Co-Production of N-Butanol and Isobutanol
Co-Production of N-Butanol and Isobutanol
Co-Production of N-Butanol and Isobutanol
CHAPTER
INTRODUCTION
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
ABSTRACT
INTRODUCTION
It is a major product since world war II and serves as a starting material for a wide
range of substances. Butyl alcohols can cause fat accumulations in the liver, heart and kidneys of
experimental animals. The largest use for butanol and its derivations is in the coating industry for
the formulation of nitrocellulose lacquers. An emerging market for butanol is latex in the form of
butyl acrylate. The more important derivatives of butanol are butyl acetate, butyl glycol ether and
plasticizers as an extraction solvent for oils, drugs and perfumes. It is an excellent diluent for br-
ake fluid formulations and also used as an extractant in the manufacture of antibiotics, vitamins
and hormones.
Isobutanol can also be used in practically all of the applications that have been
mentioned for butanol. Butanol is moderately dangerous; toxic fumes are emitted when heated to
decompos-ition. Excessive exposure can cause headache, dizziness, nausea etc. The liquid
effluent is degradeable and can be disposed after neutralisation with lime followed by
biodegradation. Liquid and gaseous effluents can also be incinerated.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Butyl acrylate
Butyl acetate
Dibutyl phthalate
Extractant for:
Antibiotics
Hormones
Vitamins
Perfume ingredient
Repellent
Paint solvent
Ink ingredient
Gasoline additive
Derivative ester precursor
Viscosity reducer in paint
Automotive polish and paint cleaner additive
BUTANOL ADVANTAGES:
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
One of the most important butanol advantages is the fact that it will reduce carbon
emissions. The EPA has released data showing that hydrocarbon, carbon monoxide, and nitrogen
oxide releases can be greatly reduced by use of butanol. Another advantage is that butanol has a
higher energy content than ethanol, almost 20% more by density. Due to its similarities to
conventional gasoline, it is able to blend much better than ethanol with gasoline. It has even
shown promise when using 100% butanol in a conventional gasoline engine. Besides these,
butanol experiences a lower chance of separation and corrosion than ethanol.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
LITERATURE SURVEY
LITERATURE SURVEY
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
HISTORY:
DEVELOPMENT OF TECHNOLOGY
Between 1852 and 1871 butyl alcohols were discovered and their structures
established. In 1871 Lieben and Rossi prepared n-butyl alcohol by reducing n-butyraldehyde.
The original observation of the butanol production by 'Clostridia' was made by Pasteur and
acetonefermentation by Schardinger. Interest in commercializing butanol-acetone fermentation
occured in 1909 primarily as a means of obtaining L- butadiene as a raw material for a synthetic
rubber.
The most wide spread means of producing butanol today is the oxo process
where propylene and syngas (CO and H2) are reacted. The oxo process or the hydroformylation
reaction was discovered by O. Roelen in 1938. The products were both aldehydes and ketones.
Most of the aldehydes produced are either reduced to alcohol directly or subjected to aldol
condensation prior to hydrogenation. High pressure cobalt catalysts oxo process was
commercialised since 1950. Ruhrchemie (Germany) used this process for producing detergent
range alcohols. Many variations of the above process have been developed and commercialised.
In the oxo reaction, carbon monoxide and hydrogen are added to carbon carbon
double bond of propylene, in the liquid phase in the presence of catalyst, (cobalt hydrocarbonyls)
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
producing 1 -butanol and some amount of iso butanol. Though there are several variations of this
process,the differences being in the reaction conditions (pressure, temperature). In the high
pressure process, operation pressure is 200-300 kg/cm2 and temperature 100-180° C. The
catalyst is Co and the product is 75% or more of butanol and the rest i-butanol. The new process
using Rh catalyst operates at much lower pressure (7-20 kg/cm2). The isomaric ratios achieved
are about 92:8 or 95:1-butanol to isobutanol. Catalystic hydrogenation of the aldehydes lead to
the formation of the corresponding alcohols. As only primary alcohols can be obtained via the
oxo synthesis it is not possible to produce secondary and tertiary butyl alcohol by this process.
In Reppe process developed in 1942, propylene, carbon monoxide and water are
made to react under pressure in the presence of a catalyst (tertiary ammonium salt of poly
nuclear iron carbonyl hydrides). The difference between this process and classic Co catalyst
hydroformylation is that at low temperature (100° C) and pressure alcohol is formed directly.
This process has not been commercially successful inspite of certain advantages it offered
compared to conventional oxo process. This is attributed to more expensive process technology.
Until the mid 1950s the manufacture of n-butanol based on acetaldehyde was the
preferred process. With the development of the oxo synthesis, this process has lost its importance
in developed countries. Acetaldehyde is produced either from ethanol or ethylene and is
aldolized to acetaldol at normal temperature and pressure in the presence of alkaline catalyst.
With conversion of about 60% the acetaldol yield is about 95%. Unreacted acetaldehyde can be
distilled off and recycled.
Various gas and liquid phase processes have proved their value for the
hydrogenation of crotonaldehyde to butanol. Copper catalyst are particularly useful. For tropical
countries with large supplies of cheap biomass as well as for the more developed countries of the
third world who do not have their own oil resources this process is alternative to oxo process.
The plants producing butanol from alcohol have been generally located near alcohol distillaries.
Propylene-syngas based plant is located as down stream of naphtha cracker or very close to that
naphtha cracking unit which is normally a part of a petrochemical complex.
CAPITAL EQUIPMENT
The other capital equipment required for oxo process are syngas compressors,
alcohol reactors, blowers, waste heat boilers besides various safety and control equipment.
NOCIL imported most of the capital equipment for their butanol plant except waste boilers. For
the alcohol route some of the plant and equipment were imported by Somaiya and Oswal units,
but today they are all available indigenously.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
In the late 1960s, Indian capability in terms of capital equipment fabrication was
restricted compared to what is today. Neverthless there are certain propritory or patented design
equipment like reformer furnace, syngas compressors, reactor and blowers are supplied by
technology supplier. Fabrication facility for reformer furnace is available in India.
The main producing units are Oswal Petro Chemicals, National Organic Chemical
Industries Limited, Somaiya Organic (I) Limited, Kolhapur Sugar Mills Limited and recently
commissioned Andhra Petro having installed capacities of 4200, 6000, 7500, 3000 and 5,000
TPA respectively. The product quality of NOCIL, Oswal and Somaiya is satisfactory and very
close to international specifications. NOCIL, one of the oldest petrochemical complex in India
commissioned their butanol plant in 1969 with capital investment of Rs. 452 lakhs, the present
replacement value of which is Rs. 5,437 lakhs. For Somaiya's plant original project cost was Rs.
411 lakhs and the present cost of expansion is Rs. 194 lakhs. The performance of these units,
over the years was satisfactory. None of the units are exclusively making butanol but
manufacturing other chemicals also. The ex works price of butanol of NOCIL is Rs 30,000 per
MT while that of Oswal and Somaiya it is Rs 38,000 and Rs. 30,500 respectively.
The major problem with the industry is feed stock, besides other constraints like
power, infrastructure etc. Both naphtha and alcohol are allocated feed stock. While one is
controlled by Central Government the other is controlled by States. Industrial alcohol prices are
altered and allocations changed by the States at times causing problem for industry. This requires
a uniform policy on alcohol by the States.
The demand of normal butanol by the end users was more than what industry could
produce. This necessitated import. The major sectors of consumption are paints and resins,
Pharmaceuticals, esters, plasticizers and others. The demand in 1984-85 was 13,465 MT while
the production was 11,965 MT and import was 1500 MT. The corresponding figures for the year
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
1991-92 are 22,000, 20,000 and 5,000 MT respectively, Estimated demand for the year 1999-
2000 AD is 46,700 MT. Unless the price is internationally competitive, export possibility is
remote.
TECHNOLOGY
The technologies for butanol manufacture are the followings
INTERNATIONAL SCENARIO
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
exclusively manufacture butanol but other chemicals as well. Oxo process is the predominant
process in operation all over the world. Countries having biomass and ethanol are following the
ethanol route and a limited few are following the fermentation process. These countries are
Brazil, South Africa and probably Argentina. Although the capacity utilization varied between
60-70% but the growth of the industry was fairly rapid. In 1976 butanol production in USA was
248,100 MT while the world production was 540,000 MT and the corresponding figures for 1984
was 700,000 MT and 1,200,000 MT respectively. Compared to this, butanol industry growth rate
in India is insignificant. In the international arena the R&D efforts, in most of the cases have
been directed towards improvement of catalyst, leading to improvement in operating conditions
with respect to lowering of pressure and conversion of raw material to finished product and
conservation of energy.
THRUST AREA
No major improvements have taken place in the ethanol based technology for
butanol in the world as well as in India. This can be attributed to the fact that oxo process is the
predominant process in the world. In India though* alcohol is available yet because of various
constraints with respect to allocation, pricing and other factors, industry efforts in utilizing
alcohol for value added products did not materialize extensively.
Industry using alcohol as a feed stock for various chemicals, continued to sustain
Their activities without much investment in terms of modernization and up gradation of
technology. Therefore, alcohol route needs a thrust to make it economically competitive with
oxo process that what it is today. Fermentation process for the manufacture of butanol along with
other valuable co-products like acetone, ethanol, carbon dioxide, hydrogen, riboflavin and
livestock feed is another very promising area where adequate thrust would bring about
substantial benefit to a tropical country like India.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
SELECTION OF
PROCESS
SELECTION OF PROCESS
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Propylene and syngas (CO and H2) are reacted. The products were both
aldehydes and ketones.
3. Fermentaion:
4.Reppe synthesis:
CHOICE OF PROCESS:
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
PHYSICAL AND
CHEMICAL
PROPERTIES
N-BUTANOL
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
ISO-BUTANOL
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Form: liquid
Colour: colourless
Odour: sweet musty
Melting point/range: -108 °C
Boiling point/range :108 °C
Flash point 28 °C; closed cup
Autoignition temperature ;428.7 °C
Vapour pressure 14 hPa; 20 °C
Density 0.801 g/cm3; 20 °C
Water solubility : partly soluble, partly miscible
Solubility in other
solvents
partly soluble
Viscosity, dynamic 4,703 mPa.s
Relative vapour density 2.55
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
OXO PROCESS OR
PROPYLENE
HYDROFORMYLATION
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Raw materials
1. Propylene (93%min)
2. Synthesis gas:
CO:46.6%
H2:49.2%
CO2: 0.5%
H2O : 0.3%
CH4: 3.4 %
Intermediates:
N-butyraldihyde
Iso-butyraldehyde
Products:
N-butanol
Iso-butanol
TWO STEPS
1.HYDROFORMYLATION:
C3H6 + CO + H2 C4H8 O
2.HYDROGENATION:
C4H8 O + H2 CH3CH2CH2CHO
Butyraldehyde(N,iso) Butanol(N,Iso)
Catalysts comparison:
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
a b c
r ' =k 0[Rh] pC p H p CO exp(-Ea/RT)
3 2 ❑
where Ea, the apparent activation energy, is equal to 79.1 kJ/mol, and the reaction
orders a, b and c are 1.03, 0.09 and 0.23, respectively. The reaction order in carbon monoxide c
is pressure dependent, and at carbon monoxide pressures above 0.15 MPa equal to 0.08. The
selectivity towards n-butyr-aldehyde is not influenced by the hydrogen and propylene pressures,
but varies strongly with the partial pressure of carbon monoxide. When this partial pressure is
lowered from 0.52 to 0.05 MPa, the selectivity increases from 10 to 30. Similarly, an increase in
temperature from 70 to 106.8 °C raises the selectivity from 6.7 to 11.5. With Kieselguhr and
polystyrene—20% divinylbenzene (XAD-2) as catalyst supports, the rate of reaction is first order
in rhodium complex concentration in the solvent ligand PPh3. The kinetics differ significantly
from those found in homogeneous hydroformylation in, for instance, toluene.
P0A −P A
W
X
=∫
d XA
A P
=¿ ∫
d
P0AA [
=
−1 ]0
P A −P A
1−a
[
1−a
=0.981 x 10−3 g . R h . s /¿ ¿
c.c C3
]
F AO 0 −r A P
a
k [ R h ] PA
0
0
k [ R h] PA 1−a
A❑
Where
− Ea −79.1
RT
=¿ (4.721 x 10−12 ¿ e 8.314 x 10
−3
T
k =k o e
And
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
[ R h ] =10.1 mol/m3.
Ea = 79100 j/mol
K= 19.77
R= 8.314 J/mol k
OXO UNIT :
P= 5.23 bar
P0A −P A
W
X
=∫
d XA
A P
=¿ ∫
A
P0A
d
=
[ −1 ]
P 0A −P1−a
A
[
1−a
=0.981 x 10
−3
]g . R h . s /¿ ¿
c.c C3
F AO 0 −r A P
a
k [ R h ] PA
0
0
k [ R h] PA 1−a
A❑
PROCESS DESCRIPTION
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
OXO UNIT:
Hydroformylation of oxo reaction:
N – Bal: I – Bal: C3 H8 = 10.2: 1 :0.2
Hydroformylation of propylene to Aldehyde
C3 H6 + CO +H2 C3 H8
Catalyst : Rhodium
Pressure : 15.7 bar
Temperature : 900C.
The Oxo reactor serves to produce Crude Butyraldehyde using propylene and
synthesis gas in presence of Rhodium catalyst by Hydroformylation.
The mixture of purified Synthesis gas containing stripped propylene and purified
propylene feedstock are mixed with recycle gas including recycled including vent gas from the
Oxo compressor. The process reactants cycle gas mixture is then fed to the Oxo reactor. Which
contains rhodium based catalyst solution.
The reaction is exothermic taking place in the liquid phase at a temperature of 90-
0
110 C and a pressure of 15.7 bar. Circulating gases and evaporating the product remove a large
proportion of the reaction heat. The balance of heat is removed by circulating tempered water
through a cooling coil within the reactor. The tempered water system is a closed loop. The water
is circulated with the tempered water circulation pump. The tempered water heat is utilized in
the propylene vaporizer, while the remainder is removed by tempered water cooler. Tempered
water cooler is titanium plate heat exchange using seawater for cooling.
The tempered water is supplied from the carbon steel surge drum. Water makeup
is given from the MP condensate system. The tempered water system is maintained under a
Nitrogen blanket in the surge drum to minimize corrosion and to maintain water quality.
The Oxo Reactor temperature is maintained 90-110 0C. Below that larger catalyst
volume is required to produce the product and a higher gas circulation rate need to remove it.
Above that range causes deactivation of the catalyst takes place, which is very expensive.
21
REC2
REC1
22
COMP-REC
PROPYLEN 17
BUTANOL CAMPAIGN
15
B9
FEEDCOMP B10 OXO-UNIT
B4
B-AL-COL
FLASH1 B-OL-COL
SYNGAS 10 21
18
16
9 19 N-BUTANO
HYDNATOR
FLASH2
I-BUTANO
23
2 25
BUTANAL
B3
SYNG
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL
2012
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
In Butanol campaign the N-Bal/I-Bal is directly fed in to the VPH converter, and
is hydrogenated to from N-Butanol or I-Butanol.
Butyraldehyde from the isomer column and from storage tank is fed directly to
the vaporizer. The vaporizer design enables to vaporize the liquid feeds. To avoid liquid
carryover to converter which can damage catalyst and to concentrate heavies in the VPH system
which have been produced by VPH side reactions.
The catalytic reaction takes place at hot spot temperature of 160-170 0C and a pressure of
4.5 kg/cm2. The hydrogenation reaction is exothermic, the heat produced is being used to
generate dump steam at 1.5kg/cm2 an 1150C from condensate to the reactor.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Hydrogenation:
N/I –Bal + H2 N/I Butanol
Pressure : 4.5 kg/cm2
Temperature : 160-1700C.
Catalyst : copper based Zinc
Butanols refining:
All the main constituents in crude butanol are relatively low boiling compounds.
The distillation was done just above atmospheric pressure. So that vacuum set is not used.
Column pressure is controlled by using Nitrogen supply and atmospheric venting.
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
6
MATERIAL AND
ENERGY BALANCES
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
1.Hydroginator:
C4H8 O + H2 CH3CH2CH2CH2OH
Butanal(N,iso) Butanol(N,Iso)
Total crude fed to reactor = 106.4/0.99 =107.46 kmol /day (since 99% convesion)
Butane to reactor = 1.26 kmol/day
Total syn gas required = 106.4/0.492 = 216.2kmol /day (since 49.2% of H2 in syn gas)
Since no side reactions at reactor conditions .the outlet of the reactor contains
98% of crude butanal exit from 1 st reactor is recovered and it is send to the 2nd reactor
the content of butanal from the outlet of first reactor = 106.4/0.98 = 108.6 kmol/day
2.Oxo unit :
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
C3H6 + CO + H2 C4H8 O
= 0.2 kmol/day
==0.2 kmol/day
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Since flash column less volatiles are collected as bottom and high volatiles are collected as top
H2 = 5.7 kmol/day
(3)butaraldehyde column :
=108.6/118.70 =0.915
XD = 0.1, XW = 0.99
= 106.4/107.46 = 0.99
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
FXF = D XD + WXW
D = 11.24 kmol/day
Distillate contents :
Bottoms of columns are fed to the 2nd reactor .the second reactor outlet are fed to flash
column .where the crude butanol (combination of n and iso butanols) separated as bottom
and the rest are flashed off.
CO = 100.7 kmol/day
F = 116.049 kmol/day
Therefore XF = 91/116.049
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
n- butanol xw = 0.995
Butaraldehyde = 0.003
Water = 0.001
Butaraldehyde = 0.003
n- butanol xD =0.001
water = 0.001
FXF = D XD + W XW
W = 91.4325 kmol/day
D = F – W =24.6165
Conclusion :
COMPRESSOR :
entering leaving
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
OXO UNIT :
selectivity =10.2:1 (N: ISO ) at T=900C & P=15.7 bar , Conversion 99.8%
C3H6 + CO + H2 C4H8 O
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
INPUT
Out put :
Input : B1
Butaraldehyde = 108.6 kmol/day
Syn gas = 233.5 kmol/day
Butane = 1.26 kmol/day
CO = 108.8 kmol/day
OUT PUT
Propane = 0.2 kmol/day
H2 = 114.9 kmol/day
Water = 0.2 kmol/day
CH4 = 7.94 kmol/day
Methane = 7.739 kmol/day
CO2 = 1.1675 kmol/day
CO2 = 1.1675 kmol/day
H2O = 0.7 kmol/day
H2 = 5.7 kmol/day
Propylene = 117 kmol/day
FLASH COLUMN I :
32 H2 = 5.7 kmol/day
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
VENT
B3
INPUT
Input :
33
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
fla s h1
S t re a m ID F L V
F rom B1 B1
To B1
P ha s e MIXED LIQUID VAP O R
S ubs t re a m: MIXE D
Mole F low lbm ol/ hr
N-B UT-01 9. 185928 8. 801158 . 3847696
IS O BU-01 . 9388018 . 8873431 . 0514586
P RO P A-01 . 7734551 . 0901058 . 6833493
CO . 0202090 7. 19606E-5 . 0201370
H2 . 5107376 5. 74143E-4 . 5101634
C H4 . 7440601 6. 65178E-3 . 7374084
C O2 . 1083939 2. 11193E-3 . 1062820
H2O . 0661386 4. 84910E-4 . 0656537
Tot a l F low lbm ol/ hr 12. 34772 9. 788502 2. 559222
Tot a l F low lb/ hr 783. 6641 702. 7929 80. 87116
Tot a l F low c uft/ hr 71. 31891 13. 60241 995. 6313
Tem pe ra ture F 194. 0000 77. 00000 77. 00000
P re s s ure ps i 227. 7092 14. 69595 14. 69595
Vapor F ra c . 1515923 0.0 1. 000000
Liquid F ra c . 8484077 1. 000000 0.0
S olid F ra c 0.0 0.0 0.0
Ent ha lpy Bt u/ lbm ol -87933. 17 -1.0334E + 5 -46581. 82
Ent ha lpy Bt u/ lb -1385. 510 -1439. 324 -1474. 113
Ent ha lpy Bt u/ hr -1.0858E + 6 -1.0115E + 6 -1.1921E + 5
Ent ropy Bt u/ lbm ol-R -80. 81411 -101. 9268 -31. 97145
Ent ropy Bt u/ lb-R -1. 273339 -1. 419636 -1. 011758
Dens ity lbm ol/ c uft . 1731339 . 7196154 2. 57045E-3
Dens ity lb/ c uft 10. 98817 51. 66680 . 0812260
Ave ra ge MW 63. 46628 71. 79780 31. 59990
Liq Vol 60F c uft/ hr 16. 83240 14. 05376 2. 778639
Distillate :
OVERHEAD
INPUT B5
Residue :
BOTTOMS
Input : Butaraldehyde = 108.6 kmol/day
Butaraldehyde = 108.6 kmol/day Butane = 1.26 kmol/day
Butane = 1.26 kmol/day
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
d istill
Stream ID FE ED DIST RESI
Temp eratu re K 3 9 3.1 4 1 0.6 4 2 1.1
P res su re atm 2 .1 0 2 .5 0 2 .5 1
Vap o r Frac 0 .00 0 0 .00 0 0 .00 0
Mole Flo w k mol/h r 4 .18 4 3 .02 5 1 .15 9
Mass Flo w k g/h r 3 09 .97 2 2 24 .08 2 85 .89 0
Vo lume Flo w l /min 7 .32 8 5 .48 7 2 .11 4
En thalpy MMBtu /h r -1.2 16 -0.8 71 -0.3 27
Mole Flo w k mol/h r
N -BUT-01 1 .09 9 0 .11 5 0 .98 4
ISOBU -01 3 .01 6 2 .84 1 0 .17 5
N -BUT-02 0 .06 3 0 .06 2 trace
ISOBU -02 0 .00 7 0 .00 7 trace
H 2O
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COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
C4H8 O + H2 CH3CH2CH2CHO
Butanal(N,iso) Butanol(N,Iso)
B6
INPUT OUTPUT
FLASH
Syn gas COLUMN 2 : kmol/day
= 216.2 CO2 = 100.7 kmol / day
37
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
VENT
B3
INPUT
38
HY DRGN TR
Stream ID REAC P ROD VAP O R LIQU ID
39
From HY DRGN TR B1 B1
To HY DRGN TR B1
P h ase VAP O R VAP O R VAP O R LIQU ID
Sub stream: MIXED
Mole Flo w lb mol/h r
N -BUT-01 8 .81 8 49 1 .0 96 3 30 2 .0 26 8 88 1 .0 69 4 42 0
ISOBU -01 .9 02 0 58 1 .3 15 2 70 1 .1 13 5 35 3 .2 01 7 34 8
P RO P A-0 1 .0 90 0 22 0 .0 90 0 22 0 .0 89 8 04 4 2 .1 7 65 3 E-4
H2 9 .76 2 06 9 .4 53 1 20 8 .4 53 0 97 0 2 .3 8 14 1 E-5
CO 9 .24 6 18 7 9 .24 6 18 7 9 .24 4 73 5 1 .4 5 19 8 E-3
CH 4 .6 74 6 14 5 .6 74 6 14 5 .6 74 3 80 9 2 .3 3 59 0 E-4
CO 2 .0 99 2 08 0 .0 99 2 08 0 .0 99 1 12 1 9 .5 8 93 0 E-5
H 2O .0 59 5 24 8 .0 59 5 24 8 .0 54 6 37 8 4 .8 8 69 8 E-3
N -BUT-02 0.0 2 .46 4 10 2 .0 47 1 59 5 2 .41 6 94 3
ISOBU -02 0.0 6 .84 4 84 6 .2 01 4 64 9 6 .64 3 38 1
Total Flo w lb mol/h r 2 9 .6 5 21 7 2 0 .3 4 32 3 1 1 .0 0 48 2 9 .33 8 41 1
Total Flo w lb /hr 9 9 9.8 18 2 9 9 9.8 18 2 3 0 8.5 41 6 6 9 1.2 76 6
Total Flo w cu ft/hr 7 0 32 .97 8 1 0 44 9 .4 0 4 3 08 .11 4 1 3 .7 1 16 2
Temp eratu re F 1 9 4.0 00 0 2 4 8.0 00 0 7 7 .0 0 00 0 7 7 .0 0 00 0
P res su re p si 2 9 .3 9 19 0 1 4 .6 9 59 5 1 4 .6 9 59 5 1 4 .6 9 59 5
Vap o r Frac 1 .00 0 00 0 1 .00 0 00 0 1 .00 0 00 0 0.0
Liq uid Frac 0.0 0.0 0.0 1 .00 0 00 0
Solid Frac 0.0 0.0 0.0 0.0
En thalpy Btu /lbmo l -44 2 07 .37 -78 1 01 .75 -48 2 03 .32 -1 .3 9 91 E+5
En thalpy Btu /lb -13 1 1.0 83 -15 8 9.1 30 -17 1 9.2 78 -18 8 9.9 67
En thalpy Btu /hr -1 .3 1 08 E+6 -1 .5 8 88 E+6 -5 .3 0 47 E+5 -1 .3 0 65 E+6
En trop y Btu /lbmo l-R -14 .04 6 12 -31 .89 4 11 1 4 .3 1 12 2 -12 4 .1 3 06
En trop y Btu /lb-R -.4 1 65 7 38 -.6 4 89 4 72 .5 10 4 41 1 -1.6 76 8 72
Dens ity lb mol/cuft 4 .2 1 61 6 E-3 1 .9 4 68 3 E-3 2 .5 5 44 4 E-3 .6 81 0 58 2
Dens ity lb /cu ft .1 42 1 61 4 .0 95 6 81 8 .0 71 6 18 7 5 0 .4 1 53 9
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL
Av erage MW 3 3 .7 1 82 1 4 9 .1 4 74 8 2 8 .0 3 69 6 7 4 .0 2 50 8
Liq Vo l 60 F cu ft/hr 3 1 .0 8 02 6 2 3 .4 3 54 5 9 .69 5 02 2 1 3 .7 4 04 3
2012
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
BUTANOL COLUMN :
Butaraldehyde = 3 kmol/day
n- butanol =1 kmol/day
OVERHEAD
B5
INPUT
Butaraldehyde = 3 kmol/day
40
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
d istill
Stream ID FE ED DIST RESI
Temp eratu re K 3 9 3.1 4 1 0.6 4 2 1.1
P res su re atm 2 .1 0 2 .5 0 2 .5 1
Vap o r Frac 0 .00 0 0 .00 0 0 .00 0
Mole Flo w k mol/h r 4 .18 4 3 .02 5 1 .15 9
Mass Flo w k g/h r 3 09 .97 2 2 24 .08 2 85 .89 0
Vo lume Flo w l /min 7 .32 8 5 .48 7 2 .11 4
En thalpy MMBtu /h r -1.2 16 -0.8 71 -0.3 27
Mole Flo w k mol/h r
N -BUT-01 1 .09 9 0 .11 5 0 .98 4
ISOBU -01 3 .01 6 2 .84 1 0 .17 5
N -BUT-02 0 .06 3 0 .06 2 trace
ISOBU -02 0 .00 7 0 .00 7 trace
H 2O
41
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
PROCESS EQUIPMENT
DESIGN
42
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
X 0 0.013 0.075 0.141 0.211 0.28 0.37 0.459 0.555 0.65 0.773 1
8 9
Y 0 0.031 0.161 0.281 0.393 0.49 0.591 0.678 0.757 0.83 0.897 1
6 1
• Top allowance for column = 0.5 m Bottom allowance for column = 0.5 m
43
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Or
• Top allowance for column = 0.5 m Bottom allowance for column = 0.5 m
Column height =Top allowance for column + bottom allowance for column
Column Diameter:
L
1. F= ∗√ (lv/¿)
V
FLv = Liquid Vapour flow factor
L = Liquid Mass flow rate (kg/s)
ρV= Density of Vapour (kg/m3)
ρL= Density of Liquid (kg/m3)
¿−lv
2. Umax=Kv∗√( )
lv
Umax= maximum vapour velocity (m/sec)
Kv= constant, which depends on tray spacing and FLV
At the top
ΡVT¿ PM /RT
44
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
ΡL = Density of n-butanol
Density of n-butanol=880kg/m3
ΡL = (880*0.9912) + (870*0.008)
= 879.216
lVT
FLv = Slop of top operating line*
√ lLT
2.6966
√
= 0.11
879.216
= 0.00609
Kv is found to be 0.09
¿−lv
Maximum Vapour Velocity, Umax¿ Kv∗√ ( )
lv
¿ 0.09∗√ (( 880−2.6966¿)/2.6966)¿
= 1.6233m/sec
= 1390.42(2.82+1)
=1.089
1.089
¿
1.2173∗2.6966
45
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
= 0.33m2
0.33
Total area =
0.65
=0.507
Column Diameter ¿ √ ¿
= 0.8036 m
AT THE BOTTOM:
PM 2
ΡVT¿
RT 2
= 73.8188
1∗89.8188
Density at Bottom ¿
0.08206∗379.426
ΡL = Density of n-butanol
= 872.868kg/m3
lVb
FLv = Slop of top operating line*
√ lLb
2.8868
= 0.11
√ 872.868
= 0.006328
Kv is found to be 0.09
46
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
¿−lv
Maximum Vapour Velocity, Umax¿ Kv∗√ ( )
lv
¿ 0.09∗√ (( 870−2.8868¿)/2.8868)¿
= 1.5598m/sec
= 1390.42(1.82+1)
=1.089
0.023088
¿
1.1698∗2.8868
= 0.00683m2
0.00683
Total area = =0.0105m
0.65
Column Diameter ¿ √ ¿
= 0.71575 m
Large value for diameter will be chosen for design, hence D = 0.806m
47
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
MECHANICAL DESIGN
48
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
a) shell:
Diametre= 0.806m
operating pressure=0.5atm=50.6625kpa=0.51645 kg/cm2
design pressure=1.1*operating pressure=55.72kpa
operating temperature=124.570c
design temperature=139.0270c
shell material=carbon steel
-tray spacing=0.5m
top disengaging space=0.3m
skirt=3m
allowable stress for shell material=34335kpa
insulation=asbestos
insulation thickness=75mm
c)skirt support:
material-carbon steel
height=3.0m
d)nozzles:
49
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
no. of nozzles=4
e) trays:
no. of trays=20
spacing=0.5m=500mm
hole diameter=5cm
thickness=3mm
weir height=50mm
material for trays=material ss
ts=PDi/2fj-p+c
Ts=thickness of shell(mm)=2.577m
P=design pressure(kg/cm2) Di=diameter of the shell(mm)
F=allowable/permissible tensile stress(kg/cm2)=950 kg/cm2
C=corrosion allowance(mm)=2mm
J=joint efficiency=0.85
ts=2.577mm
Taking the thickness of the shell as ts= 6mm
50
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
3) calculation of stress:
1)axial tensile stress due to pressure
Fap= pdi/4(ts-c) = 0.5681*1640/4(6-2) = 58.23 kg/cm2
This is same throught the column height
2)circumferential stress:
2 Fap= 2*58.23 = 116.46 kg/cm2
3)compressive stress e dead loads:
a) compressive stress due to weight of shell up to a distance x in meter
fds=weight o shell= (Π/4(Do2-Di2)* *x)/ (Π/4(Do2-Di2)
= *x = 0.0077*100 = 0.772*X kg/cm2
cross setion area of shell fds
di,do-internal and external diameter of shell
Ss-density of the shell
Fds= 0.7720 *X kg/cm2
Dm=mean diameter of the shell(cm)
Ts=thickness of the shell(cm),
51
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
C=corrosion allowance
b) Compressive stress due to the weight of the insulation at height(x)m
fd(ins)
dins=diameter of the insulation
tins=thickness of the insulation
sins=density of the insulation
dm=mean diameter of the shell = 1.802 m
sins= Π dins*tins sins(x)/Π DM[ts-c] = 575 kg/m3 = 0.000575 kg/cm3
tins=75mm = 7.5 cm
dins=dc+2ts+2tins
dins=1640+2*6+2*75 = 1802 mm = 1.802 m
dm= DC+(Dc=2ts)/2 = 1640+1640+2*6/2 = 1646 mm = 164.6 cm
C)compressive stress due to liquid&tray in the column upto height(x)m
liquid &tray weight for height(x)
fliq=[(x-0.3)/0.5+1]Π/4di*sliquid
fliq=[x-top disengaging space]/tray spacing)+1] Π/4di*sliquid
fliq= fliq/Πdm(ts-c)= (x+0.16)*5754/(Π*164.6)*(0.6-0.2) = 27.818+4.45 kg/cm2
d)tensile stress due to wind loads in self supporting vessel
fwx=Mw/z
mw=bending moment due to wind load=wind load*distance/2
z=modulus for the area of the shell=Π/4*dm2(ts-c)
fwx=0.7pwx2*2/Π*dm(ts-c) = 1.4*121.9*10-4*104/Π*164.2*(6-2)
fwx=0.825x2kg/cm2
stress due to seismic load are neglected
52
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
ftmax=fj
f=allowable stress=950kg/cm2
j=joint factor=0.85
950*0.85=0.825x2+58.23-0.77x
From this height (H)=30.60m
53
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
=4983.68kg
We=weight of water during test = Π/4*(di)2[H-pj]*
= Π/4*(1.64)2[21.3-3]*1000
=36657.04kg
Wa =weight attachments=7100kg
Wmax= 52728.42kg =517.26KN
Period of vibration at min dead wt
Tmin= 6.35*10-5(H/D)3/2 * Wmin1/2/ts1/2
Tmin= 6.35*10-5(21.3/1.64)3/2 * 950271/2/0.0061/2
Tmin= 0.374sec
K1=0.7 cylindrical vessel
K2=1.0 [vibration period less then 0.5 sec]
K2=2
P1=40-100kg/m2 p2=100-200kg/m2
54
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
55
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
= 2445.24kg
Pw(max)=0.7*2*100*1.802*21.3
=5373.564kg
56
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
COST ESTIMATION
57
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
COST ESTIMATION :
An acceptable plant must design a process that is capable of operating under conditions, which
yield a profit. Capital must be allocated for direct labor and equipment. Besides many plant expenses
many other indirect plant expenses are included and these must be included in the total cost analysis of
the plant.
A capital investment is required for any other industrial process. the capital investment plus
working capital which must be available pay salaries , keep raw materials and product on hand handle
other special items required a direct cash outlay thus in an analysis of costs, manufacturing costs and
general expenses including income tax must be taken into consideration.
Capital investment is defined as the total amount of money needed to supply the necessary plant
and manufacturing facilities plus the amount of money required as working capital for operating of the
facilities.
Fixed capital investment represents the capital necessary for the installed process equipment with
all auxiliaries that are neede for complete process operation.
Expenses for piping; instruments, insulation, foundations and site preparation are typical
examples of costs included in the manufacturing fixed capital investment.
58
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
DIRECT COST :
1.Installation cost :
Assuming 15%
It is 25 - 18% of PEC.
59
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Assuming 20%
It is 50 - 70% of PEC.
Assuming 60%.
It is 10-40% of PEC
Assuming 25%.
It is 10-70% of PEC
Assuming 45%
6.SERVICE FACILTIES
It is 30-80% of PEC.
Assuming 55%
7.YARD IMPROVEMENT
It is 10-20% of PEC
Assuming 15%.
8.LAND
It is 10-20% of PEC
Assuming 15%.
60
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
It is 15% of PEC
TOTAL=OC=Rs.3.88755 crores.
DPC=PEC+OC=1.467+3.88755=5.35455 crores.
INDIRECT COST :
These include expenses which are not directly involved with materials and labor of actual installation complete
facility.
1.ENGG.&SUPERVISION COST :
It is 15-35% of DC.
Assuming 25%
It is 30% of DC.
3. CONTINGENCY
It is 8-20% of DC.
Assuming =15%
It is 10 - 20% of FCI
Assuming 15%
61
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Manufacturing cost = fixed charges + direct production cost + plant overhead cost
1. FIXED CHARGES
a) DEPRICATION
It is 10% of FCI
b) LOCAL TAXES
It is 3 - 4% of FCI
Assume 3.5%
c) INSURENCE
It is 0.4-1% of FCI
Assume 0.5%
=Rs.8.49587 crores.
A) Raw Materials
It is 20% of TPC
=Rs.1.69917 crores
b}OPERATING Labour
62
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
It is 10-20% of TPC
Assuming 15%
d) Utilities:
It is 10-20% of TPC
Assuming 15%
e) MAINTENANCE:
It is 2 - 10.5% of FCI.
Assuming 6%
f}OPERATING SUPPLIES:
Assuming 15%
g)LABORATORY CHARGES:
Assuming 15%
It is 2-6% of TPC
Assuming 4%
63
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Assuming 60%
=1.27438+9.34544+2.08998=12.7098 crores.
GENEREL EXPENSES
ADMINISTRATION COST:
Assuming 25%
It is 2-20% of TDPC
Assuming 15%
It is 3% of TDPC
=2.00078+12.7098
=14.71058 crores.
total 2913975.
=87.41925 crores
64
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
=87.41925-12.7098
= 74.70945
=100* (15569392/121713026)
=12.79
=13
=(127798677/(15569392-121.71))
= 8 years
65
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
CHAPTER
10
SITE CONSIDERATIONS
AND PLANT LOCATION
66
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Plant layout:
The parameters considered to arrive at the plant layout are:
1.Economic considerations:
Construction and operating costs .The cost of construction can be minimized by adopting
a layout that gives the shortest run of connecting pipe between equipment and the least of
structural steel work.
2. Process requirements:
The locations of certain pieces of equipment are based on the process requirement. For
example, a condenser is placed sufficiently high so as to have a barometric leg.
3. Operation:
Equipment that needs t have frequent operator attention should be located convenient the
control room. Valves, sample points and instruments should be located at convenient positions
and heights. Sufficient working space and headroom must be provided to allow easy access to
equipment.
4. Maintenance:
Heat exchangers need to be sited to do that the tube bundles can easily be removed.
Vessels that require frequent replacement of catalyst or packing should be located on the outside
of buildings. Equipment that requires dismantling for maintenance, such as compressors and
large pumps, should be placed under cover.
67
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
5. Safety:
Blast walks way may be needed to isolate potentially hazardous equipment, and confine
the effects of an explosion. At least two escape routes for operators must be provided from each
level in process buildings.
6. Plant expansion:
Equipment should be located so that it can be conveniently tied in with any future
expansion of the process. Space should be left on pipe alleys for future needs, and service pipes
over-sized to allow for future requirements.
7. Modular construction:
In recent years, there has been a move to assemble sections of the plant as the plant
manufacturer’s site. These modules will include the equipment, structural steel, piping etc.
1.Parking
2. Canteen
3. Security
4. Training center
5. Administrative building
6. Laboratories(RAD)
7. Fire section
8. Boilers
9. Control room
10. Process
11. Storage
12. Work shop
13. Expansion
14. Lab
15. Raw materials
The various needs and conditions must be defined clearly before considering a
site to locate a factory. The main factor that is to be considered for a factory is to be
considered for deciding the location of site for a factory is that it should yield maximum
possible benefit with minimum possible efforts.
The many number of factors that are to be taken into account to satisfy the statement are broadly
divided into two groups.
1. Primary factors
68
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
2. Secondary factors
1. Primary factors:
a) Availability of raw materials:
The location f the factory is influenced by source of raw materials. It is definitely
advantageous thing if the factory is located near the source of raw material.
For the purpose of locating a factory the raw materials are classified as:
o Internal source
c) Availability of labor:
Availability of required labor in the requisite type is also an essential consideration.
Density of population is not only consideration. The people in the surrounding areas willing to
work in the factory depends on maturity of citizens, influence of local industries, live hood etc.
d) Climate and atmospheric conditions:
If the climate and atmospheric conditions are not favorable, employees may not be
willing to work. The second consideration is precision machines get spoiled.
o If there is such fluctuation of temperature.
o If the factory is within vicinity of sea breeze it requires a cool atmosphere.
In modern the temperature inside the factory is regulated by scientific
methods.
e) Market facilities:
Facilities for marketing the finished quota should be available. If the markets are near to
the factory.
o The cost of transportation will be less
69
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
f) Transportation facilities:
Economical conveyance and quick transport facilities should always be available.
Whenever the raw materials etc. are to be transported to the factory or finished products to the
markets, road, rail, water consideration.
g) Scope of expansion:
The scope of future expansion should be considered when the increase of demand for
finished good is anticipated either in short or long run.
2. Secondary factors:
The following factors are also to be taken into account before selecting a site for a
factory.
1. Cost of land
2. Laws governing the area
3. Fire protection
4. Availability of water for the employees and factory purposes
5. Availability of proper daily necessities to the employees
6. Progressive attitude of citizens of the area towards the industry
7. Mental development of people of area
8. Residential housing to employees
9. Educational facilities to the children of employees
10. Health and welfare services
Conclusion:
Practically it is not possible to select a site which will satisfy all the above conditions.
Sometimes a site satisfying all the above conditions may not be possible. In such cases
advantages and disadvantages should be weighed carefully while selecting the best site possible.
In some cases one or two factors may play greater importance.
The layout of a chemical plant is not an exact science but rather an art as it
embraces high degree of experience coupled with the need to anticipate the human element in
both in operation and maintenance. It is however the most important factor in a process plant
project in that a carefully planned functional arrangement of equipment, building and pipe work
is the key to economical construction and efficient operation.
70
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Rational design must include arrangement of processing areas storage areas and handling areas
in efficient coordination and with regard to such factors as:
o
o Future expansion
The storage facilities for the raw material, intermediate and finished products may be
located in isolated areas or in adjoining areas reduce materials handling. It may reduce an
obstacle future expansion of the plant. So here the storage tanks are laid our conveniently so that
they may not become an obstacle to future expansion site.
Expansion is kept in mind and as the question of multiplying the number of units r
increasing the size prevailing unit, is more important a site for future expansion is also provided.
Road ways of correct capacity and the right location are made so that the transportation is easier
and convenient.
71
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
PLANT LAYOUT
72
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
UTILITIES
The word "Utilities" is now generally used for the ancillary services needed in the operation of
any production process. These services will normally be supplied from a central site facility; and
will include:
Electricity.
Steam, for process heating.
Cooling water.
Water for general use.
Demineralised water.
Compressed air.
Inert-gas supplies.
Refrigeration.
Effluent disposal facilities.
Electricity
The power required for electrochemical processes; motor drives, lighting, and general use, may
be generated on site, but will more usually be purchased from the local supply company (the
national grid system in the UK).
The voltage at which the supply is taken or generated will depend on the demand. For a large site
the supply will be taken at a very high voltage, typically 11,000 or 33,000 V. Transformers will
be used to step down the supply voltage to the voltages used on the site. In the United Kingdom a
three-phase 415-V system is used for general industrial purposes, and 240-V single-phase for
lighting and other low-power requirements. If a number of large motors is used, a supply at an
intermediate high voltage will also be provided, typically 6000 or 11,000 V.
A detailed account of the factors to be considered when designing electrical distribution systems
for chemical process plants, and the equipment used (transformers, switch gear and cables).
Steam
The steam for process heating is usually generated in water tube boilers; using the most
economical fuel available. The process temperatures required can usually be obtained with low-
pressure steam, typically 2.5 bar (25 psig), and steam is distributed at a relatively low mains
pressure, typically around 8 bar (100 psig). Higher steam pressures, or proprietary heat-transfer
fluids, such as Dowtherm, will be needed for high process temperatures. The generation,
distribution and utilization of steam for process heating in the manufacturing industries.
Combined heat and power (co-generation)
The energy costs on a large site can be reduced if the electrical power required is generated on
site and the exhaust steam from the turbines used for process heating. The overall thermal
efficiency of such systems can be in the range 70 to 80 per cent; compared with the 30 to 40 per
cent obtained from a conventional power station, where the heat in the exhaust steam is wasted
in the condenser. Whether a combined heat and power system scheme is worth considering for a
73
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
particular site will depend on the size of the site, the cost of fuel, the balance between the power
and heating demands; and particularly on the availability of, and cost of, standby supplies and
the price paid for any surplus power electricity generated.
On any site it is always worth while considering driving large compressors or pumps with steam
turbines and using the exhaust steam for local process heating.
Cooling water
Natural and forced-draft cooling towers are generally used to provide the cooling water required
on a site; unless water can be drawn from a convenient river or lake in sufficient quantity. Sea
water, or brackish water, can be used at coastal sites, but if used directly will necessitate the use
of more expensive materials of construction for heat exchangers.
The water required for general purposes on a site will usually be taken from the local mains
supply, unless a cheaper source of suitable quality water is available from a river, lake or well.
DemineraLised water
Demineralised water, from which all the minerals have been removed by ion-exchange, is used
where pure water is needed for process use, and as boiler feed-water. Mixed and multiple-bed
ion-exchange units are used; one resin converting the cations to hydrogen and the other removing
the acid radicals. Water with less than 1 part per million of dissolved solids can be produced.
Refrigeration
Refrigeration will be needed for processes that require temperatures below those that can be
economically obtained with cooling water. For temperatures down to around 10°C chilled water
can be used. For lower temperatures, down to-30°C, salt brines (NaCl and CaCl2) are used to
distribute the "refrigeration" round the site from a central refrigeration machine. Vapour
compression machines are normally used.
Compressed air
Compressed air will be needed for general use, and for the pneumatic controllers that are usually
used for chemical process plant control. Air is normally distributed at a mains pressure of 6 bar
(100 psig). Rotary and reciprocating single-stage or two-stage compressors are used. Instrument
air must be dry and clean
Inert gases
Where large quantities of inert gas are required for the inert blanketing of tanks and for
purging this will usually be supplied from a central facility. Nitrogen is normally used, and is
manufactured on site in an air liquefaction plant, or purchased as liquid in tankers.
74
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Effluent disposal
Facilities will be required at all sites for the disposal of waste materials without creating a public
nuisance.
ENVIRONMENTAL CONSIDERATIONS
All individuals and companies have a duty of care to their neighbours, and to the
environment in general. In the United Kingdom this is embodied in the Common Law. In
addition to this moral duty, stringent controls over the environment are being introduced in the
United Kingdom, the European Community, the United States, and in other industrialized
countries and developing countries.
Vigilance is required in both the design and operation of process plant to ensure that legal
standards are met and that no harm is done to the environment.
Consideration must be given to:
Waste management
Waste arises mainly as byproducts or unused reactants from the process, or as off
specification product produced through mis-operation. There will also be fugitive emissions from
leaking seals and flanges, and inadvertent spills and discharges through mis-operation. In
emergency situations, material may be discharged to the atmosphere through vents normally
protected by bursting discs and relief value
The designer must consider all possible sources of pollution and, where practicable,
select processes that will eliminate or reduce (minimize) waste generation.
75
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
another company, for use as raw material in their manufacturing processes. For example, the use
of off-specification and recycled plastics in the production of lower grade products, such as the
ubiquitous black plastics bucket.
When waste is produced, processes must be incorporated in the design for its
treatment and safe disposal. The following techniques can be considered:
Gaseous wastes
Gaseous effluents which contain toxic or noxious substances will need treatment before
discharge into the atmosphere. The practice of relying on dispersion from tall stacks is seldom
entirely satisfactory. Witness the problems with acid rain in Scandinavian countries attributed to
discharges from power stations in the United Kingdom. Gaseous pollutants can be removed by
absorption or adsorption . Finely dispersed solids can be removed by scrubbing, or using
electrostatic precipitators. Flammable gases can be burnt.
Liquid wastes
The waste liquids from a chemical process, other than aqueous effluent, will usually be
flammable and can be disposed of by burning in suitably designed incinerators. Care must be
taken to ensure that the temperatures attained in the incinerator are high enough to completely
destroy any harmful compounds that may be formed; such as the possible formation of dioxins
when burning chlorinated compounds. The gases leaving an incinerator may be scrubbed, and
acid gases neutralised.
In the past, small quantities of liquid waste, in drums, has been disposed of by dumping at sea or
in land-fill sites. This is not an environmentally acceptable method and is now subject to
stringent controls.
Solid wastes
76
COPRODUCTION OF N-BUTANOL AND ISO-BUTANOL 2012
Solid waste can be burnt in suitable incinerators or disposed by burial at licensed land-fill
sites. As for liquid wastes, the dumping of toxic solid waste at sea is now not acceptable.
Aqueous wastes
The principal factors which determine the nature of an aqueous industrial effluent and on
which strict controls will be placed by the responsible authority are:
1. pH.
2. Suspended solids.
3. Toxicity.
4. Biological oxygen demand.
The pH can be adjusted by the addition of acid or alkali. Lime is frequently used to
neutralise acidic effluents. Suspended solids can be removed by settling, using clarifiers. For
some effluents it will be possible to reduce the toxicity to acceptable levels by dilution. Other
effluents will need chemical treatment.
The oxygen concentration in a water course must be maintained at a level sufficient
to support aquatic life. For this reason, the biological oxygen demand of an effluent is of utmost
importance. It is measured by a standard test: the BODS (five-day biological oxygen demand).
This test measures the quantity of oxygen which a given volume of the effluent (when diluted
with water containing suitable bacteria, essential inorganic salts, and saturated with oxygen) will
absorb in 5 days, at a constant temperature of 20°C. The results are reported as parts of oxygen
absorbed per million parts effluent (ppm). The BODS test is a rough measure of the strength of
the effluent: the organic matter present. It does not measure the total oxygen demand, as any
nitrogen compounds present will not be completely oxidised in 5 days. The Ultimate Oxygen
Demand (UOD) can be determined by conducting the test over a longer period, up to 90 days. If
the chemical composition of the effluent is known, or can be predicted from the process flow
sheet, the UOD can be estimated by assuming complete oxidation of the carbon present to carbon
dioxide, and the nitrogen present to nitrate:
Noise
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Noise can cause a serious nuisance in the neighborhood of a process plant. Care needs to
be taken when selecting and specifying equipment such as compressors, air-cooler fans, induced
and forced draught fans for furnaces, and other noisy plant. Excessive noise can also be
generated when venting through steam and other relief valves, and from flare stacks. Such
equipment should be fitted with silencers. Vendors' specifications should be checked to ensure
that equipment complies with statutory noise levels; both for the protection of employees, as well
as for noise pollution considerations. Noisy equipment should, as far as practicable, be sited well
away from the site boundary. Earth banks and screens of trees can be used to reduce the noise
level perceived outside the site.
Visual impact
The appearance of the plant should be considered at the design stage. Few people object
to the fairyland appearance of a process plant illuminated at night, but it is a different scene in
daylight. There is little that can be done to change the appearance of a modern style plant, where
most of the equipment and piping will be outside and in full view, but some steps can be taken to
minimize the visual impact. Large equipment, such as storage tanks, can be painted to blend in
with, or even contrast with, the surroundings. Landscaping and screening by belts of trees can
also help improve the overall appearance of the site.
Legislation
It is not feasible to review the growing body of legislation covering environmental
control in this short chapter. All that can be done is to give a brief resume of the principal
legislation current in the United Kingdom. Legislation and control procedures in other countries
are likely to be similar in scope and practice.
Stricter legislation and tighter control of discharges into the environment are being introduced
in most countries. The specialist texts brought out by publishers catering for management topics,
and by the government departments, should be consulted for up-to-date information on
environmental legislation.
The key legislation in the United Kingdom is:
The Environmental Protection Act (EPA), 1991, which subsumes previous acts; such as
the alkali act (1906), and the clean air act (1956/68). The act covers air pollution, noise,
and other matters causing a statutory nuisance.
The Water Resources Act, 1991, which covers discharges into inland water ways.
Consent from the National Rivers Authority (NRA) is needed for such discharges. 3. The
Water Industries Act, 1991, and the Trade Effluent Regulations, 1989, which cover
discharges into the sewers.
The Town and Country Planning Act, 1990, which covers planning consents.
Some aspects of the Control of Substances Hazardous to Health Act (COSHH)
regulations and the Health and Safety at Work Act, will also apply to waste handling,
treatment and disposal.
Legislation and control procedures in the United Kingdom are increasingly being derived
from regulations promulgated by the European Commission (E.C). All the legislation embodies
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the concept of Best Practicable Means (BPM). This requires the designer to use the most
appropriate treatment to comply with the regulation, whilst taking into account: local conditions,
current technology and cost. The concept of BPM also applies to the installation, maintenance
and operation of the plant.
Environmental auditing
Identify environmental problems associated with manufacturing process and the use of
the products, before they become liabilities.
To develop standards for good working practices.
To provide a basis for company policy.
To ensure compliance with environmental legislation.
To satisfy requirements of insurers.
To be seen to be concerned with environmental questions: important for public
relations.
To minimize the production of waste: an economic factor.
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CHAPTER
11
SAFTEY
CONSIDERATIONS
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SAFETY
The International Safety Rating System (ISRS) was established in 1864 with the
collaboration of DENTNORSKE VERITAS. It is the most comprehensive safety Management
Evaluation system and its primary objective is to measure the organization levels of the loss
activity against a set of internationally accepted criteria.
2. Proximity suit:
The fire proximity suit is designed to give protection to the personnel for the
carrying out emergency operations in close proximity of fire radiant temperature up to 28 0c.This
suit is made with aluminized fabric at outer surface and insulation layers at inner surface to give
maximum radiant heat protection. This suit consists of coat, pants, hoods, hand gloves and boots.
It should be always used along with the breathing apparatus set.
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The fire entry suit is designed rescue and emergency operations in the case of fire
emergency. This suit is made with aluminized fabric at outer surface and more insulation layers
at inner surface and more insulation layers at inner surface to give maximum heat protection and
radiant heat protection. This suit consists of coat, pants, hoods, hand gloves and boots. It should
be always used along with the breathing apparatus set.
Instrumentation:
Inculcated all the IS and OSID recommendations. The P & id attached such that
instrument actions incorporated as pressure level indication valve open or close indication pump
running indication firewater on/off.
Major Accidents: An injury within the refinery area causing disablement for a period
more than 48hrs.From the shift in which the injured worked on the day of injury or any
dangerous occurrence.
Hi-Po Accidents: An event, which have high potential (HI-PO) to cause major accident.
Incident: An event which slightly different circumstances may have resulted in harm to
personnel, damage to property or loss of production.
Property Damage: Any loss property damage more than rupees one lakh.
Industrial illness: Any illness resulting from exposure to the working environment.
Dangerous occurrence:
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Bursting of plant used containing or supplying team under pressure greater than
atmospheric pressure.
Collapse or failure of a crane, derrick which hoist or the other appliances used in raising
or lowering persons of goods any part or thereof, or the overturning of a crane.
Expolosion, fire, bursting out, leakage or Escape of any molten metal or hot liquor or gas
causing bodily injury to any person or damage to any room or place in which persons are
employed or fire in rooms of cotton pressing factories, where a cotton opener is in use.
4.Explosion of a receiver or container used for the storage at pressure of any gas or
gases(including air) or any liquid or solid resulting from the compression of gas.
Collapse or subsidence of any floor, gallery, roof, bride, tunnel, chimney, wall, building,
or any other substance.
HYDROGEN:
It is in the very nature of a fuel to have some degree of danger associated with it. The hazards
they represent are neither good, nor bad; they just exist and must be handled.
Hydrogen is not significantly more or less hazardous than other fuels. By knowing
something about its use in the past, learning some of its basic properties and behaviour, and
making comparisons with other fuels, a public made up of knowledgeable individuals can assess
hydrogen's applications and participate in the public acceptance process. Hydrogen has over the
years acquired an image of an immensely powerful and possibly threatening substance. There are
still some, for example, who can recall the experience of the Hindenburg in 1937, as well as the
cold war and the threat of the hydrogen bomb (H-Bomb). The nuclear fusion reactions involved
in the H-bomb have, of course, nothing to do with the chemical reactions involved in the use of
hydrogen as a fuel for internal combustion engines and hydrogen fuel cells.
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FOR N-BUTANOL :
Composition:
Eye Contact:
Check for and remove any contact lenses. Immediately flush eyes with running water for
at least 15 minutes, keeping eye lids open. Cold water may be used. Get medical attention
immediately.
Skin Contact:
In case of contact, immediately flush skin with plenty of water for at least 15 minutes
while removing contaminated clothing and shoes. Cover the irritated skin with an emollient.
Cold water may be used.Wash clothing before reuse. Thoroughly clean shoes before reuse. Get
medical attention immediately.
Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial
cream. Seek immediate medical attention.
Inhalation:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult,
give oxygen. Get medical attention if symptoms appear.
Serious Inhalation:
Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a
collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is not
breathing, perform mouth-to-mouth resuscitation. Seek medical attention.
Ingestion:
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CLASS B-2: Flammable liquid with a flash point lower than 37.8°C (100°F). CLASS D-2B:
Material causing other toxic effects (TOXIC).
DSCL (EEC):
R10- Flammable. R22- Harmful if swallowed. R38- Irritating to skin. R41- Risk of serious
damage to eyes.
HMIS (U.S.A.):
Health Hazard: 1
Fire Hazard: 3
Reactivity: 0
Personal Protection: h
National Fire Protection Association (U.S.A.):
Health: 1
Flammability: 3
Reactivity: 0
Specific hazard:
Protective Equipment:
Gloves. Lab coat. Vapor respirator. Be sure to use an approved/certified respirator or equivalent.
Wear appropriate respirator when ventilation is inadequate. Splash goggles.
FOR ISO-BUTANOL
Version 1.04 Revision Date 20.11.2006
1. Identification of the substance/preparation and of the company/undertaking
Trade name Iso-Butanol
Synonyms Iso-Butanol, 2-Methyl-propan-1-ol, 2-Methylpropyl alcohol, 1
Hydroxymethylpropane, Isopropyl Carbinol, i-Butyl alcohol
Use Solvents, industrial use, raw material for washing and cleaning agents, raw material for
fragrances, Paint related material Company Hitech Chemicals
2. Composition/information on ingredients
2-methylpropan-1-ol; iso-butanol
content: 99.50 %W/W
CAS-No. 78-83-1 Index-No. 603-108-00-1 EG-Nr.: 201-148-0
Symbol(s) Xi R-phrase(s) -R10 -R37/38 -R41 -R67
For the full text of the R phrases mentioned in this Section, see Section 16.
Print Date 20.12.2006 100000000534 1/6
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3. Hazards identification
Identification of the risks
R10 Flammable.
R37/38 Irritating to respiratory system and skin.
R41 Risk of serious damage to eyes.
R67 Vapours may cause drowsiness and dizziness.
5. Fire-fighting measures
Suitable extinguishing media.Specific hazards during fire fighting,Special protective
equipment for firefighters Water spray, Dry chemical, Alcohol-resistant foam Flash back
possible over considerable distance. Do not allow run-off from fire fighting to enter drains or
water courses.Wear self-contained breathing apparatus and protective suit. Further information
Standard procedure for chemical fires. In the event of fire, cool tanks with water spray.
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9. Toxicological information
Acute oral toxicity LD50 rat: 2,460 mg/kg; literature value
LD50 rabbit: 74.1 mg/kg; literature value
Acute inhalation toxicity LC50 rabbit: 2,630 mg/m3; ; 4 h; literature value
LCLo rat: 8,000 mg/m3; ; 4 h; literature value
LC50 rat: 19,200 mg/m3; ; 4 h; literature value
Acute dermal toxicity LD50 rabbit: 3,400 mg/kg; literature value
Assessment of mutagenicity.
Experiments showed mutagenic effects in cultured bacterial Cells.
13 Transport information
ADR UN-No.: 1212; Class: 3; Packaging group: III; F1; Description of
the goods: ISOBUTANOL
RID UN-No.: 1212; Class: 3; Packaging group: III; F1; Description of
the goods: ISOBUTANOL
ADNR UN-No.: 1212; Class: 3; Packaging group: III; F1; Description of
the goods: ISOBUTANOL
IMDG UN-No.: 1212; Class: 3; EmS: F-E, S-D; Packaging group: III;
Description of the goods: ISOBUTANOL
ICAO/IATA UN-No. : 1212; Class: 3; Packaging group: III; Description of the
goods: Isobutanol
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CONCLUSIONS
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REFERENCES
n-Butanol Product Information, The Dow Chemical Company, Form No. 327-
00014-1001, page 1.^ Evans D., Osborn J. A., Wilkinson G. (1968).
"Hydroformylation of Alkenes by Use of Rhodium Complex Catalyst". Journal of
the Chemical Society 33 (21): 3133–3142. doi:10.1039/J19680003133.
http://www.rsc.org/ejarchive/J1/1968/J19680003133.pdf
• Journal of molecular catalysis.9(1960)265 -274 "Hydroformylation of Alkenes by
Use of Rhodium Complex Catalyst". L A. GlCRRETSEN, W. KLUT, 56. H. VR!
XJGDENiiIL and J. d. F. SCEfOLTEN*
• De~enCofChemi~Technolo~.DelfC UniuersibofTeehno~~.Jut~naLcan 136.
Dryden’s outlines of chemical otechnology by Gopal rao
Shreve,s chemical process industries
Introduction to chemical engineering thermodynamics, smith J.M,, Van Ness,H.C.,
and Abbott,M.M., 6th edition,McGraw Hill
Perry’s chemical engineers handbook , Perry Rober H,7 th edition,McGraw Hill
http://www.cbu.edu/ ̴rprice/lectures/distill7.html, Trays probably aren’t a good idea
for columns less than about 1.5 ft in diameter (you can’t work on them) –
these are normally packed
www.neiwpcc.org/tanksconference/presentations/monday
%20presentations/Adair.Biofuels.monday.pdf
BIBLIOGRAPHY
http://www.wikipedia.com
http://www.google .co.in
http://www.adm.com
http://www.sciencedirect.com
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