co) 5) a ay 22) (5) on 2) (8) 69) United States Patent Cheung et al. LOW WATER METHANOL CARBONYLATION PROCESS FOR HIGH ACETIC ACID PRODUCTION AND FOR WATER BALANCE CONTROL Inventors: Hosea Cheung, Corpus Christi, TX (US); Michael B. Huckman, Corpus Christi, TX (US); G, Paull Torrence, Teague City, TX (US) Assignee: Celanese International Corporation, Dallas, TX (US) Notice: Subject to any disclaimer, the tem ofthis pateat is extended ot adjusted under 35 USCC. 154(b) by 486 days Appl. No. 10/328,065 Filed: Dee, 23, 2002 Prior Publication Data US 2005)0122257 AL Jun, 24, 2004 Im. cl, core 512 2006.01) US. cL 562/819 Fleld of Classification Search 562/519 See application file for complete search history. References Cited US. PATENT DOCUMENTS 309,177 A 1197S. Ebanks 3760329 A 1G41973. Paul ta, R70935 A "21074 Eubanks Shos1st A 21977 Price 5100125 A $1991. Smith Spasas A 61991 Smith US 7,005,541 B2 ‘USOO700SS41B2 (10) Patent No. (45) Date of Patent Feb. 28, 2006 S144068 A 91992 Smith S21 A 61993 Jones SASR1S3 A 1006 Tare Shon20 A A558 aon Somass A ‘lon Dive! usta AADC Sigh eal Sonia Bi "A201 Cheung a FOREIGN PATENT DOCUMENTS ep 250 180 mL 901 ip OWIATS BD 71192 (OTHER PUBLICATIONS jostkjaer and Jensen, [Ind Ean. Chem, Prod. Res. Dev, vol. 16, No. 4, 281-285 (1977) Primary Esaminer—Pavl A. Zucker (74) Attorney, Agent, or Firm—M. Susaa Spicring 6 ABSTRACT The invention relates to 2 process for the production of acatic acid by carboaylation of methanol, and reactive Serivatives thereof, in a reaction mixture using a rhodium based catalyst in low water conditions, The process is used to achieve reaction rates of a least 15 g mole, The bigh ‘ate reactions proceed at water concentrations of less than 2.0.wi %, Under certain conditions, the water coneeatration in the reaction mixture of the process is maintained at a desired concentration by al least one process step including fdding ¢ compound such as methyl acetate, dimethyl eth foctic anhydride, or mixtures of these compounds to the reaction system. The process scp of adeing the components to the reaction mixture may be combined with other process steps for controlling water concentrations in reaction mix- {res forthe earboaylation of methaneUS 7,005,541 B2 Feb. 28, 2006 U.S. Patent pea wg N woos TZ conwoyiang I uonstay wan eeeeeee--he MvUS 7,005,541 B2 1 LOW WATER METHANOL, CARBONYLATION PROCESS FOR HIGH ACETIC ACID PRODUCTION AND FOR. WATER BALANCE CONTROL. BACKGROUND OF THE INVENTION 1. Field of the Invention This inveation relates to an improved method for the manufacture of actie acid. 2. The Related Ant ‘Aa importa process for the production of acetic acid is the earbonylation ofan alkyl alcohol, especially methanol, and reactive derivatives thereof, with carbon monoxide in @ liquid reaction medium. Such carboaylation reactions are generally carried out in the presence of a catalyst eg a Group VIIT metal catalyst such as chodivm and iridium, & halogen contsining catalyst promoter, eg, methyl iodide, and water. US. Pat. No. 3,769,329 discloses the use of & Thodiumm-based carboaylation catalyst dissolved, or olber- ‘wise dispersed, in liquid resction medium or supported on an inert solid, along with a halogen-containing catalyst promoter as exemplified by methyl iodide. However, iis Understood that various catalyst systems, particularly those incorporating Group VIII metals, may be used for the production of acetic acid through the carbonylation of methanol. Generally, the earbonylation reaction is con- ‘ducted with the catalyst being dissolved ina liquid reaction medium through which earbon monoxide gas is contimi- ‘ously bubbled, U.S, Pat. No, 3,769,329 discloses that water may be added to the reaction mixture to exert a beneficial ‘effect upon the reaction rate, and water concentrations hhetween ahout 14 weight percent (wt. fe)-I5 wt, ‘% are typically used, This i sometimes eeferred to as the “high vwater” carbonylation process ‘An alternative tothe “high water” earbonylation process is the “low water” carbonylation process, as deseibed in US. Pat. Nos. 5,001,259, 5,026,908, andl 5,144,068, Watet ‘concentrations below 14’ wi. % can be used in the “low "water" carbonylation process, Employing a low water con= ‘centration simplifies downstream processing ofthe desired ‘carboxylic acid to its glacial foem. The mote water thece is jn a reaction stream, the greater the operating costs 10 remove water from the product acetic acid and the greater the capital invesiment in product recovery and purification ‘equipment. The efficiencies achieved when operating at very low Water concentrations makes it attractive to operate at the Towest water concentration possible, However, when redvc- ing the reactor Water to minimize operating and fixed coss, itis more difficult to maintain acceptably high rates of acetic acid production with good catalysts stability since the cate of the reaction decreases, asthe reactor water is decreased as ‘explained in US. Pat'No. 5,026,908. ‘One ofthe problems associated with ow water production 5s that catalyst systems, especially rhodium-based catalysts, tend to precipitate out of the reaction misture when the ‘concentration of water is decreased, especially at concen trations lower than 14 wt. %. Significant catalyst precipita- tion, of course, can lead (© reduced reaction rates, inter rupted unit operation, and complete shutdowns. It is known that catalyst stability problems may be miaimized by the use ‘of a catalyst stabilizer such as 8 soluble metal jodie oF ‘quaternary iodide salt, As discussed in U'S. Pat, No. 5,218, 143, especialy suitable salis ae the alkali metal iodides ‘such a lithium iodide since these are the most soluble and thermally stable in the reaction medium. EP-A-O161S74 describes 4 reaction system in Which aa alcobol, as exem= % o 2 plified by methanol, i cashonylated to a carboxylic acid Serivative such as acetic acid while using 2 liquid reaction ‘medium baving a low water content. The disclosure describes that this is achieved by the use of defined con- centrations of an iodide sat, alkyl iodide and corresponding alkyl ester in the liquid ‘reaction medium to. maintain ‘hodium eatalyst stability and system productivity ‘An additional problem associated. with carbonylation reactions at lower water concentrations is that, even when catalyst systems are stabilized, production rates. are adversely reduced. For example US. Pat. No. 5,760,279 iscloses than When operating under low water conditions, the realizd reaction rate may be Tess than half of what ‘would normally be expected under a given set of conditions. ‘Various techniques for increasing the production rate under low water carbonylation reaction conditions. have been proposed. Production rates are typically defined in terms of space-time yicld (STY) which is expressed in gram-moles of acetic acid produced per hour per liter of reaction medium (g-molesVt) contained in the earbonyla- tion reactor. The volume of the reaction medium is being etermined at ambient temperature in the unaerated state US. Pat. No. 5,218,143 discloses that production levels may be enhanced at low water levels ifthe reactor is operated with optimized concentrations of methyl acetate in the reaction mixture. EP-0-250189 proposes to ad hydro in the carbon monoxide feed to the action mitre 10 tenbance the production rate, US. Pat, No. 5,939,585 dis- ‘loses the use of ruthenium or osmium as extalyst promoters to enhance prodietion rates. The disclosure of this patent indicates the use of such promoters may result in STY's af Up to approximately 11 g-moll/he under low water cond tions at concentrations of less than 1 (lw. wate. US, Pa. No. 5,218,143 discloses the use of Group VIB metal catalyst ccovstbilizets for increasing STY's under low water condi- tions to as high as 9.2 gomolVhe ata water concentration of 20 wt. %. US. Pat, No, 5,760,270 indicates that the incorporation of s manganese sabiize in conjunction with ‘shod catalyst may increase STY’s up to approximately § g-moliihr a a wator concentration of 45 wi. %. US. Pat. No. 5,488,153 and GI 2,336,154 A propose the ase of bidentate phosphorus-sulfur ligands coordinated to thodum catalysts for increasing reaction rates under low wat contitions. The examples of U.S. Pat, No. 5,488,153 dis- lose the achievement of production rates up to an STY of 19.6 g-molVhe, GB 2,336,154 A diseloses reaction ates as high a 21.9 gemolihe. These reactions disclosed in these references take place under high water conditions ‘While some of the above references refer to rhodium catalyst concentrations as high as 5000 ppm, the examples in these references generally disclose chodium catalyst con centrations of about 1000 ppm oF less. US. Pat. No. 5,144,068 discloses that, at low wat concentrations, there is a synergy between the methyl fcctate an jadi salt stabilizer in the earbonylation reactor fo enhance methanol earbonylation. It also diseloses that an advantage of operating the reactor at high methyl acetate ‘concentrations is reduction inthe formation of undesirable reaction produets. la particular, propionic acid i reduced by an order of magnitude. Carbon dioxide and hydrogen, which fate formed by the water gas shill reaction, ate also reduce "Recause the earbonylation rate of reaction is strongly ‘dependent on water concentrations, itis important to main- tain water levels in the reaction mixture during the proguc- tion of acetic acid within controlled eanges to maintain bigh reaction rates, jorkjaer and Jensen [Ind Eng. Chem., Pro. Res. Dev. 16, 281-285 (1977)] discloses the stcong depen-