Acetic Anhydride Production

Contents : Process flow diagram Flash tank Packed bed reactor Distillation column ByRaman 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

Required rate of methyl acetate required after flashing = 16.4 mol/sec

High Pressure Amount of liquid Amount of steam 1 0 303K Low Pressure 1-x x 353

X =

Temperature

56.16

Required methyl acetate flow rate Input of methyl acetate in flash tank Volume of vapour of methyl acetate Methyl acetate condensate Condensate volume generation rate Total volume requirement

16.4mol/sec 35.3 mol/sec 0.4667m3/sec 18.9 mol/sec 1.409 m3/sec 2m3/sec

Assuming a rectangular flash tank And L/D = 2 Diameter = 1.082 m Length = 2.164m

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

Packed bed reactor(PBR)

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
o o o Reaction conditions: Pressure 5MPa and temperature 343K 1st order irreversible reaction model 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 : o Isothermal PBR reactor o coolant is used to maintain the constant temp. o Pressure drop is small. o L/D=6 is used, with each tube dia.(dt) =0.25m o No catalyst decay i.e. decay constant, a=1 Ref:Abdelouahab Attou,Gilles
Ferschneider,BP 3,69390 vernaison cedex ,france 14 april1999. Reaction conditions data used Feed rate(FAo ) methyl acetate Volumetric flow rate (vo) Conversion of methyl acetate (X) 16.4mol/sec 6.96*10-3m3/sec 92.53 %

Temperature of reactor(T)
Pressure of the reactor (P)
Void fraction of packing of catalyst in reactor ()

343K
5MPa 0.53 12.45*103kg/m3 6.59 *103kg/m3

Density of catalyst particles (cp) Bulk density (b= cp)=

Design equation for PBR

Equation governing PBR dX/dW = - rA/FA0 rA = 3.0286*103 exp{(8.124*104)/RT} cA W = (FA02/v0) b *ln(1/(1X))*3.0286 *103 * exp{(8.124*104)/RT} Residence time, =V/vo V = W/ b No. of tubes = D/ dt Superficial velocity Us= vo/A
Results obtained for PBR model
Weight of catalyst(W) Volume of reactor(V) Length of reactor(L) Diameter of reactor(D) Residence time() 60.67kg 9.2 m3 7.5m 1.25m 22min

Superficial velocity(Us) No tubes in PBR

5.67*10-3m/sec 5

Pressure drop in PBR

o o o Assumptions: All substrate at same velocity No back or radial mixing All product come with same residence time o Laminar flow pressure drop P/L=0.082MPa

Data used for pressure drop

Mass velocity (G)= Us Porosity() Diameter of particle(Dp) Viscosity() 5.7kg/m2-s 0.47 0.508*10-2m 0.10832Pa-s

Ergun equation(for laminar flow): P/L= =(G/ gcDp) *(/(1-)3 )* {150* /Dp}

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. 1 troy ounce(31.1gm) in($) 85 o Costing:
Total weight of catalyst(kg)
Total cost of catalyst($)

60.67
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) (nf) Acetic anhydride Methyl acetate 54.6 4.4 Mole fraction in feed (xf) 0.861 0.0694

Carbon monoxide

4.4

0.0694

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

Percentage recoveries (P.R i) Acetic anhydride Methyl acetate Carbon monoxide Total moles in Distillate .04 0.92 0.97 Moles (kmol/h) Mole fraction in distillate (xd) 0.208 0.385 0.486

54.6 x 0.04 = 2.184 4.4 x 0.92 = 4.048 4.4 x 0.97 = 4.268

D = 2.184 + 4.048 + 4.268 = 10.5kmol/h

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

Percentage recoveries (P.R i) Acetic anhydride Methyl acetate Carbon monoxide 0.96 0.08 0.03 Moles (kmol/h) Mole fraction in distillate (xd) 0.9906 0.0067 0.0025

54.6 x 0.96 = 52.416 4.4 x 0.08 = 0.352 4.4 x 0.03 = 0.132

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 , i= Ki /K

i = 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 :

average i = (top i x bottom i x feed 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

, = 13 plates

= 0.374

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 / vap 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