (lp):
Let lp = 3 dh
i.e., lp = 35 = 15 mm.
4. Tray thickness (tT):
Let tT = 0.6 dh
i.e., tT = 0.65 = 3 mm.
5. Ratio of hole area to perforated area (Ah/Ap):
Refer fig 6.3Now, for a triangular pitch, we know that
Ratio of hole area to perforated area (Ah/Ap) = (/4dh2)/ [(3/4)
lp2]
i.e., (Ah/Ap) = 0.90 (dh/lp)2
i.e., (Ah/Ap) = 0.90 (5/15)2
i.e., (Ah/Ap) = 0.1
Thus, (Ah/Ap) = 0.1
6. Plate Diameter (Dc):
The plate diameter is calculated based on the flooding
considerations
L/G {( g/ ( l}0.5 = 0.11
Now for,
L/G {( g/ ( l}0.5 = 0.11 and for a tray spacing of 457 mm.
We have from the flooding curve, ---------- (fig.18.10, page
18.7, 6th edition Perry.)
(Plant design and economics by Peter and Timmerhaus)
Flooding parameter, Csb, flood = 0.07 m/s.
Now, Unf = Csb, flood (/ 20) .0.2 [(( l - ( g) / ( g] 0.5----
{eqn. 18.2, page 18.6,
6th edition Perry.}
(Plant design and economics by Peter and Timmerhaus)
Where,
Unf = gas velocity through the net area at flood, m/s (ft/s)
Csb, flood = capacity parameter, m/s (ft/s, as in fig.18.10)
= liquid surface tension, mN/m (dyne/cm.)
( l = liquid density, kg/m3 (lb/ft3)
( g = gas density, kg/m3 (lb/ft3)
Now, we have,
= 28.57 dyne/cm.
l = 1023 kg/m3.
g = 2.52 kg/m3.
Therefore,
Unf = 0.07 (28.57/20)0.02 *[987-2.52)/ 2.52]0.5
i.e., Unf = 4.87 ft/s = 1.49 m/s.
Let Actual velocity, Un= 0.8Unf
i.e., Un = 1.19 m/s
Now, volumetric flow rate of Vapor
qo = 28488.6*94.5 / (36002.52*1000) = 0.3 m3/s.
Net area available for gas flow (An)
Net area = (Column cross sectional area) - (Down comer
area.)
An = Ac - Ad
Thus, Net Active area, An = qo/ Un = 0.3/1.119 = 0.252 m2.
Let Lw / Dc = 0.75 Where, Lw = weir length, m
Dc = Column diameter, m
, c = 2sin-1(Lw / Dc) = 2sin-1 (0.75) = 97.180
Ac =(3.14/4) Dc2= 0.7854Dc2 , m2And, c = angle Ad = [(/4) Dc2 (c
/3600)] - [(Lw/2) (Dc/2) cos (c /2)]
Ad = [0.7854 Dc2 (97.180/3600)]-[(1/4) (Lw / Dc) Dc2 cos
(97.180)]
Ad = (0.2196 Dc2) - (0.1241 Dc2)
Ad = 0.0955Dc2, m2Since, An = Ac -Ad
0.252 = (0.7854Dc2) - (0.0955 Dc2)
i .e., 0.6895 Dc2 = 0.252
Dc2 = 0.252/ 0.6895 = 0.365
Dc = 0.6 mTake Dc = 0.635 m
Since Lw / Dc = 0.75,
Lw = 0.75 Dc = 0.750.635 = 0.476 m.
Therefore, Lw = 0.476 m.
Now, Ac = 0.78540.6352 = 0.316 m2 Ad = 0.08790.635 = 0.0354 m2
An = Ac - Ad
An =0.316-0.0354
An = .2806 m2
7. Perforated plate area (Ap):
Active area (Aa)
Aa = Ac - (2Ad)
Aa = 0.316- (20.0354)
Aa = 0.245 m2
Lw / Dc = 0.476/ 0.635 = 0.75
c = 97.18 0. c = angle
1=180 0 - 97.18 0 = 82.82 0 1 = angle
Acz = 2 Lw (thickness of distribution)
= 5 20% of Ac
Where Acz = area of calming zone, m2
Acz = taking 10% of Ac = 0.02833
Also,
Awz = {(/4)Dc2 (/3600)}-{/4 (Dc-0.05)2 /3600}
Where Awz = area of waste periphery, m2
i.e., Awz = 2 5 % of Ac, taking 2% of Ac,
i.e., Awz = 0.0.0057 m2
Now,
Ap = Ac - (2Ad) - Acz Awz
Ap = 0.2833 2*0.0354 - 0.02833 - 0.0.0057 =0.1784 m2Thus, Ap =
1.720 m2
8. Total Hole Area (Ah):
Since,
Ah / Ap = 0.1
Ah = 0.1 Ap
Ah = 0.1 0.1784 =0.01784m2Thus, Total Hole Area = 0.01784 m2
Now we know that,
4*Ah = nh (.dh2) Where nh = number of holes.
nh = (40.01784)/ (.3.140.0052)
nh = 909
Therefore, Number of holes = 909.
9. Weir Height (hw):
Let hw = 45 mm.
10. Weeping Check
All the pressure drops calculated in this section are
represented as mm head of
liquid on the plate. This serves as a common basis for
evaluating the pressure
drops.
Notations used and their units:
hd = Pressure drop through the dry plate, mm of liquid on the
plate
uh = Vapor velocity based on the hole area, m/s
how = Height of liquid over weir, mm of liquid on the plate
h= Pressure drop due to bubble formation, mm of liquid
hds= Dynamic seal of liquid, mm of liquid
hl = Pressure drop due to foaming, mm of liquid
hf = Pressure drop due to foaming,
Df = Average flow length of the liquid, m
Rh = Hydraulic radius of liquid flow, m
uf = Velocity of foam, m/s
(NRe) = Reynolds number of flow
f = Friction factor
hhg = Hydraulic gradient, mm of liquid
hda = Loss under down comer apron, mm of liquid
Ada = Area under the down comer apron, m2
c = Down comer clearance, m
hdc = Down comer backup, mm of liquid
Calculations:
Head loss through dry hole
hd = head loss across the dry hole
hd = k1 + [k2 (g/l) Uh2] --------- (eqn. 18.6, page 18.9, 6th
edition Perry)
where Uh =gas velocity through hole area
k1, k2 are constants
For sieve plates
k1 = 0 and
k2 = 50.8 / (Cv)2
where Cv = discharge coefficient, taken from fig. 18.14, page
18.9, 6th edition Perry).
Now,
(Ah/Aa) = 0.01784/ 0.245 m2 = 0.073also tT/dh = 3/5 = 0.60
Thus for (Ah/Aa) = 0.07993 and tT/dh = 0.60
We have from fig. edition 18.14, page 18.9 6th Perry.
Cv = 0.730
k2 = 50.8 / 0.7302 = 95.3275
Volumetric flow rate of Vapor at the top of the Enriching
Section
qt = 0.3 m3/s.
Velocity through the hole area (Uh):
Velocity through the hole area at the top = Uh, = qt /Ah
= 0.3/0.01784 = 16.8 m/s
Velocity through hole area should be minimum because at low gas
flow rate weeping is
observed.
Now,
hd, = k2 [g/l] (Uh )2
= 95.3275(2.91/1011) 16.82
hd, top = 85.24 mm clear liquid. -------- (minimum at top)
Head Loss Due to Bubble Formation
h= 409 [/ (ldh)] --- (eqn. 18.2.a, page 18.7, 6th edition
Perry)
where surface tension, mN/m (dyne/cm)
dh =Hole diameter, mm
l = average density of liquid in the
section, kg/m3
= (987+1141)/2
= 1064 kg/m3
h=409 [17.4565 /(777.92 x5)]
h= 2.714 mm clear liquid
Height of Liquid Crest over Weir:
how = 664_)w [(q/Lw)2/3]-----------( eqn. 18.12.a, page
18.10,
6thedition Perry
q = liquid flow rate at top, m3/s
= 17747.8/ (3600788.86)
= 6.24910-3 m3/s
q = 99.05 gal/min(or GPM).
Lw = weir length = 1.425 m = 4.675 ft
q/Lw2.5 = 99.05/ (4.675) 2.5 = 2.096
now for q/Lw2.5 = 2.096 and Lw /Dc =0.75
we have from fig.18.16,
page 18.11, 6th edition Perry
Fw= correction factor =1.025
how = 1.025664[(6.24910-3)/1.425]2/3
how = 18.23 mm clear liquid.
Now,
(hd + h) = 85.24 + 2.714 = 87.95 mm ------ Design value
(hw + how) = 45 + 18.23 = 63.23 mm
Also, Ah/Aa = 0.08 and (hw + how) = 63.23 mm
The minimum value(hd + h) of required is calculated from a graph
given in Perry,
plotted against Ah/Aa. we have from fig. 18.11, page 18.7, 6th
edition Perry
(hd + h) min = 16.0 mm ------- Theoretical value.
The minimum value as found is 16.0 mm.
Since the design value is greater than
the minimum value, there is no
problem ofweeping.
Down comer Flooding:
hds =hw + how + (hhg /2) ------- (eqn 18.10, page 18.10, 6th
edition Perry)
Where,hw = weir height, mm
hds = static slot seal (weir height minus height
of top of slot above plate floor, height
equivalent clear liquid, mm)
how = height of crest over weir, equivalent clear
liquid, mm
hhg = hydraulic gradient across the plate, height of
equivalent clear liquid, mm.
In the above equation how is calculated at bottom of the section
and since the tower is
operating at atmospheric pressure, hhg is very small for sieve
plate and hence neglected.
Calculation of how at bottom conditions of the section:
q = liquid rate at the bottom of the section, m3/s
= 31619*116/(3600*1258*1000)=8.1x10-4 m3/s
= (8.1x10-4)/ (6.309*10-3) = 7.7 gal/min
Lw = weir length = Lw = 0.476 m.= 1.56 ft.
q/Lw2.5 =7.7/ (1.56)2.5 = 3.14
now for q/Lw2.5 = 3.14and Lw /Dc =0.75
we have from fig.18.16, page 18.11, 6th edition Perry
Fw= correction factor =1.030
Thus, how = 1.03664[(8.1x10-4)/0.47]2.3
how = 19.33 mm clear liquid. ----- (maximum at the bottom of
section).
Therefore, hds = 45 +19.33 = 64.33 mm.
Now, Fga = Ua g0.5 Where Fga = gas-phase kinetic energy
factor,
Ua = superficial gas velocity, m/s (ft/s),
g = gas density, kg/m3 (lb/ft3)
Here Ua is calculated at the bottom of the section.
Ua = (Gb/g)/ Aa = (28072/2.91) /(0.245x3600) = 1.24 m/s Thus, Ua
= 4.06 ft/s
g = 2.91 kg/m3 = 2.91/ (1.60184610-1) = 0.181 lb/ft3
Fga = 4.06(0.181)0.5Fga = 1.72
Now for Fga = 1.72, we have from fig. 18.15, page 18.10 6th
edition Perry)
Aeration factor = (= 0.6
Relative Froth Density = (t = 0.20
Now hl= (hds ---- (eqn. 18.8, page 18.10, 6th edition Perry)
Where, hl= pressure drop through the aerated mass over and
around the disperser,
mm liquid,
hl= 0.664.33 = 38.598 mm.
Now,
hf = hl/(t ------- (eqn. 18.9, page 18.10, 6th edition
Perry)
hf = 38.598/ 0.20 = 192.99 mm.
Head loss over down comer apron:
hda = 165.2 {q/ Ada}2 ----- (eqn. 18.19, page 18.10, 6th edition
Perry)
Where, hda = head loss under the down comer apron, as
millimeters of liquid,
q = liquid flow rate calculated at the bottom of section,
m3/s
and Ada = minimum area of flow under the down comer apron,
m2
Now,
q = 18950.03/(3600776.98) = 6.77410-3 m3/s
Take clearance, C = 1/2 = 12.5 mm
hap = hds - C = 64.33 12.5 =51.83 mm
Ada = Lw x hap = 0.4710-3 = 24.36*10-3 m hda2
hda = 165.2[6.77410-3 / 24.36x 10-3] 2
= 12.75 mm
ht = total pressure drop across the plate (mm liquid)
= hd + hl`
= 85.24 + 38.598
= 123.838 mm
Down comer backup:
hdc = ht+ hw + how + hda + hhg ---- (eqn 18.3, page 18.7, 6th
edition Perry)
Where, hdc = height in down comer, mm liquid,
hw = height of weir at the plate outlet, mm liquid,
ho =height of crest over the weir, mm liquid,
hda = head loss due to liquid flow under the down comer apron,
mm liquid,
hhg = liquid gradient across the plate, mm liquid.
hdc =123.83 + 45 + 19.33 + 12.75 + 0
= 201 mm
Let (dc = average relative froth density (ratio of froth density
to liquid density)= 0.5
hdc = hdc / (= 201/ 0.5 = 402 mm which is less than the tray
spacing of 457 mm.
Hence no flooding in the enriching sectionV. EFFICENCIES: (AIChE
Method)
A) Enriching Section:
Point Efficiency, (Eog):
Eog = 1-exp (-Nog) ----- (eqn. 18.33, page 18.15, 6th edition
Perry)
Where Nog = Overall transfer units
Nog = 1/ [(1/Ng) +(/Nl)] ---- (eqn. 18.34, page 18.15, 6th
edition Perry)
Where Nl = Liquid phase transfer units,
Ng = Gas phase transfer units
=(mGm)/ Lm = Stripping factor,
m = slope of Equilibrium Curve,
Gm = Gas flow rate, mol/s
Lm = Liquid flow rate, mol/s
Ng= (0.776 + (0.00457hw) (0.238Ua * g0.5)+ (104.6W))/ (NSc,
g)0.5 ----- (eqn. 18.36,
page 18.15, 6th edition Perry)--- *
hw = weir height = 45.00 mm
Ua = Gas velocity through active area, m/s
Ua= (Avg. vapor flow rate in kg/hr)/ (3600Avg. vapor density
active area)
= (28488.6*116/1000)/ (36000.2452.925)
Ua = 1.28 m/s
Df = (Lw + Dc)/2 = (0.635+0.47)/2 = 0.55 m
Average Liquid rate = 2040.27 kg/hr
Average Liquid Density =991 kg/m3
q = 2040.36/ (3600x991) =5.71 x 10-0.4 m3/s
W = Liquid flow rate, m3/ (s.m) of width of flow path on the
plate,
= q/Df = 5.71*10-4/0.55 = 1.0410-3 m3/ (s.m)
NSc g = Schmidt number =g (gDg) = 0.66
Number of gas phase transfer units
Ng= (0.776 + (0.0045745) (0.2381.282.9250.5) +
(104.61.0410-3))/(0.66)0.5
Ng = 0.744
Number of liquid phase transfer units
Nl = kl al ----- (eqn 18.36a, page 18.15, 6th edition Perry)
Where kl = Liquid phase transfer coefficient kmol/ (sm2 kmol/m3)
or m/s
a = effective interfacial area for mass transfer m2/m3 froth or
spray on the plate,
1= residence time of liquid in the froth or spray, s l =
(hlAa)/(1000q) ---- (eqn. 18.38, page 18.16, 6th edition Perry)
q = liquid flow rate, m3/s = 5.71*10-4 m3/s
hl = hl = 38.08 mm
Aa = 0.47 m2
l = (38.080.47 )/(10005.71*10-4) =31.34 sec
kl a = (3.875108DL)0.5 ((0.40Uag0.5) + 0.17)--- (eqn. 18.40a,
page 18.16,
6th edition Perry)
DL= liquid phase diffusion coefficient, m2/s
kl a = (3.8751088.0810-9)0.5 ((0.401.282.9250.5) + 0.17)
kl a = 1.832 m/s
Nl = kl al
i.e., Nl = 1.83331.34 =57.13
Slope of equilibrium Curve
mtop = 0.4375
mbottom = 0.84
Gm/Lm = 1.2
t = mt Gm/Lm =0.4375*1.2=0.525
b = mbGm/Lm = 0.84*1.2 = 1.002
= 0.76
Nog = 1/[(1/Ng_+/Nl)]
= 1/[(1/0.774) + (0.76/57.16)]
Nog = 1.6
Eog = 1-e-Nog = 1-exp (-Nog)
= 1-e-1.037 = 1-exp (-1.037)
Eog = 0.67
Point Efficiency = Eog = 0.67
2. Murphree Plate Efficiency (Emv):
Now,
Pelect number =NPe = Zl2/ (DE l)
Where Zl = length of liquid travel, m
DE = (6.675 x 10-3 (Ua)1.44) + (0.922 10 -4 hl) - 0.00562-----
(eqn. 18.45, page 18.17,
6th edition Perry)
where DE = Eddy diffusion coefficient, m2/s
DE = (6.675 x 10 -3 (1.266)1.44) + (0.922 10 -4 38.08) -
0.00562
DE = 7.26510-3 m2/s
Also Zl = Dc cos (c/2)
= 0.635 cos (97.18 0/2)
= 0.46 m
NPe = Zl2/ (DE l)
= 0.462/ (7.26510-3 57.13)
NPe = 5.1
Eog = 0.76 x 0.67 = 0.502
now for Eog = 0.60 and NPe = 5.1
We have from fig.18.29a, page 18.18, 6th edition Perry
Also available in seventh edition
Emv/ Eog = 1.28
Emv = 1.28 Eog = 1.280.67 =0.81
Murphree Plate Efficiency = Emv = 0.81
3. Overall Efficiency ( EOC):
EOC = log [1 + E(- 1)]/log ----- (eqn. 18.46, page 18.17, 6th
edition Perry)
Where E/Emv= 1/(1 + EMV [(/ (1-()]----- (eqn. 18.27, page 18.13,
6th edition Perry)
Emv = Murphee Vapor efficiency,
E. = Murphee Vapor efficiency, corrected for recycle effect of
liquid entrainment.
(L/G) {(g/(l}0.5 = 0.039
for (L/G){g/l}0.5 = 0.039 and at 80 % of the flooding value,
We have from fig.18.22, page 18.14, 6th edition Perry
(= fractional entrainment, moles/mole gross down flow =
0.076
E = Emv 1/[1 + Emv [(/ (1- ()]]
= 0.81[(1+0.81[0.076/ (1-0.076)])]
E= 0.773
Overall Efficiency = EOC = log [1 + E(- 1)]/log
EOC = log [1+ 0.7730(0.76-1)]/log 0.76
Overall Efficiency = EOC = 0.726
Actual trays = Nact = NT/EOC = (ideal trays)/ (overall
efficiency)
Where NT = Theoretical plates,
Nact = actual trays
Nact = 17/0.72623.41=25
Thus actual trays in rectifying section = 13
Thus, Actual trays in the Stripping Section = 12
Total Height of distillation column= 25ts = 25457 = 11425 mm =
11.425 m
Design of autoclave
INTRODUCTION
Autoclaves have been used in industry for many decades. As
technology has progressed so has autoclave design, initially from
basic riveted steam heated vessels to vessels fabricated utilizing
the latest welding techniques with highly sophisticated
computerized control systems
The industries that make use of autoclaves have also evolved
over the years. Initially used in the textile, timber, food,
sterilizing and rubber industries, autoclaves are now essential
items in the advanced composites and Investment casting
industries
Commercial pressure autoclaves have been in operation since mid
1950s. Historical production data suggest that these early
autoclaves were originally designed with excess capacity (Bere
zowsky, Collins, Kerfoot, and Torres, 1991). Process development
initially consisted of tests in batch autoclaves. While in some
cases this stage had been followed by continuous pilot plant tests
in multi-compartment autoclaves, in many cases the batch test
residence times were extended to the continuous commercial stage
using some factor, resulting in an over estimation of the required
autoclave volume. In some other instances the continuous stage of
testing had not been performed or its results could not be
interpreted as a continuation of batch tests due to differences in
ore composition, grind size and reactor conditions. In such cases,
it would be important to be able to scale-up the batch test data to
a multi-compartment continuous mode using a sound approach that
takes into account both the physical and chemical aspects of the
leaching reaction as well as the reactor configuration.
For use in the production of advanced composite materials, a hot
atmosphere autoclave has to achieve the following criteria:
Fail to safety, safety systems
Achieve the required internal environment (ie. heat and
pressure)
Programmable temperature control and uniform temperature
distribution
Programmable pressure control
Computerised process control, monitoring and data logging
Not only the autoclaves are made of a no. of different
materials,but the sizea,general design and arrangement for heating
are so varied that one might forgive a chemist,used only to most
common forms,for failing to some of the rare types of modern
apparatus as being autoclave at all.
Two particular types of autoclaves have beenselected as covering
the most important ranges of high pressure work.These are
1. High pressure autoclaves
2. Low pressure autoclaves
Autoclaves can be made of Iron,steel,copper bronze or tin but
some kind of the steel is by the far the most common material used
in their manufacture on account of its great strength.Modern
practice supports use of nickel steel and nickel chrome steel for
those autoclaves designed to withstand very high pressure.
Autoclaves are made of very large size,from small labortary
pieces of apparatus of few hundered cubic centimeters capacity to
huge pans capable of holding a charge of twenty thousand
gallons.
Autoclaves are generally cylindrical in shape,height being from
2-3 times the diameter.Bottom may be ellipsoidal or dishad
bottom.In order to give strength all sharp vurves or angles
axcluded from design the top of the autoclave known as cover is
fixed on to flanges
Many of the different materials, are used for packing of the
joints. The commonest packings are lead,copper,aluminium and
asbestos.Not only does the choice of material used on type of
autoclave ,but also depend on pressure.It is more common one type
to fix one or more safety valves of the ordinary steam boiler type
to an autoclave.But these were constantly getting chocke