Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates

Definitions

• This invention pertains to a novel process for the production of acetic acid, methyl acetate or a mixture thereof by the carbonylation of methanol or methanol source. More specifically, this invention pertains to a process wherein a mixture of methanol or a methanol source, a halide and carbon monoxide are contacted in the vapor phase with a supported catalyst comprising iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladixim, platinum and rhenium deposited on a catalyst support material.
• the novel process provides a number of advantages, including improved production rates, with respect to known processes for the manufacture of acetic acid, methyl acetate or a mixture thereof from methanol .
• Iridium also is an active catalyst for methanol carbonylation reactions but normally provides reaction rates lower than those offered by rhodium catalysts when used under otherwise similar conditions.
• U.S. Patent 5,510,524 teaches that the addition of rhenium improves the rate and stability of both the Ir—I and Rh—I homogeneous catalyst systems.
• European Patent Application EP 0 752 406 Al teaches that ruthenium, osmium, rhenium, zinc, cadmium, mercury, gallium, indium, or tungsten improve the rate and stability of the liquid phase Ir—I catalyst system.
• the homogeneous carbonylation processes presently being used to prepare acetic acid provide relatively high production rates and selectivity.
• heterogeneous catalysts offer the potential advantages of easier product separation, lower cost materials of construction, facile recycle and even higher rates.
• Patent 5,488,143 describes the use of alkali, alkaline earth or transition metals as promoters for supported rhodium for the halide—promoted, vapor phase methanol carbonylation reaction.
• Pimblett in U.S. Patent 5,258,549, teaches that the combination of rhodium and nickel on a carbon support is more active than either metal by itself.
• European Patent Application EP 0 759 419 Al published 26 February 26, 1997, after the filing date of Provisional Application No. 60/037,186 cited above, pertains to a process for the carbonylation of an alcohol and/or a reactive derivative thereof.
• EP 0 759 419 Al discloses a carbonylation process comprising a first carbonylation reactor wherein an alcohol is carbonylated in the liquid phase in the presence of a homogeneous catalyst system and the off gas from this first reactor is then mixed with additional alcohol and fed to a second reactor containing a supported catalyst.
• the homogeneous catalyst system utilized in the first reactor comprises a halogen component and a Group VIII metal selected from rhodium and iridium.
• the homogeneous catalyst system also may contain an optional co—promoter selected from the group consisting of ruthenium, osmium, rhenium, cadmium, mercury, zinc, indium and gallium.
• the supported catalyst employed in the second reactor comprises a Group VIII metal selected from the group consisting of iridium, rhodium and nickel, and an optional metal promoter on a carbon support.
• the optional metal promoter may be iron, nickel, lithium and cobalt.
• Patent 5,185,462 describe heterogeneous catalysts for halide- promoted vapor phase methanol carbonylation based on noble metals attached to nitrogen or phosphorus ligands attached to an oxide support.
• Panster et al. in U.S. Patent 4,845,163, describe the use of rhodium-containing organopolysiloxane—ammonium compounds as heterogeneous catalysts for the halide—promoted liquid phase carbonylation of alcohols.
• Patent 4,417,077 describe the use of anion exchange resins bonded to anionic forms of a single transition metal as catalysts for a number of carbonylation reactions including the halide—promoted carbonylation of methanol.
• supported ligands and anion exchange resins may be of some use for immobilizing metals in liquid phase carbonylation reactions, in general, the use of supported ligands and anion exchange resins offer no advantage in the vapor phase carbonylation of alcohols compared to the use of the carbon as a support for the active metal component.
• Nickel on activated carbon has been studied as a heterogeneous catalyst for the halide—promoted vapor phase carbonylation of methanol, and increased rates are observed when hydrogen is added to the feed mixture.
• Relevant references to the nickel—on—carbon catalyst systems are provided by Fujimoto et al. In Chemistry Letters (1987) 895-898 and in Journal of Catalysis, 133 (1992) 370—382 and in the references contained therein. Liu et al., in Ind. Eng. Chem. Res . , 33 (1994) 488-492, report that tin enhances the activity of the nickel—on- carbon catalyst.
• Mueller et al. in U.S.
• Patent 4,918,2108 disclose the addition of palladium and optionally copper to supported nickel catalysts for the halide—promoted carbonylation of methanol.
• nickel—based catalysts In general the rates of reaction provided by nickel—based catalysts are lower than those provided by the analogous rhodium— based catalysts when operated under similar conditions.
• Other single metals supported on carbon have been reported by Fujimoto et al. in Catalysis Letters, 2 (1989) 145-148 to have limited activity in the halide- promoted vapor phase carbonylation of methanol. The most active of these metals is Sn. Following Sn in order of decreasing activity are Pb, Mn, Mo, Cu, Cd, Cr, Re, V, Se, W, Ge and Ga.
• This invention pertains to a vapor phase process for the preparation of acetic acid, methyl acetate or mixtures thereof by contacting methanol vapor with carbon monoxide in the presence of a catalyst comprising iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material. Operation in the vapor phase distinguishes the present process from most of the prior art pertaining to methanol carbonylation wherein the reaction is carried out in the liquid phase utilizing a dissolved (homogeneous) catalyst.
• the present invention provides a process for the preparation of acetic acid, methyl acetate or a mixture thereof which comprises the steps of: (1) feeding a gaseous mixture comprising methanol, carbon monoxide, and a halide selected from chlorine, bromine, iodine and compounds thereof to a carbonylation zone which (i) contains a supported catalyst comprising iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material and (ii) is maintained under carbonylation conditions of temperature and pressure; and (2) recovering a gaseous product comprising acetic acid, methyl acetate or a mixture thereof from the carbonylation zone.
• the process of the present invention Compared to the majority of prior art, heterogeneous processes which operate under conditions in which the reactants and/or products are present as liquids, the process of the present invention, by operating entirely in the vapor phase, eliminates catalyst dissolution (leaching from the catalyst support) , which occurs in the known heterogeneous processes operating in the presence of liquid components. Furthermore, the known operations in the presence of liquids are subject to the same problems associated with mass transfer of CO into a liquid reaction medium and the same upper limits associated with the homogeneous processes are observed. The process of the present invention provides faster rates and at lower pressures as a consequence of operating with a very active catalyst in the vapor phase. Lastly, when compared to the known, rhodium—catalyzed, vapor phase processes, which represent the best operation known to date, the catalyst used in our novel process is considerably less expensive, yet performs at a comparable rate.
• the catalyst for the process of the invention comprises a mixture of iridium and at least one second metal selected from ruthenium, molybdenum, tungsten, palladium, platinum and rhenium deposited on a catalyst support material.
• a catalyst support material examples include carbon and the oxides or mixed oxides of silicon, aluminum, zinc, zirconium, or titanium.
• the preferred support materials are selected from the wide variety of carbon, activated carbon, and silicon oxide sources available commercially. Oxides of aluminum, or materials containing oxides of aluminum are least preferred.
• the catalyst is prepared by
• step (2) (2) combining the solution of step (1) with the support material; (3) slowly evaporating the solvent; and, optionally, (4) heating the dried catalyst from step (3) at elevated temperature in a stream of inert gas or in a vacuum. Variations in this method of catalyst preparation are well known to those skilled in the art and may be used.
• the compound or form of iridium used to prepare the catalyst generally is not critical, and the catalyst may be prepared from any of a wide variety of iridium containing compounds. Indeed, iridium compounds containing myriad combinations of halide, trivalent nitrogen, organic compounds of trivalent phosphorous, carbon monoxide, hydrogen, and 2,4—pentanedione, either alone or in combination, are available commercially and may be used in the preparation of the catalysts utilized in the present invention. In addition, the oxides of iridium may be used if dissolved in the appropriate medium.
• the preferred sources of iridium is one of it chlorides, such as the hydrated trichloride and any of the various salts of hexachloroiridate(IV) .
• Use of either iridium trichloride or the hexacholoroiridate complexes should be comparable on the basis of cost, solubility, and performance.
• the compound or form of the second metal compound used to prepare the catalyst generally is not critical, and the catalyst may be prepared using any of a wide variety of compounds containing ruthenium, molybdenum, tungsten, palladium, platinum or rhenium.
• a wide variety of compounds of these elements containing various combinations of halides, acetates, nitrates, trivalent nitrogen, organic compounds of trivalent phosphorous, carbon monoxide, hydrogen, and 2,4—pentanedione, either alone or in combination, are available commercially and may be used in the preparation of the catalysts utilized in the present invention.
• the oxides of these materials may be used if dissolved in the appropriate medium.
• the compound used to provide the second metal preferably is a water soluble form of the metal (s). Based on their availability and cost, the preferred sources are the various acetates, nitrates, and halides of the second metals.
• the most preferred source among these salts would be dictated by its solubility (preferably water solubility) which can vary widely across this list of useful second components.
• solubility preferably water solubility
• the halides are generally available and quite soluble.
• the content of iridium and the second component present on the catalysts can vary over a wide range, for example from 0.01 to 10 weight percent for each metal. However, the preferred catalysts contain 0.1 to 2 weight percent of each component.
• the second metal component of the catalysts utilized in the present invention preferably is ruthenium or molybdenum.
• the supported carbonylation catalysts which are particularly preferred comprise (i) iridium and ruthenium or (ii) iridium and molybdenum deposited on a catalyst support material selected from carbon, activated carbon, and silicon oxide wherein the iridium and ruthenium each constitute 0.1 to 2 weight percent of the weight of the catalyst.
• the methanol utilized in the process normally is fed as methanol, it can be supplied in the form of a combination of materials which generate methanol reactant.
• examples of such combination of materials include (i) methyl acetate and water and (ii) dimethyl ether and water.
• both methyl acetate and dimethyl ether are formed within the reactor and, unless methyl acetate is the desired product, they are recycled with water to the reactor where they are later consumed to form acetic acid.
• the presence of water in the gaseous feed mixture is not essential when using methanol, the presence of some water is desirable to suppress formation of methyl acetate and/or dimethyl ether.
• the molar ratio of water to methanol can be 0:1 to 10:1, but preferably is in the range of 0.01:1 to 1:1.
• the amount of water fed usually is increased to account for the mole of water required for hydrolysis of the methanol alternative. Therefore, when using either methyl acetate or dimethyl ether, the mole ratio of water to ester or ether is in the range of 1:1 to 10:1, but preferably in the range of 1:1 to 3:1.
• acetic acid it is apparent that combinations of methanol, methyl ester, and/or dimethyl ether are equivalent, provided the appropriate amount of water is added to hydrolyze the ether or ester to provide the methanol reactant.
• the gaseous mixture fed to the carbonylation zone also contains a halide component selected from chlorine, bromine, iodine and compounds thereof.
• the preferred halide components are selected from bromine, bromine compounds and, especially, iodine and iodine compounds which are gaseous under the carbonylation conditions of temperature and pressure.
• the halide components may be fed in various forms although the preferred forms are as an alkyl halide, especially as methyl halide, the hydrogen halide, or as the molecular halide, i.e., I 2 , Br 2 , or Cl 2 .
• the molar ratio of methanol (or methanol equivalents) to halide or halide compound may vary substantially but typically is in the range of 1:1 to 10,000:1, with the preferred range being between 5:1 and 1000:1.
• the carbon monoxide may be fed to the carbonylation zone either as purified carbon monoxide or as a mixture of hydrogen and carbon monoxide.
• a small quantity of hydrogen may be useful in maintaining optimal catalyst activity, e.g., CO:hydrogen volume ratios of 99.5:0.5 to 95:5, the ratio of carbon monoxide to hydrogen, the presence of hydrogen, is believed to be of only minor importance.
• CO:hydrogen ratios of 100:0 to 25:75 all seem to be useful.
• the preferred CO:hydrogen ratios normally are in the range of 99:1 to 2:1.
• the process of this invention is operated in the vapor phase and, therefore, is practiced at temperatures above the dew point of the product mixture, i.e., the temperature at which condensation occurs.
• the process may still be operated over a wide range of temperatures, provided the temperature exceeds the dew point of the product effluent. In practice, this generally dictates a temperature range of 100 to 350°C, with temperatures in the range of 150 to 275°C being particularly useful. As with temperature, the useful pressure range is limited by the dew point of the product mixture.
• a wide range of pressures may be used, e.g., pressures in the range of 0.1 to 100 bars absolute (bara) (10 to 10,000 kPa) .
• the process preferably is carried out at a pressure in the range of 1 to 50 bara (100 to 5,000 kPa) , most preferably, 3 to 30 bara (300 to 3,000 kPa) .
• Catalyst Example 2 The procedure of Catalyst Example 2 was repeated twice: once, to prepare a catalyst containing only palladium as the active metal (Comparative Catalyst C—IV) ; and second, by substituting 303.5 mg (1.166 mmol) of rhodium trichloride trihydrate for the iridium trichloride hydrate, to prepare a catalyst containing rhodium and palladium (Comparative Catalyst C—V) .
• Example 2 The procedure described in Example 1 was repeated except that 331.06 mg (1.166 mmol of tungsten) of ammonium tungsten oxide [ (NH ) 6 W 12 0 1 ) «5 H 2 0] was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst V) which contained 1.08 weight percent Ir and 1.03 weight percent tungsten on activated carbon.
• Example 2 The procedure described in Example 1 was repeated except that 205.85 mg (1.166 mmol of molybdenum) of ammonium molybdenum oxide [ (NH 4 ) 6 Mo 7 0 24 ) «5 H 2 0] was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Catalyst VI) which contained 1.05 weight percent Ir and 0.52 weight percent molybdenum on activated carbon.
• COMPARATIVE CATALYST EXAMPLE C-6 The procedure described in Example 1 was repeated except that 1.153 g (4.665 mmol) of chromium acetate monohydrate was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VI) which contained 1.09 weight percent Ir and 0.29 weight percent chromium on activated carbon.
• Example 2 The procedure described in Example 1 was repeated except that 290.4 mg (1.166 mmol) of cobalt acetate tetrahydrate was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VII) which contained 1.08 weight percent Ir and 0.33 weight percent cobalt on activated carbon.
• COMPARATIVE CATALYST EXAMPLE C-8 Comparative Catalyst C—VII
• Example 2 The procedure described in Example 1 was repeated except that 106.46 mg (1.166 mmol) of ferrous chloride was substituted for the ruthenium trichloride hydrate to obtain a catalyst (Comparative Catalyst C—VIII) which contained 1.09 weight percent Ir and 0.32 weight percent iron on activated carbon.
• the upper portion of the tube constituted the preheat and reaction (carbonylation) zones which were assembled by inserting a quartz wool pad 410 mm from the top of the reactor to act as support for the catalyst, followed sequentially by (1) a 0.7 g bed of fine quartz chips (840 microns), (2) 0.5 g of one of the catalysts prepared as described in the preceding examples, and (3) an additional 6 g of fine quartz chips.
• the top of the tube was attached to an inlet manifold for introducing liquid and gaseous feeds.
• the six g of fine quartz chips acted as a heat exchange surface to vaporize the liquid feeds. Care was taken not to allow any liquid feeds to contact the catalyst bed at any time, including assembly, start—up, operation, and shutdown.
• the remaining lower length of tubing (product recovery section) consisted of a vortex cooler which varied in length depending on the original length of tubing employed and was maintained at approximately 0—5°C during operation.
• the gases were fed using Brooks flow controllers and liquids were fed using a high performance liquid chromatography pump.
• the gaseous products leaving the reaction zone were condensed using a vortex cooler operating at 0—5°C.
• the product reservoir was a tank placed downstream from the reactor system.
• the pressure was maintained using a modified Research control valve on the outlet side of the reactor system and the temperature of the reaction section was maintained using heating tape on the outside of the reaction system.
• Feeding of hydrogen and carbon monoxide to the reactor was commenced while maintaining the reactor at a temperature of 240°C and a pressure of 17.2 bara (250 psia; 1,720 kPa) .
• the flow rate of hydrogen was set at 25 standard cubic cm.
• Catalysts II—VI and Comparative Catalysts C—I — C—IX were utilized in the carbonylation of methanol according to the above—described procedure.
• the Production Rate i.e., the moles of Acetyl Produced per liter of catalyst volume per hour, provided by each of Catalysts II—VI and Comparative Catalysts C—I — C—IX is shown in Table III. TABLE III

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)

Priority Applications (4)

Applications Claiming Priority (4)

Publications (1)

Family

ID=26681586

Family Applications (1)

Country Status (8)

Cited By (10)

Families Citing this family (20)

Citations (3)

Family Cites Families (19)

• 1998
  • 1998-01-22 US US09/010,776 patent/US5900505A/en not_active Expired - Lifetime
  • 1998-01-30 ES ES98903859T patent/ES2165669T3/es not_active Expired - Lifetime
  • 1998-01-30 JP JP53311898A patent/JP3917191B2/ja not_active Expired - Fee Related
  • 1998-01-30 DE DE69802909T patent/DE69802909T2/de not_active Expired - Lifetime
  • 1998-01-30 EP EP98903859A patent/EP0968165B1/en not_active Expired - Lifetime
  • 1998-01-30 CN CN98802231A patent/CN1246842A/zh active Pending
  • 1998-01-30 CA CA002278738A patent/CA2278738A1/en not_active Abandoned
  • 1998-01-30 WO PCT/US1998/001835 patent/WO1998033759A1/en not_active Ceased

Patent Citations (3)

Also Published As

Similar Documents

Legal Events