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US005144068A

United States Patent [19]

[11] Patent Number:

Smith et a1.

[45]

[54] METHANOL CARBONYLATION PROCESS

[75]

Inventors:

[73] Assignee;
[ * ] Notice:

Date of Patent:

5,144,068
* Sep. 1, 1992

FOREIGN PATENT DOCUMENTS

Brad L. Smith, Portland; G. Paull

1468

Torrence, Corpus Christi; Adolfo

Aguil, Corpus Christi; James 5.

Alder Corpus Chnsn an of Tex
Hoechst Celanese Corporation,
Somerville, NJ

940 3/1977 United Kingdom '

OTHER PUBLICATIONS
Forster, D. et al., Homogeneous Catalytic Reactions of
Methanol with Carbon Monoxide, Journal of Molecular
Catalysis, 17 (1982) 299-314.
Roth, 1. P. et al., Low Pressure for Acetic Acid via Carbo
nylation, Chem. Tech., Oct. 1971, 600-605.

The portion of the term of this patent

subsequent to Mar. 19, 2008 has been
dlsclalmed'

Primary Examiner-Vivian Garner

Attorney, Agent, or FirmDonald R. Cassady

[21] App]. No.: 615,846

[57]

[22]

Division of Ser. No. 870,267, Jim. 3, 1986, Pat. No.

An alcohol such as methanol is reacted with carbon

monoxide in a liquid reaction medium containing a
rhodium catalyst stabilized with an iodide salt, espe
Ciany Phi? iodide along with alkyl iodide Such 5

5,001,259 which is a continuationdmpan of Sen NO

699,525, Feb. 8, 1985, abandoned, which is a continua-

methyl iodide and alkyl acetate such as methyl acetate

in specified Proportions with '3 ?nite concentration of

Filedl

Jan- 79 1991
Related US. Application Data

[60]

ABSTRACT

tionqmpm of Sen NO_ 606,730, May 3, 1934, aban-

water in the reaction medium the product is the carbox

cloned.

ylic acid instead of, for example, the anhydride. The

present reaction system not only provides an acid prod

[51] Int. Cl.5 ..................... .. C07C 51/12; C07.C 53/08

uct of unusually low water Content at unexpectedly

[52]

US. Cl. ..... ............ ..............

562/519, 203/77;

favorable reaction rates but also, whether the water

[58]

_
203/81, 203/88 560/232, 562/607; 562/608
Fleld of Search ....................................... .. 562/ 519

content is low or, as in the case of prior-art acetic acid

technology, relatively high is characterized by unex_

[56]

References Cited
Us PATENT DOCUMENTS
5,001,259

3/1991

Smith et al. ....................... .. 562/519

pectedly high catalyst stability; i.e., it is resistant to

catalyst precipitation out of the reaction medium.
16 Claims, 25 Drawing Sheets

U-S. Patent

Sep. 1, 1992

Sheet 3 of 25

q
<1
1

miOE
Q

US. Patent

Sep. 1, 1992

Sheet 4 of 25

5,144,068

FIG.4
Mel Dependence 5:: Methanol Ca:':cr.y.a:i:n - Baal". Autcclave

15
472 ppm Rh
27 arts 2400A:

2 Ht! 820

14

Balance 30A:
190 C
28.2 atn. abs.

l2

10

mSuI'lesO/A,LYchr

US. Patent

sep. 1, 1992

Sheet 7 of 25

5,144,068

FIG.7
Race of Rh Pzecipitaticn in 1):: Presence of 21'.

(Batch Glass vessel)

1000 p

900

800

1000 _=;:': an
Balance 1-16.15:
El. sparge

O sue as a'::ve

500

pRhloms/,hr
400

300

200

100

Base case, 15 was 2-1 0

600 ;:_:m Rh
2

1O

15
Lil,

20
wt!

25

3O

35

US. Patent

Sep. 1, 1992

Sheet 12 of 25

5,144,068

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