C H A P TER 6

C A R B O N Y L A T IO N O F M E T H Y L A C E T A T E T O

A C E T IC A N H Y D R ID E U S IN G A H O M O G E N E O U S

N IC K E L C O M P L E X C A T A L Y S T
6.1 IN T R O D U C T IO N :

T h e im p ortan ce o f C i chem istry and its role in the d e v e lo p m e n t o f n ew ro u tes

for b ulk as w ell as speciality ch em ica ls has b e e n d iscu ssed in d etail in C h ap ter 1 .

A c e tic anhydride is an im portant bulk ch em ica l w ith ap p lication s in the p ro d u ctio n

o f ex p lo siv es (h ex o g en ) and for th e syn th esis o f a n um ber o f sp eciality ch em ica ls

req u ired in dye stuffs and p h arm aceu tical industry. It is a lso u sed in etch in g and

p o lish in g o f m etals, sem icon d u ctor m an u factu re and acety la tio n o f c e llu lo se and

variou s fragrance alcoh ols to transform th em into valu e ad d ed esters [ M ary

H o w e-G ra n t (1991)]

T h e m ajor com m ercial routes for the m an ufacture o f a ce tic anhydride are :

1 ) T herm al d ecom p osition o f a cetic acid with k ete n e as an in term ed ia te

[A ltern sch oefer et.al., (1966)]

2) T herm al d ecom p osition o f a c e to n e w ith k eten e as an in term ed ia te [Jeffreys

(1964)]

3) O xidation o f acetald eh yd e with cob alt or m an gan ese catalyst [A llen and

A g u ilo (1968)]

4) C arbonylation o f m ethyl a ceta te using a h o m o g en eo u s catalyst [B A S F

(1951)]

F or the p rocesses based on a cetic acid and a ceto n e, tem p eratu re in the range

o f 973-1073 K is required for th e g en era tio n o f k eten e ( C H 2 = C = 0 ) . K e te n e s is

reactive in nature and highly u n stab le lead in g to form ation o f sid e products. In the

a ceta ld eh y d e process, eq u im olar am ou n t o f w ater is g en era ted with the anhydride.

A recen t process is based on the carbon ylation o f m ethyl a ce ta te using h o m o g e n e o u s

catalysis. T en n e ssee E astm an has su ccessfully com m ercialised this tech n o lo g y in

1983 using a R h com plex catalyst. H ow ever, due to the high cost o f Rh and lim ited

resou rces, it w ould be w orthw hile d ev elo p in g an alternative and ch eap er catalyst

250
w ith high activity and selectivity. T h e p resen t w ork was u n d erta k en with the aim of

investigating the role of nickel com plex catalysts in carbonylation of m ethyl acetate

to acetic anhydride.

In this Chapter, a brief sum m ary of the literatu re on different catalyst systems

and th e experim ental results on the carbonylation of methyl acetate using nickel

com plex are presented.

6.2 LITERA TUR E S U R V E Y :

6.2.1 G eneral background :

T he carbonylation of methyl acetate to acetic anhydride can be rep resen ted as

catalyst
CH3 COOCH3 + CO------------------------- >(CH3C0)20 (6.1)

This reaction is exotherm ic with a h eat of reaction of 22.6, k cal/m o l and usually

needs a catalyst. The catalysts consisting of metal complexes of Rh, Ir, Ru, Co and

Ni , N- and P- containing pro m o ters, and iodides and acetate salts are usually

recom m ended [ Zoeller, et.a l, (1992), G au th ier and Perron (1985)]. The first rep o rt

on the carbonylation of methyl acetate was published in 1951 by BASF w herein Co,

Ni or Fe carbonyl complexes w ere used as catalysts at high CO pressures ( 6 x 10^-7

X 1Q4 kPa). A detailed study on this subject began only after the oil crisis in seventies.

Also, the availability of m ethanol produced from CO and H 2 , boosted the research

activity in this area. This is evident from a num ber of articles, patents and

publications on this subject in the last decade [ M itsubishi (1977) and (1985),

R hone-Poulenc, (1985) and (1986), E astm an K odak (1980), Larkins et.al., (1983),

Shell (1985), A greda e t.a l, (1992) and Z o eller et.al., (1992)]. This process has also

been com m ercialised by Tennessee E astm an (Division of E astm an K odak) in 1983

[Z oeller et.al., (1992) and A greda e t.a l, (1992)] and a detailed description of the

251
process is given by Cam pbell et.al., (1985). A sum m ary of literatu re on the catalysts

and prom oters used in carbonylation of methyl acetate is given in T able 6.1. Some

im portant results are discussed below ;

6.2.2 C atalysts and com m ercial p rocesses :

6.2.2.1 R hodium C atalysts :

T he carbonylation of methyl acetate to acetic anhydride has been extensively

studied with R h complex catalyst. A num ber of patents as well as papers describe the

activity and selectivity of different types of R h catalysts. The rhodium catalysts have

higher activity and selectivity at relatively m ilder operating conditions ( 423-473 K

and 1.02 x 10^ to 10 x 10^ kPa)[K uckertz (1976), Schrod et.al., (1983), Luft and

Schrod (1983), Polichnowski (1986), Jen n er (1989) and Z o eller et.al., (1992)].

Luft and Schrod (1983) have studied the carbonylation of methyl acetate using

a rhodium catalyst and have evaluated the optim um operating conditions. The effect

of C r(C O ) 5 as a prom oter was also studied and it was found that in the presence of

C r(C 0 )6 , the induction period of the reaction was reduced. Conversions in a range

of 50-80% and selectivity for acetic anhydride > 99% is reported. Several authors

describe the im provem ent in activity by addition of various prom oters such as 1 ,2 , 6

trim ethyl pyridinium iodide, Li(OAc), different N- and P- containing com pounds [

C hen D ean, et.al., (1990), Luft and Schrod (1983)]. Z o eller et.al., (1992) have

observed that the rate of reaction is enhanced in the presence of cations such as Li +,

N a + ,B u 4 N + , AI + 3, etc.

Supported rhodium catalysts with salts of Na, Mg, Ca and La as prom oters were

also investigated for carbonylation of methyl acetate [Showa Denko (1982) and

G eb h ard and G erhard (1987)]. The reaction was feasible at 503 K and 10^ kPa to

give 4 x 10'^, kg of acetic anhydride per hour. R hodium supported on C, S i02,

AI 2 O 3 were also studied for carbonylation of methyl acetate to acetic anhydride at

252
 U
hH
H
W
U

o
H
W
t-
(fl 05 CO
H <u
u 00
W e 05 "5 U5
O <u t- S 00 00
u nJ cs OJ 05
0) <U -o f - i cd "O
C
"O
ffj .i: ot- ^ o 0 CO
u 00 3
X rS 3 "u u 05 ca
H K CT) c/^ (/) O
w
cun
(y
o 'tn'
z ■£ 2 ucd 1-^
>>m
C
o
I—I
C3 •-«
r* (U CO r' 0"
u
V) .2 ci t/1
u -3 o w "3
*0•«
S>^ -a
ci •41^ _u w 0^ W
>-9 OJ ■5 U S Si Jum ) uy
o l c <
a •*3-» *(rt
z kC 5 crt 73 a a. i;; I— U5 aV)
o <£
m
3tf) •?0' kO iO
<• o {/) - o
CO
CO o krt
W ei ^ a.
hJ
CQ 2 5 0
u
g
Q 5 3
•w 00 CO
c/5 C3 00 t- o
Tf 00'
►
—s
Q. 00
(n o CO
C
H 0
c/2 H
>-
< L. -o , 50
a Gh =
0r*
Q r- CO 0 0 ’“ - 3 - o >05 Q0 o
0 o o ^ = = ^^S - = 'S -5
Z u '^ = S
C14 ' 60 ^ ‘-' > o 5P
O O U Z •- 2 U 5 8
w
> -w
ci
^S 1* >—
)I
V 0)
D OJ 5 4
(j) C3 ^
-w V3 ?5-5
a C3 >» _« t. •;; J2 "S ^
0 ^ O U O ^o— 2 -w« — w ^ jT
^^ o
0) = ^
H 5 5 Pi C H cs
<;
r-H
a c/3 CO
h

253
 CO CO
00 00
Oi
CO
00 •PiT OS
05 T5 -o QO
rH (n tN CO a
>
►> a cd C
s u 0 -a dj «
<V T3 ^ TJ -T5 -a a;
bO u a; u. o; -o c 2 Q _
Cfl c u CO o (S "o
to *N c 00
c
_2 O 2 0
1i®«05 =^ 05
S
0) c "3 05 »-H S _j 3 c8 -S 05
ei Cfi cu 0 ^ O d h-1 H u ^

- >»
•1>^> >> M -*.»
.2 *>
a 0 ’> ’> 2 -
P o ^ <v ^
CA y u TJ y m > ^
CO ■3 ii ^ ii' s a;
*C 0 w
2 Sc S S'S
W) w
a ^
.i:cn oj T3 -s V- I ci 5?
S ^ <3s O
a c lo
iO o
cn !fl hJ CO Oi 1X1 O M o 00 »-<

o o kO
d

CO
GO
CO CO 00
I irt iO ir: o
c-0

-o u (y a;
Qh <: £
CU ct3 o * n
CO W) s ^
-*->
o
m 'J CO
is Q.

X
4) "3 V
o t~,Q
JN HH ^ ^
O — OJ
r)
u "O S -S

o 00 05

254
 -a
r. «>
<y
c 13 "c3
CO •4^
0) 5 S « ~ ^ s C3
OJ 0) u '-I •- (S <U OJ
Q CO
ci -2
^ ^^ 'JZ
a ^i: s^
s 0? c^
q; O
>— Ci 13 05 tri 05 P3 50 ^ 3 .-i 00
Q a bO 05 -C cd «3 .« CO 0) -C Q
1-^ rH
U N C m cu2 o cih

G
TJ <V
s r- 1 a) >
03 a T3 c "o -a
<0 Cfl •(/)
■■« 2 2 0) —
0 S ^ "3
0 w
0 i)
3
.Si s TO 3 c .2 CO
cO .2
c; 2 J
eM Ij<v 3 -0 2
o
2
~v
c H M
« II 0)
c/3 .2 3
£ -«(/)-» CO
CO
1
■>> P rH O. 3 >1

o
o
lO b-I O
o CM
iO
o CM

CO
CO
CO CO
<N
CO
kT3

u
o c3
o hj hj o
2
u
o --

3
h-4 m
o; o; 0) cu
n u u CJ
<J
r5 r:) rr! V S <
y u 0 a.
z
§ 5 u
a

o 00 C5

255
 N >>
c u
--«3 D
* )-M s bri
id Cd CO Q
•-M "u 05 -*^ 00 -a
cd u 05 OJ 05 r-
a .i!
cd tH OJ
{h
V
V
1-H CB V
Q)
lO s r> CO 0 CO =
I s bO CO 3
05 cd
00 a "3 1
05
05 cn
05 "S
n= 00 05 00
Cd •4^
> 1 1-H <04^) 0 0) O 1-H
0 -H 1-H 2
5 c 0

<!
O
0)
2 :§
CD
15 0 -3 -TO
>> a u ^ c; oj
0 Pi w 0 =0 =
s? -0 vO
^ 0bN = 0= 0
05 tH O; GO
CD O Cfl 05 u ®2 ' i 2 '■§
I
kA a
cQ I 0a) • 0) c; i) 0)
Ci w CO cn ^ > » = > ,=

oo
o o c» o CO
00 t- lO fc
o CM

o 00 CO CO CO
o 05 00 00 05
'3' Tf CO

u
0C) I
O <0-^ o ’- — 0)
~c ^ O ^"3
O ^
<3 o o y S (i; TO
E -:3 ^ "2
cr u
c u
= P i

0) X o
0)
O 9 «
(8 ^o
J2
"o
Si
o
O I I I O
6 V 5
O n: 2 U
r)
S
IX
fc m CD 00
CM CM CM CM CM CM CM

256
 s o
u 05
ct3 05
to
o -a ^ tH
■4i^ o;
OJ CO 2
ts
cd Tc3 Ui
cn ?S t- flj 2
.£ !3 C -S ^
>
c >
n u
lO 3 2 -M «
<4^ o
3 00 m *N 05 J 2
o = tl tio *
o C3 05 , 1 CC rti o ^ 0 051-H
U a c o cS > C o
a:
ou
T3
to •4^
0 V
0^
fl
ti "O
0
c oc c .2 ^ «
00 W) ^
CD 2 c <
i3
CO CO
2I— C
£ CO O

O
u
o § O 00
o CO CO
2 o 1—(
o
~o
00
^ QO
O
CO CO K ^ CO
h- rH
lO
s ®

<u
>> S V
„ u ^« |_
'
— 3
>>-20^ + >> o r> •4^
— -a ffi 4e) O T3 ~0
~ ^ - S N-
« ^ K ^ CU
= •= ,-f C- l £ -0 T3 0 a-
^ 2 U 0) o
— 1)
1
rr

HaH
;
00 S
u
O
X
c <v u O O O «
U
0 u U 0 u ^
0 o o o 0 u
U u u Pi cd
(M
-1M A
c5

o cs CO U5
« CO CO CO CO rt

257
415-453 K and 1.11 x 1(P-1.51 x 10^ kPa C O pressure, w herein > 95% selectivity

to acetic anhydride was achieved. H owever, the activity obtained with the

heterogeneous catalysts was lower than th a t with the hom ogeneous catalysts.

C om m ercial processes :

T ennessee Eastm an in collaboration with H alcon SD have developed a novel

technology for acetic anhydride by carbonylation of methyl acetate using coal as a

basic feed stock [Zoeller, et.al., (1992), A greda et.al, (1992)]. The coal derived gas

is first converted to m ethanol and esterified with acetic acid to methyl acetate.

M ethyl acetate obtained is then carbonylated to acetic anhydride using

[R h(C O )2l2]’ in the presence of methyl iodide and Lil as prom oters. T he first

com m ercial plant with a capacity of 2,22,000, TPA is in o peration since 1983, at

Kingsport, USA.

T he typical operating conditions of the industrial reactor are 433-463 K and

2.02 X 10^ - 5.05 X 10^ kPa. A schem atic flow sheet of this process is presented in Fig.

6.1 [Cam pbell, et.al., (1985)]

H oechst has announced a new process for co-production of acetic! acid and

acetic anhydride simultaneously by carbonylation of m ethanol and methyl acetate

using a Rh catalyst with phosphonium or am m onium iodide prom oters. A sim ilar

process has also been announced by British Petroleum . A com parison betw een

different processes to produce acetic acid and acetic anhydride from m ethanol

a n d /o r methyl acetate is given in Table 6.2 [Papp and Baerns (1991)].

6.2.2.2 Nickel catalysts :

The nickel catalysed carbonylation of methyl acetate to acetic anhydride was

first reported by Reppe, et.al., (1956) with NiBr 4 -(Ph 3 PB u ) 2 catalyst. The reaction

conditions were 453-463 K and 65 x 10^ - 70 x 10^ kPa pressure and the yield

obtained was only 43%. After a gap of nearly two decades, several patents have been

filed on carbonylation of methyl acetate at lower tem perature and pressure using Ni

258
 ■8 LU
Q
cr
Q
tr
UJ
CD
(T
O
CO
Q o
< h-
Ll I
CJ
cr <
<t u_
(C o
o
< q :
CL

> iij
QQ
LU CQ
- 2 o
oc o D
to Cl
o
1- o
o* QL
0
Q.
u q:
cr UJ UJ
<S)
X
1 I h-
^ 8 cr
> ^ o
u_
z
o
CO
i CO
u I3 UJ
o
2 oo o
q:
q: z cl
o o
V) c
UJ <
O
u
s
o —I
o Q <
X

(X>
6
Ljl

259
 T A B L E 6.2

R E A C T IO N C O N D IT IO N S F O R C A R B O N Y L A T IO N OF
M E T H A N O L AND M E T H Y L A C E T A T E U SED BY
D IFF E R E N T PR O D U C E R S

C o n d itio n acetic a ce tic a ce tic acid^ a c e tic acid,

a cid a n h y d rid e anh yd rid e anh yd rid e
M o n s a n to E a stm a n H o e ch st BP

te m p e ra tu re 463-468. K 463, K > 423. K 456, K

P re ssu re 30-35 a t m 50 a t m > 10 a tm 30 a t m
c a ta ly s t Rh Rh Rh Rh
c o m p le x [ R h ( C O ) 2l 2] " L i + [ R h ( C O ) 2l 2] - L i + [R h (C 0 h l2 ]-P (R )4 + [ R h ( C O ) 2l 2] “ N (R '
c o c a ta ly s t . V I e l/ L il M e l/L i I M e l/P s a lts M e l / N sa lt
Zr com pound

Ref. : H e lm u t P app and M a n f r e d B a e rn s in S tu d ie s in surface science and

c a ta ly s is , V'ol 64. ed. L. G u c zi, (1 9 9 1 )

260
catalysts m od ified w ith N - or P- con tain in g ligands and m eth yl io d id e as a p ro m o ter

[N a g lieri and R izk alla and W innick (1 9 7 6 ), Isshiki et.al., (1 9 8 3 ) and G a u th ie r and

P erron (1 9 8 2 )]. V ariou s types o f n ick el co m p lex es such as N i(C O ) 4 , N il 2 and N i-b is

acetyl a ce to n a te in the p resen ce o f m ethyl io d id e and alkali m etal io d id es h ave b een

rep o rted for carbonylation o f m ethyl a ce ta te to a cetic anhydride w ith 74.2%

c o n v ersio n o f m ethyl a ceta te and 45-66.9% yield o f a cetic anhydride [R izk a lla

(1 9 8 4 ), M itsubishi (1985) and Isshiki et.al., (1983)]. G au th ier and P erron (1 9 8 2 )

h ave rep orted the carbonylation o f m ethyl a ce ta te in the p resen ce o f p rom oters such

as M eP + PPh 3 l", N a l at 453 K and 7 x 10 ^ kPa C O pressure. T h ere is only o n e

p u b lica tio n describing the activity and selectivity o f N i-iso q u in o lin e catalyst system

for carbon ylation o f m ethyl a ce ta te to a ce tic anhydride [ K elkar, et.al., (1993)].

V ap or p hase carbonylation o f m ethyl a ceta te to acetic anhydride using

N i-catalyst has b een stu d ied by Shikada et.al., (1 9 8 5 ) and (1 9 8 7 )] in the p r ese n c e o f

C H 3 I as a prom oter. A t 523 K and 3.03 x 10^ - 5 x 10^ kPa pressure, 5 0 -7 0 %

selectiv ity to acetic anhydride is reported. A c etic acid form ation was also ob serv ed

e v en th o u g h the reaction was carried out under w ater free con d ition s. In g en eral the

activity and selectivity with su pp orted catalysts was much low er com pared to the

h o m o g e n e o u s system s.

T hus, from the literature, it w as ob served that nickel com p ou n d s with a variety

o f p rom oters w ere found to be active for carbon ylation o f m ethyl acetate, h ow ever,

in m any cases p oor conversions and selectivity w ere ob tain ed . M ost o f th ese reports

are p a ten ted and only a few p ub lished reports are availab le [ K elkar, et.al., (199 3 )].

T h e refo re a d eta iled study on th e role o f solven ts, co-catalysts and p rom oters w ou ld

b e d esirab le. A system atic k inetic study b ased on the effect o f d ifferen t p aram eters

on the rate o f reaction will also be usefu l in understanding the reaction m ech anism .

261
6.2.2.3 O th er c a ta ly s ts :

G authier et.al., (1985) have reported carbonylation of methyl acetate to acetic

anhydride with C 0 X 2 or Co 2 (C O ) 2 and M ePh 3 I" p ro m o ter at 483 K and 2.5 x 10"^

kPa C O pressure.

Luft and Schrod (1983) have studied the carbonylation of methyl acetate using

an iridium catalyst. A very high selectivity ( > 9 9 % ) was rep o rted at 473-493 K and

3.03 X 10^ kPa. They have also exam ined various transition m etal catalyst systems

the activity of which varied in the following o r d e r ;

R h > Ir > Pd ~ Ru > Ni = Os = Pt

A Palladium catalyst such as Pd( 0 A c) 2 /N -m ethyl pyrrolidone was reported to

be active for carbonylation of methyl acetate to acetic anhydride at 473 K and 0.1 x

10^ - 3 x 10"^ kPa pressure [Mitsubishi (1982)]. T he selectivity to acetic anhydride

was 89.5% with traces of C H 3 C H (O A c ) 2 form ation.

E rpenbach e t.a l, (1992) have reported the carbonylation of methyl acetate to

give acetic anhydride with bim etallic N il 2 -R hC l 3 catalyst and M el and Bu 3 PMe"'' I"

pro m o ter at 463 K and 7.17 x 10^ kPa CO pressure with 99% selectivity to acetic

anhydride.

K elkar and Chaudhari (1990), have shown that Ru catalysts such as

R u C b (P P h 3 )3 , H 2 R u(C O )(PP h 3 ) 3 and trans-R u(C O ) 2 C b (P P h 3 ) 2 are also active

for carbonvlation of methyl acetate to acetic anhvdride at 513 K and 6.87 kPa CO

pressure with selectivity ranging from 74-93%.

K ozitsyna and Moisev (1990) have shown that a Pt catalyst in conjunction with

B F 3 is active for carbonylation of methyl acetate at 293-298 K and 100 kPa CO

pressure to give 3 x 10'2, kmol Ac 2 0 /km ol of Pt.

262
6.2.3 Kinetics and Mechanism ;

6.2.3.1 Rhodium catalysts :

T he kinetics and m echanism of Rh catalysed carbonylation of methyl acetate

to acetic anhydride has been studied by various authors [ Schrod e t.a l, (1983),

Polichnowski (1986), G authier-Lafaye and P erron (1985) and Z o eller et.al., (1992)].

Schrod e t.a l, (1983) have studied the kinetics and m echanism using U V and insitu

IR spectroscopy. Based on their study they concluded that the reaction was 1st o rder

in both R h and methyl iodide, and independent of methyl acetate concentration and

CO partial pressure beyond 1.51 x 10^ kPa. The orders with respect to the catalyst

and methyl iodide varied depending on the concentration of P P h 3 used. It was also

shown th at the presence of Cr com pounds such as C r(C 0 )5 reduces the induction

period of the reaction without affecting the rate of reaction which was attrib u ted to

efficient conversion of inactive Rh(III) species to Rh(l) species. T he following rate

equation has been proposed ;

k,k2iRh(a)][CH3lHL)
^ ------------

w here r = rate of reaction ; L = PPh 3 ; R h(a) = R h[(C O )2l2]'

It was found that the catalytically active species present under the reaction

conditions was [R h(C O )2l2]’ and R h(C O )I(P P h 3 )2 . The species [R h(C O )2l2]' was

p resent in significant am ount, while R h(C O )I(P P h 3 ) 2 concentration was very small.

Based on the kinetic and spectroscopic study, a catalytic cycle for carbonylation of

methyl acetate to acetic anhydride has been proposed ( Fig. 6.2) [Schrod and Luft

(1983)].

Polichnowski (1986) and Zoller et.al., (1992) have also studied the kinetics and

m echanism of carbonylation of methyl acetate to acetic anhydride using a Rh

complex catalyst in the presence of methyl iodide and Lil as prom oters. The kinetics

263
 to

<J>'
to Q
X
O LiJ
(/)
> <-
1^
00
cr>
<
O

X
LU —
I o

0)
O
o Q
O
cr
_ X
Z)
— lA
O '----
O
X m
^ fe
o h-
c\i
X LU Lu
(M X
jr o to
ro o o' I- <
x: O o o CL
CL ro
Q. CC X
ro
CJ X o
X
o h-
LjJ
CO

C\J X
o
o o
u, o
O to \ /
u -c ^x: <
Q_ — Q - — *-1 Q -i
“jz LU > -
cr CL / \
cn z .
o o
CL OQ
o cr
cr <
CL o

OJ

<J3

o
264
of the reaction over a tem p eratu re range of 443-483 K showed th at the effect of Lil,

R h and C H 3 I concentrations on the rate of reaction was som ew hat complex. The

dependance of rate on Rh and C H 3 I concentration was a function of Lil

concentration. This behavior was explained on the basis of change in rate

determ ining step of the reaction. It was observed that at lower Lil concentration, the

rate determ ining step is the consum ption of acetyl iodide by its reaction with methyl

acetate or Uthium acetate while, at high Lil concentration, oxidative addition of

m ethyl iodide to Rh complex is the rate determ ining step. At higher Lil

concentration, methyl acetate can react with Lil to give Li(OA c).

Insitu IR spectroscopy at higher tem peratures and pressures showed that

[R h(C O ) 2 l 2 l ' ^nd [R h(C O ) 2 l 4 ]‘ were the active catalytic species present under

reaction conditions. However, w hen 5% hydrogen was used in the gas phase,

[R h (C O ) 2 l 4 ]' disappeared com pletely and [R h(C O ) 2 l 2 ]' was the dom inant species

u nder the reaction conditions. A m odified reaction mechanism has been proposed

by Polichnowski (1986) (see Fig. (6.3)).

6.Z.3.2 Nickel catalysts :

G au th ier et.al., (1985) have studied the carbonylation of methyl acetate to

acetic anhydride at 25 x 10^ kPa. The catalyst system used was N i(C 0 ) 4 in

com bination with M ePPh 3 + l' and Li(OA c) and the reaction m echanism as shown

below was proposed:

Ni(co), + r \ i ( c o ) 3 r *co (6.3)

Ni(C0)3l*+ CH 3 14=3-=^ CH 3 ^ 1 ( 0 0 ) 3 ! 2 (6.4)

Ni ( CO) 3 l 2 CH 3 (CH3CO).\i(CO)2l2 (6.5)

Ni ( CO) 2 l 2 (COCH 3 ) ' + C0 CH 3 COI + :\MI(C0 ) 3 (6.6)

+ CH .COOCIl., CII 3 I + CH.jCO.'iVr (6.7)

265
 >
o rx X
o
- J 1-
LU
fe ^
I- o
o
ro ro
I I
O o t 2
o O LU I -
o O <
CM LU
o X >-
o h-
o o 0
m
a: I cr CT)
01
<

^ Q 3
O LU 00
Q- CO
^ >- Z
O
O <
H-
< <fi
O $
o
c/) UJ z
=; Q X
o
< Q
H
X o o
<J Q.
LU

2
Q Q
LU O LU
X X l-
X o
o 5 s <
0=0 0=0 Q. F-
0 o O LjJ LU
to 0=0 cr X O
ro
1 X a. K <
o o
ro
(XI
6

266
 CH3 COI + CH3 CO2 M* 4=-=^ (CH3 C0 ) 2 0 + ( 6 .8 )

N elson and co-workers (1986) have also studied the carbonylation of m ethyl

acetate with Ni catalyst in presence of Li prom oter in N-methyl pyrrolidinone as a

solvent at high pressure. Insitu IR spectroscopy showed the presence of N i(C O ) 3 l‘

and N i(C 0 )4 . From this study, they showed that N I(C 0 ) 3 l ' was the active species in

carbonylation of methyl acetate to acetic anhydride.

6.2.33 O th er catalysts :

Schrod et.al., (1983) have reported the carbonylation of methyl acetate to

acetic anhydride using Ir catalyst in the presence of C H 3 I and P Ph 3 . They found that

the rate of reaction was 1st o rder with respect to Ir, independent of methyl iodide

concentration and zero order with respect to methyl acetate. From insitu IR

spectroscopic studies, it was observed that the oxidative addition of methyl iodide

was not rate determining.- It was also found that the overall rate determ ining step

was the rearrangem ent of the alkyl complex to the acyl complex. A catalytic cycle for

this reaction has been proposed ( see Fig. 6.4).

6.3 SC O PE A ND O BJECTIV ES O F TH E P R E SE N T W O R K :

It is evident from the literature survey that rhodium is the best and m ost widely

used catalyst for carbonylation of methyl acetate. Kinetic and m echanism using this

catalyst is studied in detail and a process based on Rh catalyst has also been

com m ercialised by Tennesse Eastm an [A greda et.al., (1992)]. It has been found that

Ni catalysts also exhibit good activity and selectivity and the reaction conditions used

are com parable with that of rhodium system. However, no reports on the kinetics of

this reaction using a Ni catalyst have been published. It is with this objective th at the

p resent work was undertaken with N i-isoquinoline catalyst system, to study the

effect of reaction conditions on the initial rate of the reaction. A rate equation has

also been proposed.

267
 Q.
Q.

O
O
Q ^
ro LU
X (/) 59
o ^ < r>

<
I-
<
o
ro
CM X Q)
LU

^ (T
o X
o o
CO

— LU
9 I-
£ ?
LU
LU ^
X <
I-

U- > -
o X
I-
LU
O -

V to CO

X Li_
o < o
X
O 2
LU O
i=
<

LU > -
CO
o o
Q- QD
o cr
cr <
Q- D

(i)
6
ro
I
O
260
6.4 E X P E R I M E N T A L :

6.4.1 M aterials :

C atalyst precursor N iC l2-6H 20 supplied by Loba Chemicals, India was used.

Solvents acetic acid was obtained from SD ’s Chem ical Ltd., India, while methyl

acetate and methyl iodide and product acetic anhydride of AR quality w ere

pro cu red from B D H laboratories, Bombay. T he purity of these chem icals was found

to be > 99.5% by G LC analysis. D etails regarding CO and hydrogen are sam e as

given in earlier section ( section 2.2.1). Isoquinoline ligand was obtained from Fluka,

A .G . Switzerland. The catalyst complex N iIq 4 Cl2 was prepared by a procedure

described earlier ( section 22.2.3)

6.4.2 E xperim ental and analytical:

T he experim ental set up used was sim ilar to that described in C h ap ter 2

(section 2.2.3). Carbonylation of methyl acetate using nickel complex was carried

out in a 3 X 10*'^, m^ capacity reactor of Parr Instrum ents Co., U.S.A.

T he experim ental procedure used for carbonylation of methyl acetate was the

sam e as described earlier (section 2.2.3). The product of the reaction is highly

m oisture sensitive and easily converted to acetic acid. T herefore, the autoclave was

dried throughly before the start of the experim ent. M oisture content in acetic acid

was analysed by Karl Fischer m ethod to ensure that the solvent acetic acid used was

free from m oisture. R eactant methvl acetate was refluxed with acetic anhvdride and

freshly distilled methyl acetate was used for the experiments.

T he analytical m ethod used and the conditions for GC analysis were sim ilar to

that described in section 3.2.4

269
6.5 R ESU LT S A N D D ISC U S SIO N :

C arbonylation o f m ethyl a ceta te to acetic anhydride w as stu d ied using

N iC l 2 -6H 2 0 and N iC l 2 lq 4 co m p lex e s w ith m ethyl iod id e as a p ro m o ter at 4 9 8 ,K and

6871 kPa total pressure. It w as ob served that in all the ca ses th e m ajor product

form ed was acetic anhydride w ith sm all am ou n t o f m eth an e. T h e role o f solven ts,

co-catalysts and prom oters on th e activity and selectivity o f th e catalyst w as stu d ied

at 498 K. Initial rate data w ith respect to differen t reaction c o n d itio n s w as also

o b ta in ed . T he term s average activity, con version and selectiviy are d efin ed as :

, ^ Acetic a n h y d r i d e formed
A verage a c t iv i t y ( k m o l / k g / h r ) = ---------------------------------------- (6.9)
c a t a l y s t x time

( m eth yl a c e t a t e ) , ( m e t h y l a c e ta te )
Conversion (%) = -------------------------------------------------------------------.viOO
(m ethy l acetate),

(6.10)

^ Acetic a n h y d ri d e formed ,
Selectivity (%) = ---------------------------------------- vlOO (6.11)
Vlethyl a ceta te consumed

Prelim inary experim ents on carbonylation o f m ethyl a ce ta te to acetic

anhydride w ere carried out with N iC l 2 .6 H 2 0 as catalyst precursor and iso q u in o lin e

ligand in acetic acid solvent. In th ese cases the con version o f m ethyl a ce ta te was

found to be > 90% , w h ile the selectivity to acetic anhydride w as around 76% and

20.35% tow ards acetic acid. T h e form ation o f acetic acid was m ainly due to

co n v ersio n o f acetic anhydride to acetic acid by the reaction w ith w ater m o lec u le s

from the catalyst precursor N iC l 2 .6 H 2 0 . In the exp erim en ts carried out with

N iC l 2 lq 4 as a catalyst precursor the selectivity towards a cetic anhydride was very

high (~ 95.5% ). T h erefore, further work was carried out using N iC l 2 lq 4 as a catalyst

precursor.

T h e effect o f solvents, co-catalysts and prom oters on the average activity and

selectivity o f the catalyst was studied and the results are d iscussed b elow

27 0
6.5.1 Effect o f tem perature :

T h e effect of tem p eratu re on the initial rate of reaction was studied in a

tem p eratu re range of 478-508 K. T he results on the am ount of CO consum ed vs time

and the initial rate data are p resented in Figures 6.5 and Fig. 6.6. The initial rate of

reactio n increased with increase in tem p eratu re w ithout affecting the selectivity

tow ards acetic anhydride.

6.5.2 Effect o f solvents :

T he effect of solvents on the average activity and selectivity of the catalyst was

studied with N iCl2lq4 catalyst at 498 K, 4260 kPa CO pressure and 961 kPa

hydrogen partial pressure (Total pressure = 6871 kPa). The results are p resen ted in

T able 6.3. Carboxylic acid solvents w ere found to be the best solvents for

carbonylation of methyl acetate. Highest activity (2.04 x lO'^ k m o l/k g /h r) was

o b tained with acetic acid as a solvent with a selectivity of = 95.80%. W ith iso-butyric

acid as a solvent, the activity was marginally lower ( 1.79 x 10‘2 k m o l/k g /h r) and the

selectivity was not much affected (= 93.34%). With toluene as a solvent the average

activity was very poor (3.6 x lO'^ k m o l/k g /h r). The selectivity towards acetic

anhydride also dropped down to 88.44%, while the selectivity towards m ethane

increased to 8.86%. With n-hexane and dichlorom ethane as the solvent no activity

was observed. Only m ethane form ation was detected with n-hexane as the solvent.

T he results in T able 6.3 indicate that acetic acid shows the best activity for

carbonylation of methyl acetate, hence, for all further work acetic acid was chosen

as the solvent.

6.5.3 Effect of co-catalysts :

T he effect of a co-catalyst (SnPh 4 ) on the average activity was studied at 443 K

with NiCl2lc|4 catalyst at a total pressure of 6871 kPa (Table 6.4). It was observed

that the reaction with NiCl 2 lq 4 catalyst did not proceed at 443 K indicating that a

271
 I'iine, I X 1 0 “ ’, s

FIGURE 8.5 : A PLOT OF CO CONSUMED vs TIME

EFFECT OF TEMPERATURE
Rcat^l.ion c'ondilions;
Coiicii. of Melliyl a ce t .a lf : I.LIO, k i i i o l / i n '
Conon. of ( 11,1 ' : O.GI. k n i o l / i n
CoiifM. of Ni('l:;lii, : L1 .IU) x H) Umol/ni'
Coiicn. ol' isoiiiiiiioliiK! : O.IM, l <mo l/ i n
Partial p i e s s u i e of CO ; kPa
Partial p r e s s u r e of Hj : 9 6 1. 52, kPa

272
 6q

V)
eo
5t
e
"o
a
^ 4 -
o

K
C
■2 2 -:
o
CO
a; D/

o
Oj

a
a;
0 rmTTTTTi' I I r I I I I ri I I t I I I I I'M I I 7 I I I Tn i i p ri'rr i n-i"r
460 470 4H0 490 500 5 0
reiiiperaLure, 1', K

FIGURE G.6 : EFFECT OF TEMFEIMTURE ON

THE RATE OF REACTION
Reacti on c oi ui iUons :
Concn, (if a c e t a t e : 1 . 2 (>, l a n o l / n i ’
(.'oiicn. of Cir,! ; O.fi l, Uiii ol/ in'
Concn. of NiCljhij : :j.3(3 x 10 k iu ol/m ’
Concn. of i s o q u i n o l i n e : 0. 13, k i n o l / n i
F’artial p re s s u r e of CO : -12(>0, kPa
Partial p i o s s t i i e of H2 : 961. 52 , kl'a

2 7 3
 T A B L E 6.3

E F F E C T OF SOLVENTS ON T H E A C T IV IT Y A N D
S E L E C T IV IT Y O F N IC K E L CA TA LY ST

Solvent Total time Average Conversion Selectivitv

used time activity xlO^ of methyl %
min kmol/kg/hr acetate(%)
.AcoO Methane
-Acetic acid 150 2.04 92.53 95.80 3.59
Isobutyric acid 145 1.79 80.90 93.34 4.42
Toluene 191 0.36 22.47 88.44 8.26
n-hexane 80 0.00 17.97 0.00 10.45
Dichloro 200 0.00 4.54 0.00 0.00
methane

Reaction Conditions;

Ni(Iq),Cl3 3.36 X 10~^ kmol/m"

Isoquinoline 0.13, kmol/nr*
Methyl acetate 1.26, kmoi/in'^
Methyl iodide 0.64, kmol/nr
Partial pressure of CO 4260. kPa
Partial pressure of hydrogen 961.52. kPa
Temperature 498, K
Agitation speed 700, rpm

274
certain m in im u m tem p eratu re is n ecessary for th e in itia tio n o f the reaction .

H ow ever, o n ad d ition o f SnPh 4 as a co-catalyst the re a ctio n p ro ceed s sm ooth ly

under th e se con d ition s with an average activity o f 6.5 x lO'^ k m o l/k g /h r w ith 90%

selectivity to a cetic anhydride. T h e activity is com p arab le to that ob served at higher

tem p eratu res (478 K) w ithout S nP h 4 . A d d ition o f a seco n d co-catalyst (P d C b ) was

found to have not m uch effect on the activity as w ell as the selectiv ity o f the catalyst

( se e T a b le 6.4). T h e se results ind icate that the carb on ylation o f m ethyl a ce ta te to

acetic anhydride using N iC b Iq 4 can be carried out at low er tem p eratu res (443 K) in

the p resen ce o f S nP h 4 as a co-catalyst.

6.5.4 Effect of iodide prom oters :

T h e activity and selectivity o f N iC l 2 lq 4 catalyst in the p resen ce o f d ifferen t

iodid e p rom oters was studied at 498 K and 6871 kPa total p ressu re ( see T a b le 6.5).

It was ob served that highest activity was ob tain ed with C H 3 I as a p rom oter.

C om b in in g C H 3 I with a metal iod id e p rom oter such as Lil or N a l d ecrea sed the

average activity as w ell as the selectivity o f the catalyst. M etal iod id e p rom oters

alon e sh ow ed a poor activity for carbonylation o f m ethyl a ce ta te . T h erefo re, all

further runs w ere perform ed with m ethyl iodid e as a p rom oter.

6.5.5 Effect of ligand concentration :

T h e effect o f free isoq u in olin e con centration on the initial rate o f reaction was

stu d ied at 498 K with N iC l 2 lq 4 catalyst. T he results are p resen ted in Fig 6.7, It was

ob served that the initial rate o f reaction increases with in crease in isoq u in olin e

con cen tration upto 2.5 x lO'^ kmol/m-^ and then rem ains con stan t.

6.6 K IN ETIC S T U D Y :

In o r d e r to s t u d y t h e kinetics o f t h e r e a c t i o n , t h e effect o f r e a c t i o n c o n d i t i o n s

such as catalyst concentration, methyl acetate concentration, methyl iodide

c o n c e n t r a t i o n , acetic a n h y d r i d e c o n c e n t r a t i o n , C O partial p r e s s u r e a n d hydrogen

275
 T A B L E 6.4

E F F E C T OF C O -C A T A L Y S T S O N T H E A C T I V I T Y A N D
S E L E C T IV I T Y O F N IC K E L C A T A L Y S T

Cocatalyst Total time Average Conversion Selectivity

used time activity xlO^ of methyl %
min kmol/kg/hr acetate {%)
.^CoO Methane
nil“ 360 0.69 75.35 95.85 3.25
ml' 150 2.04 92.53 95.80 3.59
nil 300 - - - -

SuPh4 300 0.64 62.92 89.01 4.46

SnPh4 316 0.66 65.86 90.18 4.67
SnPh4/PdCl2 322 0.67 71.91 87.40 3.89

Reaction Conditions;

Ni(Iq)-.Cl2 3.36 X 10~'. kmol/m"

Isoquinoline 0.13. kmol/nr
Metiiyl acetate 1.'JG. i<mol/m*
Methyl iodide 0.t)4. kinol/m^
Partial pressure of CO 4260. kPa
Partial pressure of hydrogen 961.52. kPa
Temperature 443. K
Agitation speed 700. rpm

a Temperature = 478. K
b I'emperature = 198. K

2 76
 T A B L E 6.5

E F F E C T OF P R O M O T E R S ON T H E A C T IV IT Y A N D
S E L E C T IV IT Y O F N IC K E L CATALY ST

Prom oter Total tim e Average Conversion Selectivity

used time activity xlO^ of methyl %
min k m o l/k g /h r acetate (%)
.\c20 M ethane
Mel 150 2.04 92.53 95.80 3.59
M el/L il ISO 0.92 56.25 85.21 3.46
M el/N al 218 0.6S 48.64 84.50 4.43
N al 124 0.19 7.27 98.41 2.76
LiL2H20 242 0.52 46.75 82.65 4.87

Reaction Conditions:

Ni(Iq)4Cl2 3.36 X 10“ ^ kinol/nr

Isoquinoline 0.13, kmol/m^
Metiiyl acetate 1.26, kmol/m^
M ethyl iodide 0.64, kmol/m^
P artial pressure of CO 4260, kPa
P artial pressure of hydrogen 961.52. kPa
Tem perature 498. K
A gitation speed 700, rpm

277
o 3-
S

;3
CtJ

O
•x;

cS
d;
2 T— I— I— I— I— I— I— I— 1— I— I 1---- 1— I— I— I— I 1— I I “ T“ T T 1— I ■ I — r " T — T"

0.0 0.1 0.2 0.3

Ligand concn., L, k m o l / i n ^

P^IGURE 6.7 : EFFECT OF LIGAND CONCENTKATION

ON THE RATE OF REACTION
R e a c tio n c o n d itio n s :
Concn. o f M e U i^ 'l a c e t a t e : 1 .2 6 , k n i o l / n i ^
Concn. o f CMal : 0 .6 4 , k n i o l / n i
Concn. o f N i C l 2| q 4 : 3 - 3 6 x 10 , k m o l / n i ’
P a rtia l p r c s s v i r e o f CO : 1 2 6 0 , k l ’ a
P a rtia l p re s s u r e o f H2 ; 9 6 1 .5 2 , kP a

2 78
p artial p ressure on the initial rate o f reaction w as stu d ied at 498 K. T h e range o f

variab les in vestigated for k inetic study are p resen ted in T a b le 6 . 6 . T h e initial rate o f

rea ctio n w as calcu lated as d iscussed in sec tio n 2.3.4. T h e results are p rese n ted in th e

fo llo w in g sectio n

6.6.1 Effect o f catalyst concentration :

T h e effec t o f catalyst con cen tration on th e initial rate o f reaction w as stu d ied

at a con stan t isoq u in olin e con cen tration (1.68 x 10*2 k m o l/m ^ ). T he CO

con su m p tion vs tim e data are p resen ted in Fig 6.8 and the initial rates ca lcu la ted

from th ese data are p resented in Fig 6.9. T h e rate o f reaction w as found to in crea se

with increase in the catalyst con cen tration , how ever, the overall order o f the

reaction w as less than unity.

6.6.2 Effect of m ethyl iodide concentration :

T h e effect o f m ethyl iodid e con cen tration on the initial rate o f reaction was

stu d ied at 498 K. T h e results are p resen ted in Fig 6.10 and Fig 6.11. T h e rate was

found to increase with increase in C H 3 I con cen tration upto 6.4 x 10'^ k m o l/m ^ and

then rem ains nearly constant.

6.6.3 Effect of m ethyl acetate concentration :

T h e effect o f m ethyl a ceta te con cen tration on the initial rate o f reaction was

stu d ied at 498 K with 4260 kPa C O pressure and 961 kPa h ydrogen partial p ressure.

A p lot o f C O con su m ed vs tim e is p resen ted in Fig 6.12 and the initial rate d ata is

p resen ted in Fig 6.13. T h e initial rate o f reaction increases w ith increase in m ethyl

a ce ta te con centration upto 1.26 k m o l/m ^ and th en rem ains con stan t.

6.6.4 Effect of acetic anhydride concentration :

T h e effect o f acetic anhydride con cen tration was stu d ied in the range o f 0-1.06

km ol/m -^ at 498 K and the results on the C O con su m p tion vs tim e and initial rate

279
 T A B L E 6.6

R A N G E OF V A R IA B L E S IN V E S T IG A T E D F O R K IN E T IC
STUD Y

Tem perature, K 49S

C oncentration of catalyst, kmol/m^ 1.6S X 10-" to 6.73 xl O- "
C oncentration of methyl acetate, kmol/m^ 0.62 to 2.52
C oncentration of m eth\’l iodide, kmol/m^ 0.32 to 1.25
C oncentration of acetic anhydride, kmol/m^ 0.11 to 1.06
P artial pressure of H t, kPa 0 to L.924 X 103
P artial pressure of CO. kPa 0.2b7 to 1.IJ24 X 10-*

280
o
B

O
X
<
>>
T3
<U
B
1to3
C
o
o
o
o

0 ■i I (i
rim e , t X 10 s

FIGURE 6 .H : A PLOT OF CO CONSUMFD vs TIMK

EFFECT OF CATALYST CONCENTRATION
Kcncl ion coiidi I inns:
Concn. of Methyl a c e t a t e : 1.26, k i n o l / n i ^
Concn. of CHjl ; 0.6-}, k i n o l / m
Concii. of i socpi inol ine : 0. 13, k i n o l / u i
Pai'ti.'il iJi'ossnre of CO : I2f)0, kPa
I’arlial jjressure of : 9G1.52, k l ’a

281
 r’
T 1■
I7 7 1 11T IT 1
6
Catalyst c o n c n ., C x 10 2, 1
k m o l1/ i/n3

FIGURE 6 . 9 : EFFECT OF CATALYST CONCENTRATION

ON THE RATE OF REACTION
R e a c tio n c o n d itio n s :
Concn. o f M e t h y l a c e t a t e ; 1 .2 6 , k n i o l / i i i ®
Concn. o f C I I 3I : 0 .6 4 . k n i o l / n r ^
Concn. o f is o < [u in o lin e ; 0 .1 3 . U n i o l / m '
P a rtia l ] ) i e s s u r e o f CO : *1260, ki>a
P a i'tia l p re ssu re o f : 9 0 1 .5 2 , k l ’ a

202
 -3
Time, t x 10

FIGURE 6 . 1 0 : A PLOT OF CO CONSUMED v s TIME

EFFECT OF METHYL IODIDE CONCENTRATION
Reacti on c o n d i t i o n s :
Concn. of Methyl a c e t a t e : 1.26, k nao l/ m^
Concn. o f NiCljlq^ : 3. 36 x 10 kmol/in^
Concn. of i s o q u i n o l i n e : 0. 13, k m o l / m
Partial p r e s s u r e of CO : 4 2 60 . kPa
Partial p r e s s u r e of Hg : 9 6 1. 5 2, kPa

283
 M ethyl iodide co n cn ., E x 10, k n io l/in ^

FIGURE 6. 1 1 : EPTECT OF METHYL IODIDE

CONCENTRATION ON THE RATE OF REACTION
R eaction co n ditions:
Concn. of M etliyl a c e t a t e :1 .2 6 , k n io l/m ^
Concn. of N i C l 2i q 4 : 3 . 3 6 x 10 k n io l/in ^
Concn. of is o q u in o lin e :0 . 1 3 , k n io l/m
P artial p r e s s u r e ' o f CO : 4 2 6 0 , k P a
Partial p r e s s u r e o f H j : 9 6 1 .5 2 , k P a

284
 -3
'I'iine, t X 10

FIGURE 6 . 1 2 : A PLOT OF CO CONSUMED v s TIME

EFFECT OF METHYL ACETATE CONCENTRATION
Reaclioii c on d i t i o n s :
Coucn of CU3 I ; 0 .64, l y u o l / m “
Concn of NiCljIqj : 3. 36 x 10 , kinol/^iu^
Concn of i s o t n ii n ol in e : 0. 13, k i n o l / n i
P a l l i a p r o s s ii io hf CO : ‘12f50. k l ’a
i'ai I ia p icssMi o of H, : {)61.5:j. kl'a

285
o
a

K
C
o
o
CC

<4-1
0
4)
«3
01

0 1
M eth}i acetate co n cn ., B, k m o l/iir

FIGURE 6 . 1 3 ; EFFECT OF METHYL ACETATE

CONCENTRATION ON THE RATE OF REACTION
R eaction conditions:
Concn. o f CIlsI : 0.64. k n io l/n > ^
Concn. o f N i C l 2l q 4 : 3 . 3 6 x 10 , k n i o l / n i *
Concn. of iso<juinoline : 0.13, k m o l / n i
Partial p r e s s u r e ' o f C O : 4 2 6 0 . k l ’a
P artial pressure of ; 961.52, k P a

286
d ata are p resen ted in Figs 6.14 and 6.15 respectively. T he initial rate of reaction

decreases with increase in acetic anhydride concentration. In o rd er to confirm that

the inhibition in rate was due to increase in acetic anhydride concentration a typical

experim ent was carried out in which 1.25 k m ol/m ^ methyl acetate, 0.64 k m ol/m ^

methyl iodide and 2.12 km ol/m ^ of acetic anhydride (the total volum e of the

reaction liquid was m ade upto 1 x lO"^, m^ with solvent acetic acid) was charged to

the reacto r and the reaction was continued as usual. It was observed th a t the

reaction did not proceed at all. The reactor was cooled and 0.63 km ol/m ^ of fresh

methyl acetate was added along with w ater to convert part of the acetic anhydride

to acetic acid and the reaction was continued again. It was observed that the reaction

now proceeds smoothly (conversion = 80.42 % ; selectivity = 92.36%).

6.6.5 Effect o f CO partial pressure :

Tlie effect of CO partial pressure on the initial rate of reaction was studied at

498 K in the range of 1374-5496 kPa. In all these experim ents the hydrogen partial

pressure was kept constant at 961 kPa. The results on CO consum ption vs time and

the initial rate d ata are presented in Figs 6.16 and 6.17. T he rate of reaction was

found to increase linearly with increase in CO partial pressure.

6.6.6 E ffect of hydrogen partial pressure :

T he effect of hydrogen partial pressure was studied in the range of 0 to 1924

kPa and the results on the initial rate data are presented in Fig 6.18. The rate of

reaction was found to increase with increase in hydrogen partial pressure.

6.6.7 R ate equation :

Based on the observed trends with respect to different p aram eters it is possible

to propose a rate equation. As the mechanism of the carbonylation of methyl acetate

with Ni catalyst is not fully understood an em pirical rate equation of the following

form was proposed :

287
 »
-3
rime, t X 10

FIGURE 6 . 1 4 : A PLOT OF CO CONSUMED v s TIME

EFFECT OF ACETIC ANHYDRIDE CONCENTRATION
I^eaclion c on d i t i o n s :
Concn. of Methyl a c e t a t e ; 1.26. k i n o l / n i ^
Concn. of CII3I : O.G-I, k i n o l / n i
Concn. of NiCl 2 iq 4 : 3 .36 x 10 , k i n o l / i n ^
Concn. of i s o q u i n o l i n e : 0. 13, k n i o l / n i
Partial p r e s s u r e o f CO : 4 2 60 , kPa
Partial p re s s u r e of Hg : 9 6 1 .5 2, kPa

208
0 .0 0 .4 0 .8 1.2
A c e tic a n h y d rid e c o n c n ., F, k n io l/in ^

FIGURE 6 . 1 5 : EFFECT OF ACETIC ANHYDRIDE

CONCENTRATION ON THE RATE OF REACTION
R e a c tio n c o n d itio n s :
Concn. o f M e t h y l a c e t a t e : 1 .2 (i. k n i o l / i n ’
Concn. o f CII3I : 0 .0 4 . ls ,n io l/in '
Concn. o f N i C l 2l q 4 ; 3 .3 6 x 1 0 '“ , k n i o l / i n “
Concn. o f is o q u in o lin e : 0 .1 3 , k i n o l / n i
P a rtia l p r e s s u r e 6 f CO : 4 2 6 0 , k P a
P a rtia l p r e s s u r e o f Hz ; 9 6 1 . 5 2 , k P a

209
 lim e, t X 10 s

FIGURE 6 . 1 6 : A PLOT OF CO CONSUMED v s TIME

EFFECT OF PARTIAL PRESSURE OF CO
Reacti on conclilions:
Concn. of Methyl a c e t a t e : 1.26, k i n o l / i n *
Concn. of CH3 I ; 0. 64, k j n o l / m
Concn. of NiCljIq^ : 3. 36 x 10 ", Uinol/^n»
Concn. of i so (| i ii nol in e : 0. 13, Icniol/ni'
Partial i ) i e s s u i e o f : 9G1.52, k l ’a

290
 o 3
S

X2
<
cc:
c
o
o
CO I

<*-!
o
0)
CO
PS
0 ■f “ T - T - !-I ' I T T I t I - I - - l- T '- T - T t - r ~ ' r '7 ' I I I 1 ' V 1 I I T I

0 2U00 4000 GOOO

CO p a r t i a l p r e s s u r e . P a, k P a

FIGURE 6 . 1 7 : EFFECT OF CO PARTIAL

PRESSURE ON THE RATE OF REACTION
R e a c tio n c o n d itio n s :
Concn. o f M e t h y l a c e t a t e : 1 .2 6 , k m o l / n i ^
Concn. o f CII3I ; 0 .6 4 , l y n o l / i n '
Concn. o f N i^ l^!f^ ^ : 3.3 G x 10 k n » o l/n i^
Concn. o f is o c ju in o lin e : 0 .1 3 , k n i o l / m ' ’
P a rtia l pressure o f : 9 6 1 . 5 2 , kF’ a

291
 H y drogen p a r t i a l p r e s s u r e , U, kP a

FIGURE 6 . 1 8 : EFFECT OF HYDROGEN PARTIAL

PRESSURE ON THE RATE OF REACTION
Re acti on co iui it io ns :
Concn. of Melliyl a c e t a t e : 1.26. k i n o l / i n ^
Concn. of CH3I : 0. 64, l y n o l / i n
Concn. of NiCl 2lq 4 : 3 .36 x 10’ ", kn»ol/^ni’
Concn. of i s o( |u in d li n e : 0 .13, k n i o l / n i
Partial p re s s u r e of CO : 42 60 , kPa

292
 k o A B , C ’'E='( 1 + a D " )

w here

R \ = rate of reaction , k m o l/m ^ /s

kg = rate constant

A = Partial pressure of CO, kPa

Bi = C oncentration of methyl acetate, km ol/m ^

C = C oncentration of catalyst, km ol/m ^

E = C oncentration of methyl iodide, km ol/m ^

D = Partial pressure of hydrogen, kPa

F] = C oncentration of acetic anhydride, km ol/m ^

T he values of the rate param eters k. K g, Kp, a. b, x and y were evaluated by an

optim isation routine based on M arquardt m ethod [M arquardt (1963)] and the

values for these param eters at 498 K were 4.39 x 10'^, 82.45, 1.38, 0.0597, 0.7931.

0.70 and 0.61 respectively. Thus the final rate equation can now be w ritten as :

k o A B , C “ ' “ E“^ ' ( 1 - 0 . 0 5 9 7 D “^ ” ' )

= ^ ^ 5 ^ (6.13)
(1 - K , B , ) ( ! - K f F , ) 2

T he rates predicted using equation 6.13 were found to agree with the

experim ental rates within an erro r of ± 8% (see Fig 6.19). This indicates that

equation 6.13 fits the rate data satisfactorily.

This rate equation is valid for data at 498 K only. T herefore, to obtain a

com prehensive rate model, further work at different tem peratures is necessary.

293
E x p e rim e n ta l r a te , R* x 10^, k r n o l / i n ^ / s

FIGURE 6 . 1 9 : A PLOT OF Ra EXPERIMENTAL

v s Ra p r e d i c t e d a t 4 9 8 K

294
6.7 C O N C L U SIO N S :

T he carbonylation of methyl acetate to acetic anhydride was studied at 498 K

with N iC b Iq 4 catalyst and methyl iodide promoter. T he effect of reaction

conditions on the rate of reaction was studied and the im portant observations made

are summarised below :

1) Effect of promoters on the activity of the catalyst indicates that methyl

iodide is a better prom oter than Lil or Nal.

2) The reaction can be carried out at lower tem peratures in the presence of

SnPh 4 as a co-catalyst.

3)Acetic acid was found to be the best solvent for this reaction.

4)The rate of reaction increases with increase in catalyst concentration.

5) The rate of reaction increases with increase in methyl iodide concentration

and then nearly remains constant at higher concentrations.

6) The rate of reaction increases with increase in methyl acetate concentration

upto 1.26 km ol/m ^ and then remains constant.

7)The rate of reaction increases linearly with increase in C O partial pressure.

8) The following rate equation has been proposed :

1 - 0 . 0 5 9 7 D “- ^ ' )

2 9 5
6.8 REFERENCES :

Agreda, V. H; Pond, D. M and Zoeller, J. R., Chem. Tech., 172, (1992)

Allen, G. C and Aguilo, A., Adv. Chem. Ser., 76, 363, (1968)

Alternschoefer, T; Spes, H and Vornehm, L., Chem. Ing. Tech., 38, 963, (1966)

BASF, FR. Pat. 1073437, (1951)

Bhattacharyya, S. K and Palit, S. K., J. Appl. Chem., 12, 174, (1961)

Campbell, T. F; Pfefferkorn, R and James. F, Rounsaville, Verlag Chemie,

Vol. A l, p. 72,(1985)

Chen, D ean; Pan, Tianyuan; Yu. Xiangjen.. Fenzi, Cuihua, 4(4), 314, (1990)

Chen, Dean; Huang, Shizhuan; Bai, Zhengu., Fenzi, Cuihua. 6(1), 57, (1992)

Cook, John and Drurv, D. J (BP Chemicals Ltd), Eur. Pat. Appl. EP 98,689,
(1984)

Cook, John (BP Chemicals Ltd), Eur. Pat. Appl. EP 129,332. (1984)

Eastm an Kodak Co. EP 64986 and EP 64989, (1980)

Erpenbach, Heinz; Gradl, Reinhard: Jaegers, Erhcud and Seidel, Andreas, EP

483,536,(1992)

Galicci. J; Lafave, G. J and Perron, R. (Rhone-Poulenc de Base), Eur. Pat.

Appl. Fr. D em ande FR 2,533,959, (1983)

Gauthier-Lafave. J and Perron, R. (Rhone-Poulenc Chem ie de Base), Eur. Pat.

Appl. EP 67,777,(1982)

Gauthier-Lafaye, J and Perron, R. (Rhone-Poulenc Industries S. A), Eur. {at.

Appl. EP 50,084,(1982)

Gauthier-Lafaye, J and Perron, R, (Rhone-Poulenc C hem ie Di Base), Eur. Pat.

Appl., EP 77,746,(1983)

Gauthier-Lafaye, J; Perron, R. L and Colleuille, Y„ Bull. Chim. Soc. Fr., 353,

(1985)

G erhard, L a n d Gebhard, R. Ger. Offen. DE 3511048. (1986)

G erhard, L a n d Gebhard. R. Ger. Offen. DE 3511050. (1986)

2 9 6
G ebhard, R and G erhard, L, Chem. Ing. Tech., 59(6), 485, (1987)

H oechst G er.P at 2836084, (1980)

Isshiki, T; Kojima, Y; Mivauchi, Y and Kondo, T (Mitsubishi Gas Chemical

Co., Inc), Eur. Pat. Appl. EP 55,622, (1982)

Isshiki, T; Kojima, Y; Miyauchi, Y and Kondo, T (Mitsubishi Gas Chemical

Co., Inc), Eur. Pat. Appl. EP 70,180, (1983)

Jeffreys, G. V, “The manufacture of acetic anhydride”, 2nd ed., Institution of

chemical engineers, London, (1964)

Jenner, G. Appl. Catal. 50(2), 99. (1989)

Kelkar, A. A and Chaudhari, R. V., J. Mol. Catal., 63, L29, (1990)

Kelkar, A. A; Ubale, R. S and Chaudhari, R. V., J. Mol. Catal.,80, 21, (1993)

Kozitsyna, N. Yu and Moisev, 1.1., Kinet. Katal., 31(1), 251, (1990)

Kuckertz, Herbert, (Hoechst, A. G.) Ger. Offen. 2,450,965, (1976)

Larkins. T. H; Polichnowski, S. W; Tustin. G. C and Young, D. A., US Pat.

4,374,070, (1983)

Luft, G. and Schrod, M., J. Mol. Catal, 20, 175-84, (1983)

Luft, G erhard and Trabolt, Peter., Eur. Pat. Appl EP 332,969, (1989)

Mary Howe-Grant, Encyclopedia of Chemical Technology, 4th edition. Vol. 1

Ed. John Wiley and sons, (1991)

M arquardt, D. W, J. Chem. Soc. Ind. Appl. .Math., 2, 431, (1963)

Mitsubishi Chemicals Industries Co. Ltd., Jon. Kokai Tokkvo JP 82 21,337,

(1982)

Mitsubishi Gas Chemicals Industries, Fr. Pat. 2408571, (1977)

Mitsubishi Gas Chemicals Industries, US Pat. 4544511, (1985)

Naglieri, Anthony and Rizkaila, (Halcon Int. Inc..), US 4,002,678, (1977)

Naglieri. Anthony and Rizkaila. N.. (Halcon Int. Inc.,), US 4,002,677, (1977)

2 9 7
Nelson. G.O; Middlemas, E. C and Polichnowski, S. W., presented to the
N.Y.Acad. of Sci. March 13, (1986)

Papp, H and Baerns, M in “Studies in surface science and catalysis”, Vol. 64 ,

Elsevier Science Publishers, p. 430, Ed. L. Giczi, (1991)

Polichnowski, S. W., J. Chem. Edn., Vol. 63, p. 206, (1986)

Rengsti, Alfred and Sinzinger, Franz., Ger. Offen. D E 3,516,250, (1986)

R eppe, W ; Friedrich, H; Nikilaus V. Kuvepow and W atter Morsch, US

2,729,651, (1956)

Rhone-Poulenc, US Pat. 4511517, (1985)

Rhone-Poulenc, US Pat. 4618460, (1986)

Rizkalla, N (Halcon SD group. Inc.), Ger. Offen, DE, 3,335,594, (1984)

Rizkalla, N and Winnick, C. N (Halcon International Inc.) Ger. Offen 2,

610,035,(1976)

Roth, J. F; Craddock, J. H; Hershman, A and Paulik. F. E., Chem. Tech., 23,

600, (1971)

Shell US Pat. 4536354,(1985)

Schrod, M and Luft, G., Ind. Eng. Chem. Prod. Res. Dev., 20(4), 649, (1981)

Schrod, M ; Luft, G.and Grobe, J., J. Mol. Catal., 22, 169-178, (1983)

Shikada, T; Hiroshi, Yagita; Kohji Amata; Kaoru Fujimoto and Hiro, O.

Tominaga., Ind. Eng. Chem. Prod. Res. Dev., 24, 521, (1985)

Shikada, T; Fujimoto, K and Tominaga, H„ ACS Sym. Ser, 328, (ind. Chem.
via C j process), 177, (1987)

Showa Denko, K. K., Jpn. Kokai Tokkyo Koho JP 57,176,921, (1982)

Trabold, Peter; Steinacker, Frank and Luft Gerhard., Chem. Ing. Tech., 61(7),
556,(1989)

Vogt, Wilhelm; Glaser, Hermann and lagers, Erhcud (Hoechst A. G), Ger.
Offen. DE, 3,300,256, (1984)

Vogt, Wilhelm; Glaser, Hermann and Koch. J (Hoechst A. G), Ger. Offen. DE,
3,148,006, (1983)

2 9 8
Zoeller, J. R; Agreda, V. H; Cook, S. L; Lafferty, N. L; Polichnowski, S. W and
Pond, D. M., Catalysis Today, 13, 73, (1992)

2 9 9