Acetic Anhydride Production

Contents :

• Process flow diagram

• Flash tank
• Packed bed reactor
• Distillation column
By-
Raman Kumar
Priyaranjan
Ravindra
Process Flow Diagram

Fig : Process flow diagram for acetic anhydride production plant

Flash Tank

%flash
heat energy available due to change in pressure
= 𝐸𝑛𝑒𝑟𝑔𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑓𝑜𝑟 𝑐𝑕𝑎𝑛𝑔𝑒 𝑜𝑓 𝑝𝑕𝑎𝑠𝑒
Required rate of methyl acetate required after flashing = 16.4 mol/sec

High Pressure Low Pressure

Amount of liquid 1 1-x

Amount of steam 0 x

Temperature 303K 353

X = 56.16

Required methyl acetate flow rate 16.4mol/sec

Input of methyl acetate in flash tank 35.3 mol/sec
Volume of vapour of methyl acetate 0.4667m3/sec
Methyl acetate condensate 18.9 mol/sec
Condensate volume generation rate 1.409 m3/sec
Total volume requirement 2m3/sec

Assuming a rectangular flash tank

And L/D = 2
Diameter = 1.082 m
Length = 2.164m
 Packed bed reactor(PBR)
Why PBR
o Better contacting between the feeds
of reaction
o Provides the highest flow conversion.
o Tube bundles within the reactor
provides better packing of catalyst

Major challenges of using PBR

o Channeling of the gas flow
o Difficult to control the temperature
o Hot spots occur during exothermic
reaction

Ref:www.umich.edu/~essen/html/01chap/html/in
dustrial.htm
 Reaction Kinetics
• Reaction conditions:
o Pressure 5MPa and temperature 343K
o 1st order irreversible reaction model
o Ruthenium based homogeneous catalyst
• Rate equation:
• R = -dcA/dt =KcA=3.0286*103exp{(8.124*104)/RT} cA

Ref: college of chemical engineering,Qindgado University of science and technology .

http://xbzrb.qust.edu.cn/WEB2006-5/E06-05-03
 PBR modelling
• Assumption for PBR :
Reaction conditions data used
o Isothermal PBR reactor
o coolant is used to maintain the Feed rate(FAo ) - 16.4mol/sec
methyl acetate
constant temp.
Volumetric flow 6.96*10-3m3/sec
o Pressure drop is small. rate (vo)
o L/D=6 is used, with each tube Conversion of 92.53 %
dia.(dt) =0.25m methyl acetate (X)
Temperature of 343K
o No catalyst decay i.e. decay reactor(T)
constant, a=1 Pressure of the 5MPa
reactor (P)
Ref:Abdelouahab Attou,Gilles Void fraction of packing 0.53
Ferschneider,BP 3,69390 vernaison cedex of catalyst in reactor (ϵ)
,france 14 april1999.
Density of catalyst 12.45*103kg/m3
particles (ρcp)
Bulk density (ρb= 6.59 *103kg/m3
ρcpϵ)=
 Design equation for PBR
Equation governing PBR Results obtained for PBR model
• dX/dW = - rA’/FA0 Weight of catalyst(W) 60.67kg
• rA = 3.0286*103 exp{(- Volume of reactor(V) 9.2 m3
8.124*104)/RT} cA Length of reactor(L) 7.5m
• W = (FA02/v0) ρb *ln(1/(1- Diameter of reactor(D) 1.25m
X))*3.0286 *103 * exp{(- Residence time() 22min
8.124*104)/RT} Superficial velocity(Us) 5.67*10-3m/sec

• Residence time, =V/vo No tubes in PBR 5

• V = W/ ρb
• No. of tubes = D/ dt
• Superficial velocity Us= vo/A
 Pressure drop in PBR
• Assumptions: • pressure drop P/L=0.082MPa
o All substrate at same velocity
o No back or radial mixing
o All product come with same
residence time
Data used for pressure drop
o Laminar flow
Mass velocity 5.7kg/m2-s
Ergun equation(for laminar flow): (G)= ρUs
P/L= Porosity() 0.47
=(G/ ρ gcDp) *(ϵ/(1-ϵ)3 )* {150* ϵ/Dp}
Diameter of 0.508*10-2m
particle(Dp)
Viscosity() 0.10832Pa-s
Ref:Kate Taylor,Anthony G Smith,Stuart Ross and martn
Smith,second international conference on CFD in process
industires,6-8 dec,1999
 Catalyst cost estimation
• Catalyst used: Ruthenium
• Catalytic condition:
o the catalyst is added in the form of ruthenium oxide i.e. Ruo2
o During carbonylation process ruthenium will form coordination
complex with CO ligand.
o Costing: 1 troy ounce(31.1gm) in($) 85
Total weight of catalyst(kg) 60.67
Total cost of catalyst($) 165818.6

Ref:CatalystHandbookUSA.pdf-Johnson Matthey Catalyst,c-2008

http://apps.catalysts.basf.com/apps/eibprices/mp/
 Designing of distillation column
Given:
• composition of component
• purity of distillate and bottoms required
• The quality of the feed
• Height-to-diameter ratio should be less than 20
• Total feed is = 63.4 kmol/hr
Feed in (kmol/h) Mole fraction in
(nf) feed (xf)
Acetic anhydride 54.6 0.861
Methyl acetate 4.4 0.0694
Carbon monoxide 4.4 0.0694
Assumption of percentage recoveries (P.R) for top product

Percentage recoveries Moles (kmol/h) Mole fraction in

(P.R i) distillate (xd)

Acetic anhydride .04 54.6 x 0.04 = 2.184 0.208

Methyl acetate 0.92 4.4 x 0.92 = 4.048 0.385

Carbon monoxide 0.97 4.4 x 0.97 = 4.268 0.486

Total moles in Distillate D = 2.184 + 4.048 + 4.268 = 10.5kmol/h

Assumption of percentage recoveries (P.R) for bottom product

Percentage recoveries Moles (kmol/h) Mole fraction in
(P.R i) distillate (xd)

Acetic anhydride 0.96 54.6 x 0.96 = 52.416 0.9906

Methyl acetate 0.08 4.4 x 0.08 = 0.352 0.0067
Carbon monoxide 0.03 4.4 x 0.03 = 0.132 0.0025

Total moles in bottom W = 51.324 + 0.352 + 0.132 = 52.9 kmol/h

Calculations of K-values and relative volatilities for the feed stream :
Pt = Total pressure ( 760 mmHg ) , T = 113.66 *C

Antoine equation is :

Ki = Pisat/ Pt , αi= Ki /K
αi = Relative volatility of components
K = vapor-liquid distribution ratio of a component

Similarly
Calculations of K-values and relative volatilities for the top (95.4 *C)
and bottom (122.39 *C) product

Average Relative volatilities :

αaverage i = (αtop i x αbottom i x αfeed i)1/3

If relative volatilities of components is less than 1.1 , distillation becomes very

expensive
calculation of minimum no of plates by using Fenske equation :

N min = 7.82
calculation of minimum reflux ratio , RD min by using underwood eqn :

minimum reflux ratio RD min comes out , RD min = 3.933

RD actual = 1.5 x RD min = 5.899
calculation of actual plate no by using Gilliand correlation:

X = = 0.284 , = 0.374

= 13 plates

calculation of NR and Ns for the feed location by using kirk bridge method:

log (NR/NS) = 0.206 log [(W/D)*(Xfhk/XfLk)*(XbLk/XdHk)2]

NR = Nactual - Ns
Ns (number of plate of stripping section) = 6 ,
NR (number of plate of rectifying section) = 7
calculation of column Diameter and Height
(molecular weight of mixing) = 62.155 kg/kmol
vapor density of mixture is :

= 1.916 kg/m3

liquid density of mixture is :

= 1075.44 kg/m3

uv fluid velocity is : assuming Plate spacing lt = 0.5 m

= 1.072 m/s

Diameter of the column :

Diameter Dc = [14 x W / ρvap x uv x 11 ]1/2 = 0.744 m

Height of the column : H = lt x (N+1) = 0.5 x (13 + 1) = 7 m

Total production of acetic anhydride from the plant = 52.416 kmol/hr , which is 99 % pure

References :
Coulsion and richardson volume 6 3rd edition pg 517 , 542, 504 , 1993
Mcabe smith unit operations of chemical engineering 7th edition pg 722-724
Mass transfer operations Robert Treybal 3rd edition