MANUFACTURING METHODS

1. Methanol carbonylation
2. Acetaldehyde oxidation
3. Ethylene oxidation
4. Anerobic fermentation
1. Methanol carbonylation:

Methanol and carbon-monoxide both formed via

synthesis gas are reacted together in the liquid phase, with some water
to keep the catalyst in solution at moderate temperatures of about 450k
and pressure of 30atm.

CH3OH(l) + CO(g) → CH3COOH(l) ∆H= -137kj/mol

A rhodium iodine based catalyst system was first used.

The catalyst has recently been improved. Based on iridium in place of
rhodium. The cavita process yields more than 99% ethanoic acid is
obtained.

The manufacture of ethanoic acid using the cavita process:

 The reactor
 Distillation column to remove methanol,water and carbon-
monoxide. Proponoic acid is removed on further distillation.

The main reason of the improvement is that much less water is

needed to keep iridium complex in solution compared with the
amount needed with the rhodium complex. Thus by reducing the
consumption of energy on distillation. The cost of purifying the
product falls by an estimeed 30% this means the green house gas
emissions are also reduced.

The two reactants methanol and carbon-monoxide are

mixed with iridium chloride and hydro chloric acid in ethanoic acid
which acts as a solvent. Iodomethane, CH3I is also added which
forms a complex ion [Ir(CO)2I3CH3]-, which is considered to be the
circular catalytic species. A ruthenium compound is added which
acts as a promoter.
 2.Acetaldehyde Oxidation:

Prior to the commercialization of the Monsanto process,most

acetic acid was produced by oxidation of acetaldehyde.this remains the
second most important manufacturing method,although it is usually
uncompetitive with the carbonylation of methanol.

The acetaldehyde may be produced via oxidation of butane or

light naptha ,or by hydrationof ethylene.when butane or light nptha is
heated with in the presence of various metal ions,including those of
manganese,cobalt and chromium proxides from and then decompose to
produce acetic acid according to the chemical equation.

2C4H10 + 5O2 →4CH3COOH + 2H2O

The typical is conducted at temperatures and pressure skill

keeping the butane a liquid.typical reaction condition are 150ₒc and 55 atm
side products may be altered to produce more of then when
needed.however,the separation of acetic acid from these by products adds
to the cost of the process.
Under the similar conditions and using similar catalysts as are
used for butane oxidation,the oxygen in air to produce acetic acid can
oxidise acetaldehyde.

2CH3CHO + O2 → 2CH3COOH
 Using modern catalyst,this reaction can have an acetic acid yield
greater than 95% the major side products are ethyl acetate,formic acid and
formaldehyde.all of which have lower boiling points than acetic acid are
readily separated by distillation.
 3.Ethylene Oxidation:

Acetaldehyde may be prepared from ethylene via the wacker

process,and then oxidized as above in more recent times,chemical
company show a denko,which opened an ethylene oxidation
plant,commercialized a cheaper single stage conversion of ethylene to
acetic acid.the process is catalyzed by a palladium metal catalyst
supported on a heteropoly acid such as tungstosillic acid.it is thought be
competitive with methanol carbonylation for smaller plants(100-250)kpa
depending on the local price of ethylene.the approach will be based on
utilizing a novel selective photo catalytic oxidation technology for the
selective oxidation catalysts,the selective oxidation process will use UV
Light to produce acetic acid at ambient temperature and pressure.

The liquid phase oxidation of acetaldehyde (using air or oxygen) in

the presene of manganese acetate,cobalt acetate or copper acetate in still
used,especially in Europe.this route to acetic acid production generally
use acetaldehyde as an intermediate via oxidation of ethylene(wacker
process).

Show a denko has developed a one step vapor phase process for the
of acetic acid by direct oxidation of ethylene.owing to relatively reduced
capital out lines needed,the show a denko ethylene based process is
claimed to be economical for 50000-100000 tonn/year acetic acid
plants,is based on a supported palladium catalyst containing there
compnents.the reaction takes place in a fixed bed reactor at 150-
160ₒc.selectivity to acetic acid is believed to be over 86%
 4.Anaerobic Fermentation:

Species of anaerobic bacteria,including members of genus

isotridium or acetobacterian can convert sugars to acetic acid directly,with
out using ethanol as an intermediate.the overall chemical reaction
conducted by these bacteria may be represented as ,

C6H12O6 →3CH3COOH

The acetogenic bacteria produce acetic acid from one carbon

compounds,including methanol,corbon monoxide or a mixture of carbon
monoxide and hydrogen.

2CO2 + 4H2 → CH3COOH + 2H2O

This ability of clostridium to utilize sugars directly or to produce acetic

acid from less clarity inputs,mean that these bacteria could potentially
produce acetic acid more efficiently than ethanol oxidizers like aceto
bactor.however clostridium bacteria are less acid tolerant than aecto
bactor.even the most acid tolerant clostridium strains can produce vinegar
of only a few present acetic acid,compared to acetobactor than to produce
it using clostridium andthen concentrate.it as a result although acetogenic
bacteria have been known their industrial use remains confined to few
much applications.
 DESCRIPTION OF METHANOL
CARBONYLATION METHOD

Methanol carbonylation:

Methanol and carbon-monoxide both formed via synthesis

gas are reacted together in the liquid phase, with some water to keep the
catalyst in solution at moderate temperatures of about 450k and pressure
of 30atm.

CH3OH(l) + CO(g) → CH3COOH(l) ∆H= -137kj/mol

A rhodium iodine based catalyst system was first used.

The catalyst has recently been improved. Based on iridium in place of
rhodium. The cavita process yields more than 99% ethanoic acid is
obtained.

The manufacture of ethanoic acid using the cavita process:

 The reactor
 Distillation column to remove methanol,water and carbon-
monoxide. Proponoic acid is removed on further distillation.
The main reason of the improvement is that much less water is needed to
keep iridium complex in solution compared with the amount needed with
the rhodium complex. Thus by reducing the consumption of energy on
distillation. The cost of purifying the product falls by an estimeed 30%
this means the green house gas emissions are also reduced.

The two reactants methanol and carbon-monoxide are mixed with

iridium chloride and hydro chloric acid in ethanoic acid which acts as a
solvent. Iodomethane, CH3I is also added which forms a complex ion
[Ir(CO)2I3CH3]-, which is considered to be the circular catalytic species. A
ruthenium compound is added which acts as a promoter.
 PROCESS FOLLOWING STEPS:

Methanol carbonylation following three steps

1.methane oxidation
2.methane hydrogenation
3.methane carbonylation

METHANE OXIDATION:

CH4 + ½ O2 → CO + 2H2
Conversion → 100%
Catalyst → platinum and rhodium
Instantaneous reaction.

METHANE HYDROGENATION:

CH4 + H2O → CH3OH + H2

Conversion → 50%
Catalyst → 85% of methyl bisulphate(CH3OSO3H)
Reaction upto 2 hours
METHANOL CARBONYLATION:

CH3OH + CO → CH3COOH
Conversion → 99%
 MATERIAL BALANCE

BASIS: one day of production (operation)

Production =( 3*10000*1000)/300 =100000 kg/day

Molecular weights:
Methane = 16 water = 18
Oxygen = 32 methanol = 32
Carbon monoxide = 28 acetic acid = 60
Hydrogen = 2

Calculations:

on the basis of final product according to that we find out acetic acid
production in moles = 100000/60
=1666.67 kmoles /day
According to methanol carbonylation reaction:
One mole of CH3COOH → 1 mole of CH3OH
1666.67 kgmoles/day →
Conversion 99% = 0.99
CH3OH moles = 1666.67/0.99
=1683.5 kgmoles/day
1mole CH3COOH → 1 mole of CO
1666.67 moles →

=1683.5 kmoles/day
According to methane reacts with water:

1 mole of CH3OH → 1 mole of CH4

1683.5 kmoles/day →
Reaction with 50% conversion
= 1683.5/0.5
=3367kmoles/day
CH4 = 3367kmoles/day
H2O = 3367kmoles/day
H2 = 1683.5kmoles/day

According to methane oxidation:

CH4 + ½ O2 → CO + 2H2
 1 mole of CO → 1 mole of CH4
1683.5 kmoles/day →

= 1683.5/1
CH4 = 1683.5kmoles/day
1 mole of CO → 1/2 mole of O2
1683.5 kmoles/day →
O2 = 841.75kmoles/day

1 mole of CH4 → 2 moles of H2

1683.5 kmoles/day →
= 3367 kmoles/day

FEED:

Total moles of CH4 = 3367 kmoles/day + 1683.5 kmoles/day

= 5050.5kmoles/day
Total moles of O2 = 841.75 kmoles/day
Total moles of CO = 1683.5 kmoles/day
Total moles of H2O = 3367 kmoles/day
Total moles of CH3OH = 1683.5 kmoles/day
Total moles of H2 = 1683.5 + 3367
=5050.5kmoles/day

PRODUCTS:

CH3COOH = 1666.67 kmoles/day

 QUANTITATIVE FLOW DIAGRAM

BASIS: one day of operation.

Reactants process products

 ENERGY BALANCE

From methane oxidation

CH4 + ½ O2 → CO + 2H2
∆Hf of CH4 → -74850 kj/kmol
∆Hf of O2 → 0 kj/kmol
∆Hf of CO → -110530 j/mol
∆Hf of H2 → 0 j/mol

∆H1 = 1683.5(-110530)+841.75(0)- (-74850)1683.5+0

= -60067280 kj/day

From methane hydrogenation

CH4 + H2O → CH3OH + H2
∆Hf of CH3OH → -238660j/mole
∆Hf of H2O → -285800 j/mole

∆H2 = 1683.5(-238660) – (-285800)3367 – (74850)3367

 = 812524440 kj/day

From methanol carbonylation

CH3OH + CO → CH3COOH

∆Hf of CH3COOH → -483520

∆H3 = (-483520)1666.67 – (-238660)1683.5 – (-110530)1683.5

= -218006913.4 kj/day

Total ∆H = -60067280 + 812524440 - 218006913.4

= 534450246.6kj/day
=6185.766 kw
 DESIGN OF HEAT EXCHANGER

DATA:
SHELL SIDE TUBE SIDE
Inner dia = 25 inch number of tubes = 250
Baffle space = 12 inch length = 16inch
Passes = 1 OD, BWG, pitch = ¾ inch,
16 BWG,1 inch square pitch
Passes = 6

HEAT BALANCE:

m CH3COOH = 1666.67 kmol/day

= 1666.67*60/24 kg/hr
= 4166.675 kg/hr
mCH3COOH = 9185.945 lb/hr

Q = mL + mCp∆T
= m(L + CP∆T)
= 9185.945(173 + 0.56*140.4)
 = 2311404.225 btu/hr
Q = 2311404.225 btu/hr

Q = mwCp w∆TW
2311404.225 = mw * 0.96 * 108
mw = 2140.89/0.96 lb/hr
= 2293.636 lb/hr

Q = 2311404.225 btu/hr
mw = 22293.636 lb/hr
mCH3COOH = 9185.945 lb/hr

qs = mcp∆T
= 9185.945 * 0.56 * 140.4
= 722235.74
Temperature:
Sub cooling: hot cold difference
244.4ₒF 176ₒF 68.4ₒF
104ₒF 68ₒF 36ₒF
Condensing:
Hot cold difference
244.4ₒF 176ₒF 68.4ₒF
244.4ₒF 68ₒF 176.4ₒF

∆Ts = 68.4 – 36
ln(68.4/36)
=50.478ₒF

∆Tc = 176.4 – 68.4

ln(176.4/68.4)
= 113.998ₒF

∆T = Q/∑(q/∆T)
= Q/(qs/∆ts + qc/∆tc)

= 2311404.225
722235.74 +1589768.485
50.478 113.998
= 81.824ₒF
CONDENTION:

HOT FLUID:SHELL SIDE COLD SIDE:TUBE SIDE

4. Tv = 244.4ₒF 4. at1 = 0.302 in2

Do = 0.75/12 at = Nt at1/144n
= 0.0625ft = 250 * 0.302
G1 = w/(3.14 * NE * D0) 144*6
= 9185.945 =0.08738 ft2
3.14*250*0.0625
= 187.134 lb/hr.lin.ft 5. Gt = W/at
ASSUME: = 22293.636/0.08738
h0 = 150 = 255134.3099
Tavg = 244.4ₒF Ta = 122ₒF
Tw = Ta + h0(TV – TA)/(hio+ho) Velocity = Gt/3600℮
= 122 + 150(244.4-122) = 255134.3099
150+338.933 3600*62.5
Tw = 159.55ₒF =1.1339 fps
hi = 410
Tf = TV + TW/2 hio = 410*(0.62/0.75)
= 244.4 + 159.55/2 = 338.933
 = 201.97ₒF
Kf = 0.099 btu/hr.ft2(ₒf/ft)
Sf = 1.05
ὐ = 0.48 cp
ho = 160

CLEAN OVER ALL COEFFICIENT Uc:

UC = hi * hio
ho + hio
= 160*338.933/(160+338.933)
= 108.69
Qc = mL
= 9185.945*173
=1589168.485 btu/hr
Qc = UAc∆TC
Ac = 1589168.485/108.69*113.998
Ac = 128.257 ft2
SUB COOLING:
4. as = ID* C1*B
144 pt
 = 25*0.15*12
144*1
= 0.521 ft2
5. GS = W/as
= 9185.945/0.521
= 17631.372
6. Ta = 244.4+104
2
= 174.2ₒF
ὐ = 0.58 cp
De = 0.95/12
= 0.0792ft
Res = DeGS/ὐ
= 0.0792 * 17631.372
0.58 * 2.42
= 994.8736
7. jH = 16
8. at Ta = 174.2ₒF
K = 0.099 btu/hr ft2(ₒF/ft)
(Cp* ὐ/k )1/3 = (0.57*0.58*2.42/0.099)1/3
= 2.00675
9. h0 = jH*k*De(cp* ὐ/k)1/3
= 16*0.099*2.00675/0.0792
= 40.135

CLEAN OVERALL COEFFICIENT:

Us = hio* ho/(hio + ho)

=40.135*338.933/(40.135+338.933)
= 35.885
AS = qs/(us∆ts)
= 722235.7397/(35.885*50.478)
= 398.78 ft2
As + Ac = 527.037 ft2

Uc = AsUS + ACUC/(AS+ AC)

=398.78*35.85 + 128.25*108.69
398.78+128.257
UC = 53.598

DESIGN OVERALL COEFFICIENT UD:

Ud = Q/A*∆T
 A = 250* 161 *a11
= 250*16*0.1963
=785.2 ft2

Ud = 2311404.225
785.2*81.824
= 35.976
DIRT FACTOR:
RD = UC – UD/(UCUD)
= 53.598-35.976 = 0.0091388
53.398*35.97
 PRESSURE DROP

HEIGHT OF ZONES: 1. Res = DGt/ὐ

Condensing : = 0.0517*255134.3095
Le = aCL/AC 0.82*2.42
=16*128.257/527.037 = 6647.069
= 3.8937ft Res = 6647.069
Condensation: f = 0.0003 ft2/in2
At tv = 244.4ₒF
= 0.39cp 2. ∆Pt = fGt2ln/5.22*10^10DS
ὐ = 0.39*2.42 = 0.0003*(255134.3095)
= 0.9438 lb/ft hr 5.22*10^10*0.0517*1*1
Res = DeGs/ὐ = 0.6946 psi
= (0.0792*17631.372)/0.9438
= 1479.55 3. ∆Pr = 4n/s(v2/2g)
f = 0.0029 ft2/in2 = (4*6)/1*0.0084
mol.wt = 60 = 0.2016 psi
pressure = 1atm

ƥ=60/(359*(704.4/492)*(14.7/14.7))
 = 0.11673/62.5
= 1.867*10^-3 4. ∆PT = ∆Pr + ∆Pt
= 0.8962 psi
2. N+1 = 12L/B ∆P T = 0.8962 psi
= 12*3.8937/12 Allowable pressure
N+1 = 3.8937
Ds = 2.08ft

3. ∆Ps = ½( fGs2Ds (N+1) )

5.22*10^10*De*S
= ½(0.0029*(17631.372)2*2.08*3.8937)
5.22*10^10*0.0792*1.867*10^-3
∆Ps = 0.47296 psi
Allowable pressure
FOR REACTOR 1
Volume of Reactor = 1683.5 kmoles/day
= 1683.5*16 kg/hr
= 1122.33 kg/hr
= 2474.314 lb/hr
O2 = 841.75 kmoles/day
=841.75/24*16 kg/hr
= 1237.161 lb/hr
CO = 1683.5 kmoles/day
= 1683.5*428/24
= 4330.0552 lb/hr
H2 = 3367*2/24kg/hr
= 618.599 lb/hr
ρ CH4 =0.006574 lb/gal
ρ O2 =0.01334 lb/gal
ρ CO =0.011456 lb/gal
ρ H2 =0.00075 lb/gal

=2474.374/0.006574+1237.161/0.01334+4300.0552/0.011456+618.579/0.
00075
= 929197.49 gal/hr
REACTOR= 2
Methane =3367*16/24 kg /hr
=4948.64 lb/hr
ρ methane = 0.006574
H2O = 3867*18/24 kg/hr
= 5567.22 lb/hr
ρ H2O =8.345
H2 =1683.5*2/24 kg/hr
=309.290 lb/hr
ρ H2 =0.00075
CH3OH =1683.5*32/24 kg/hr
=4948.64 lb/hr
ρ CH3OH =7.93775
=4948.64/0.006574+5567.22/8.345+309.290/0.00075+4948.64/7.93775
=1166436.985 gal/hr

REACTOR 3
CH3OH =1683.5*32/24
=4948.64 lb/hr
ρ CH3OH =7.93775
CO =1683.5 kmoles/hr =4330.0552 lb/hr
ρ CO =0.00075
CH3COOH =1666.7*60/24 kg/hr
= 9186.11 lb/hr
ρ CH3COOH =10.5235 lb/gal
=4948.64/7.93775+4330.0552/0.00075+9186.11/10.5235
= 5774342.666 gal/hr
REACTOR 1
τ =0.01 sec
Total flow rate = 929197.49 gal/hr
Volume = 258*0.01 = 2.58 gal
For design purpose added 20% more
Volume = 2.58*1.2 = 3.1 gal
Choose 10 gal reactor (carbon steel) $17200
REACTOR 2
Total flow rate =1166436.585 gal/hr
= 1166436.585/3600
=324.010 gal/sec (τ=0.01)
Volume=0.1*324.010 gal
Current volume =32.4010*1.2($32000)
REACTOR 3
Total flow rate =5774342.666 gal/hr
= 1603.984 gal/sec
τ =0.1 sec
Volume =0.1*1603.984 $61200
=160.3984 gal
Heat exchanger area=527.037 ft2
Cost-$50300
Material-cabon steel
Purchased cost for complete unit
2015 - 1530
2016 - 1545
Cost of reactor 1(2016) =1545/1530 *17200
$17369
Purchased cost for complete unit:
ITEM DESCRIPTION PURCHASED
COST $
R-1 Methane oxidation 17369
R-2 Methane 32314
hydrogenation
R-3 Methane 61800
carbonylation
H-1 Heat 50793
exchanger(cooler)
H-2 Heat exchanger 50793
UNIT-1 Membrane 100000
separation unit
UNIT-2 Gas-lquid 100000
separation unit
total 413069
ITEM % OF COST $
PURCHASED
EQUIPMENT
COST
Purchased 100 413069
equipment cost
Purchased 47 194142
installation
Instrumentation 18 74352
and controls
Piping 66 272625
Electrical 11 45437
Buildings 18 74352
Yard 10 41306.9
improvements
Service 70 289148
Land 6 24784
TOTAL DIRECT 346 1429215.9
PLANT COST
Engineering and 33 136312
supervision
Construction and 41 169358
expenses
TOTAL DIRECT 420 1734886
AND INDIRECT
COST
Contractor fee 21 86744
Contingency 42 173489
TOTAL FIXED 483 1995119
CAPITAL COST
INVESTMENT
Working capital 86 355239
TOTAL COST 569 2350358

Fixed capital investment =1995119*1586/904*70

= Rs.24.5 cr
Total capital investment = 2350358*1586/904*70
= Rs28.86 cr
Turn over ratio = Gross annual sales/Fixed capital investment
1 = Gross annual sales/F.C.I
Gross annual sales =245020034
Let 30% is profit =245020034*0.3
=73506010 /yr
Depreciation by straight line method
Life of the equipment =10 years
Depreciation = (245020034-0)/10
= 24502003 Rs
= 24.5crores
Pay out period:-
Pay out period = F.C.I/(depreciation/yr+avg.profit/yr)
= 245020034/924502003+73506010
= 2.5 year.