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United States Patent [19] _ [11] Patent Number: 5,144,068 Smith et a1. [45] Date of Patent: * Sep. 1, 1992

[54] METHANOL CARBONYLATION PROCESS FOREIGN PATENT DOCUMENTS

[75] Inventors: Brad L. Smith, Portland; G. Paull 1468 - - Torrence, Corpus Christi; Adolfo 940 3/1977 United Kingdom ' Aguil, Corpus Christi; James 5. OTHER PUBLICATIONS Alder Corpus Chnsn an of Tex Forster, D. et al., Homogeneous Catalytic Reactions of

[73] Assignee; Hoechst Celanese Corporation, Methanol with Carbon Monoxide, Journal of Molecular Somerville, NJ Catalysis, 17 (1982) 299-314.

Roth, 1. P. et al., Low Pressure for Acetic Acid via Carbo [ * ] Notice: The portion of the term of this patent nylation, Chem. Tech., Oct. 1971, 600-605.

subsequent to Mar. 19, 2008 has been - - Primary Examiner-Vivian Garner

dlsclalmed' Attorney, Agent, or FirmDonald R. Cassady [21] App]. No.: 615,846 [57] ABSTRACT [22] Filedl Jan- 79 1991 An alcohol such as methanol is reacted with carbon

monoxide in a liquid reaction medium containing a Related US. Application Data rhodium catalyst stabilized with an iodide salt, espe

[60] Division of Ser. No. 870,267, Jim. 3, 1986, Pat. No. Ciany Phi? iodide along with alkyl iodide Such 5 5,001,259 which is a continuationdmpan of Sen NO methyl iodide and alkyl acetate such as methyl acetate 699,525, Feb. 8, 1985, abandoned, which is a continua- in specified Proportions with '3 ?nite concentration of 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

_ 203/81, 203/88 560/232, 562/607; 562/608 content is low or, as in the case of prior-art acetic acid [58] Fleld of Search ....................................... .. 562/ 519 technology, relatively high is characterized by unex_ [56] References Cited pectedly high catalyst stability; i.e., it is resistant to

Us PATENT DOCUMENTS catalyst precipitation out of the reaction medium.

5,001,259 3/1991 Smith et al. ....................... .. 562/519 16 Claims, 25 Drawing Sheets

U-S. Patent Sep. 1, 1992 Sheet 3 of 25

< q 1 1

miOE

Q

US. Patent

IIOAc S'l'Y , mules/L/hr

15

14

l2

10

Sep. 1, 1992 Sheet 4 of 25 5,144,068

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

472 ppm Rh 27 arts 2400A: 2 Ht! 820 Balance 30A: 190 C 28.2 atn. abs.

US. Patent

Rh loss , ppm/hr

1000 p

900 I

800

500

400

300

200

100

Base case, 15 was 2-1 0 600 ;:_:m Rh 2

Sheet 7 of 25 5,144,068 sep. 1, 1992

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

(Batch Glass vessel)

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

O sue as a'::ve

/ 5 1O 15 20 25 3O 35 Lil, wt!

US. Patent Sep. 1, 1992 Sheet 12 of 25 5,144,068

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