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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/48—Silver or gold
  • B01J23/52—Gold
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
  • C07C2523/48—Silver or gold
  • C07C2523/52—Gold

Definitions

• the present invention relates to a method for the vapor phase carbonylation of alkyl alcohols, ethers and ester-alcohol mixtures to produce esters and carboxylic acids. More particularly, the present invention relates to a vapor phase carbonylation method catalyzed by a supported catalyst which includes an effective amount of gold. The process is particularly useful for the carbonylation of methanol to produce acetic acid, methyl acetate and mixtures thereof.
• Acetic acid is used in the manufacture of a variety of intermediary and end-products.
• an important derivative is vinyl acetate, which can be used as monomer or co-monomer for a variety of polymers.
• Acetic acid itself is used as a solvent in the production of terephthalic acid, which is widely used in the container industry, and particularly in the formation of PET beverage containers.
• Carbonylation of methanol is a well-known reaction and is typically carried out in the liquid phase with a catalyst.
• a thorough review of these commercial processes and other approaches to accomplishing the formation of acetyl from a single carbon source is described by Howard et al. in Catalysis Today, 18 (1993) 325-354.
• liquid phase carbonylation reaction for the preparation of acetic acid using methanol is performed using homogeneous catalyst systems comprising a Group VIII metal and iodine or an iodine-containing compound such as hydrogen iodide and/or methyl iodide.
• Rhodium is the most common Group VIII metal catalyst and methyl iodide is the most common promoter.
• These reactions are conducted in the presence of water to prevent precipitation of the catalyst.
• solid heterogeneous carbonylation catalysts offer the potential advantages of easier product separation, lower cost materials of construction, facile recycle, and even higher rates.
• Rhodium was the first heterogeneous catalyst used in vapor phase carbonylation.
• Schultz in U.S. Patent 3,689,533, discloses using a supported rhodium heterogeneous catalyst for the carbonylation of alcohols to form carboxylic acids in a vapor phase reaction.
• Schultz further discloses the presence of a halide promoter.
• Schultz in U.S. Patent 3,717,670 goes further to describe a similar supported rhodium catalyst in combination with promoters selected from Groups IB, IIIB, IVB, VB, VIB, VIII, lanthanide and actinide elements of the Periodic Table.
• Iridium is also 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.
• iridium as a homogeneous alcohol carbonylation catalyst, Paulik et al., in U.S. Patent 3,772,380, describe the use of iridium on an inert support as a catalyst in the vapor phase, halogen-promoted, heterogeneous alcohol carbonylation process.
• 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
• U.S. Patent 5,218,140 to Wegman, describes a vapor phase process for converting alcohols and ethers to carboxylic acids and esters by the carbonylation of alcohols and ethers with carbon monoxide in the presence of a metal ion exchanged heteropoly acid supported on an inert support.
• the catalyst used in the reaction includes a polyoxometallate anion in which the metal is at least one of a Group V(a) and VI(a) is complexed with at least one Group VIII cation such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd or Pt as catalysts for the halide-free carbonylation of alcohols and other compounds in the vapor phase.
• the process does not utilize a halide cocatalyst.
• Patent 4,776,987 and in related disclosures describe the use of chelating ligands chemically attached to various supports as a means to attach Group VIII metals to a heterogeneous catalyst for the halide-promoted vapor phase carbonylation of ethers or esters to carboxylic anhydrides.
• Drago et al. in U.S. 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.
• a number of solid materials have been reported to catalyze the carbonylation of methanol without the addition of the halide promoter.
• Gates et al. in Journal of Molecular Catalysis, 3 (1977/78) 1-9, describe a catalyst containing rhodium attached to polymer bound polychlorinated thiophenol for the liquid phase carbonylation of methanol.
• Smith et al. in European Patent Application EP 0 596 632 Al, describe the use of mordenite zeolite containing Cu, Ni, Ir, Rh, or Co as catalysts for the halide-free carbonylation of alcohols.
• Feitler in U.S. Patent 4,612,387, describes the use of certain zeolites containing no transition metals as catalysts for the halide-free carbonylation of alcohols and other compounds in the vapor phase.
• the present invention is a heterogeneous vapor phase carbonylation process wherein a gold solid supported catalyst is used.
• the process includes feeding a gaseous mixture of reactants comprising lower alkyl alcohols, ethers and ester-alcohol mixtures and carbon monoxide to a carbonylation zone containing a solid supported catalyst comprising a catalytically effective amount of gold associated with a solid support material that, desirably, is inert to the carbonylation reaction.
• Another aspect of the invention relates to a carbonylation catalyst for producing esters and carboxylic acids in a vapor phase carbonylation process having a solid supported catalyst component and further includes a halogen and/or halide containing compound, (collectively referred to herein as a "halide").
• a carbonylation catalyst for producing esters and carboxylic acids in a vapor phase carbonylation process having a solid supported catalyst component and further includes a halogen and/or halide containing compound, (collectively referred to herein as a "halide").
• It is another object of the invention is to provide a carbonylation method that results in higher yields of acetic acid with minimum formation of ethers, aldehydes, and other undesirable by-products.
• the vapor-phase carbonylation process of the present invention utilizes a solid supported catalyst having a catalytically effective amount of gold associated with a solid support material.
• the process of the present invention is particularly useful for the continuous production of acetic acid, methyl acetate and mixtures thereof.
• the inventors have found the solid gold catalyst of the present invention is comparable to a solid iridium catalyst, when used in vapor phase carbonylation. It was surprising to find that gold is an effective catalyst since rhodium, iridium, and nickel are the only metals that have previously been disclosed as being active carbonylation catalysts as single metals. It was especially surprising that gold would provide such good catalyst activity since gold has been routinely omitted from the prior disclosure of transition metals useful only as mere promoters of carbonylation catalysts. In fact, gold is considered as being so inert that it is routinely used to line reactor vessels.
• the carbonylation process of the present invention comprises feeding a gaseous mixture of an alkyl alcohol, ether, ester, or mixture thereof and carbon monoxide to a carbonylation zone and recovering a gaseous carboxylic acid, ester, or mixture product.
• the carbonylation zone is maintained under vapor-phase carbonylation conditions of temperature and pressure and contains a supported catalyst comprising a catalytically effective amount of gold associated with a solid support material.
• a catalytically effective amount of gold is associated with a solid support material that is inert in a carbonylation reaction environment.
• the term "catalytically effective” is used herein to refer to catalysis of the carbonylation of a carbonylatable compound.
• gold atoms are "associated" with the solid support material when the gold atoms are disposed on, through, and/or near the solid support as a result of any type of chemical and/or physical relationship.
• a material suitable for use as the solid catalyst support material in the present invention is a porous solid having a size of from about 400 mesh per inch to about 0.5 mesh per inch.
• the shape of the solid support is not particularly important and can be regular or irregular and include extrudates, rods, balls, broken pieces and the like disposed within the reactor.
• the support is preferably carbon, or activated carbon, having a high surface area.
• Activated carbon is well known in the art and may be derived from a variety of sources including coal, peat, and coconut shells having a density of from about 0.03 grams/cubic centimeter (g cm 3 ) to about 2.25 g/cm 3 .
• the carbon can have a surface area of from about 200 square meters/gram (m 2 /g) to about 1200 m 2 /g.
• solid support materials may be used, either alone or in combination, in accordance with the present invention include pumice, alumina, silica, silica-alumina, magnesia, diatomaceous earth, bauxite, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and combinations thereof.
• the compound or form of gold used to prepare the catalyst generally is not critical, and may be selected from any of a variety of compounds containing gold, their respective salts, and mixtures thereof.
• Particularly useful gold compounds include gold halides, cyanides, hydroxides, oxides, sulf ⁇ des, and phosphine complexes either alone or in combination. Such materials are available commercially and may be used in the preparation ofthe catalysts used in the process ofthe present invention.
• Gold oxide may be used if dissolved in the appropriate medium.
• the compound used to provide the gold component is preferably in a water-soluble form.
• Preferred water-soluble gold sources include halides, particularly the tetrahaloaurates. The most preferred hydrogen tetrahaloaurates are hydrogen tetrachloroaurate (HI) and hydrogen tetrabromoaurate (III).
• the amount of gold on the support can vary from about 0.01 weight percent to about 10 weight percent, with from about 0.1 weight percent to about 2 weight percent being preferred.
• the weight percent of gold is determined as the weight of gold atoms compared to the total weight ofthe solid supported catalyst composition.
• the catalyst ofthe present invention is very effective in carbonylation when there are essentially no other metals associated with the support besides gold. It is particularly noteworthy that the gold catalyst ofthe present invention is effective even when the catalyst is substantially free of rhodium, iridium, and nickel. "Substantially free” indicates that any presence of rhodium, iridium, or nickel is limited to trace amounts, such as the trace amount of these elements found to be naturally present with gold.
• metals besides gold may be associated with the support as part ofthe catalyst composition, either as promoters, as co- catalysts, or as inert metals, as long as the amount of gold present is an amount sufficient for the gold to effectively catalyze carbonylation in the presence ofthe other associated metal.
• the ratio ofthe weight of gold to the weight ofthe other metal is preferably greater than 1 :1, with a ratio of at least about 2:1 being more preferable.
• Suitable metals for association with the support, besides gold include alkaline or alkaline earth metals, lanthanides, tin, vanadium, molybdenum, and tungsten. The inventors have found that the lanthanides, tin, and tungsten are the most promising promoting metals for use with the gold catalyst.
• the present solid supported catalyst may be prepared by depositing gold on the solid support material to form a composition wherein a catalytically effective amount of gold is associated with the solid support material.
• the deposition of gold may be conducted by any means sufficient to cause the gold to associate with the support including but not limited to methods employing heat, electrolyzing, physical embedding, sonification, impregnating, co- precipitation.
• the preferred method of depositing the gold on the support is by dissolving or dispersing a gold compound in an appropriate solvent, and contacting, preferably impregnating, the support with the gold solution to provide a wet solid support material. The gold atoms are then associated with the support when the solvent is removed by drying the wet support material.
• a slurry ofthe gold metal can be poured over or injected into the support material.
• the support material may be immersed in excess solutions of the active components with the excess being subsequently removed using techniques known to those skilled in the art.
• the solvent or liquid is evaporated; i.e. the solid support is dried so that at least a portion ofthe gold is associated with the solid support. Drying temperatures can range from about 100°C to about 600°C. One skilled in the art will understand that the drying time is dependent upon the temperature, humidity, and solvent. Generally, lower temperatures require longer heating periods to effectively evaporate the solvent from the solid support.
• the liquid used to deliver the gold in the form of a solution, dispersion, or suspension is a liquid having a low boiling point, i.e., high vapor pressure at a temperature of from about
• suitable solvents include carbon tetrachloride, benzene, acetone, methanol, ethanol, isopropanol, isobutanol, pentane, hexane, cyclohexane, heptane, toluene, pyridine, diethylamine, acetaldehyde, acetic acid, tetrahydrofuran and water.
• the carbonylation catalyst further includes a halide promoter.
• halide is used generically and interchangeably with “halogen”, “halide” or “halide containing compound” and includes both the singular or plural forms. It is preferable that the halide is present as a vaporous part ofthe catalyst composition, thus providing a two-phase catalyst system. However, the halide may also be present as a liquid or as a solid, as long as the halide component is in sufficient contact with the gold component so as to provide gold-halide complex formation.
• the halide promoter is a catalyst component instead of a reactant, in that it is essentially non-consumed in the present carbonylation process.
• the halide may be introduced at the catalyst preparation step or, preferably, is introduced into the carbonylation reactor with the gaseous reactants.
• the halide promoter may include one or more of chlorine, bromine and/or iodine compounds and is preferably vaporous under vapor-phase carbonylation conditions of temperature and pressure.
• Suitable halides include hydrogen halides such as hydrogen iodide and gaseous hydriodic acid; alkyl and aryl halides having up to 12 carbon atoms such as, methyl iodide ethyl iodide, 1-iodopropane, 2-iodobutane, 1-iodobutane, methyl bromide, ethyl bromide, and benzyl iodide.
• the halide is a hydrogen halide or an alkyl halide having up to 6 carbon atoms.
• preferred halides are hydrogen iodide, methyl bromide and methyl iodide.
• the halide may also be a molecular halide such as I 2 , Br 2 , or Cl 2 .
• the vapor phase carbonylation process ofthe present invention is conducted by contacting the vapor phase reactants with the catalyst by flowing them through or over the catalyst. This is accomplished by feeding a gaseous mixture comprising the reactants to a carbonylation zone containing the solid supported gold catalyst ofthe present invention.
• the present heterogeneous vapor-phase process preferably operates entirely in the gas phase, i.e., none ofthe compounds or materials present in the carbonylation zone or reactor exists in a mobile liquid phase.
• a gaseous product comprising a carboxylic acid, an ester thereof, or a mixture thereof are recovered from the carbonylation zone.
• the solid supported catalyst ofthe present invention is most beneficially used in a vapor phase carbonylation process.
• the vapor phase reactants are passed through or over the catalyst.
• Vapor-phase carbonylation is typically operated at temperatures above the dew point ofthe product mixture, i.e., the temperature at which condensation occurs.
• the dew point is a complex function of dilution, product composition and pressure, and particularly with respect to non-condensable gases such as unreacted carbon monoxide, hydrogen, or inert diluent gas
• the process may still be operated over a wide range of temperatures, provided the temperature exceeds the dew point ofthe product effluent. In practice, this generally dictates a temperature range of about 100°C to 500°C, with temperatures in the range of 100°C to 325°C being preferred and temperature of about 150°C to 275°C being particularly useful.
• the useful pressure range is limited by the dew point ofthe product mixture.
• a wide range of pressures may be used, e.g., pressures in the range of about 0.1 to 100 bars absolute.
• the process preferably is carried out at a pressure in the range of about 1 to 50 bars absolute, most preferably, about 3 to 30 bar absolute.
• Suitable feedstock for the present process includes lower alkyl alcohols, ethers, ester and esters-alcohol mixtures which may be carbonylated using the catalyst ofthe present invention.
• feedstock includes alcohols and ethers in which an aliphatic carbon atom is directly bonded to an oxygen atom of either an alcoholic hydroxyl group in the compound or an ether oxygen in the compound and may further include aromatic moieties.
• the feedstock is one or more lower alkyl alcohols having from 1 to 10 carbon atoms and preferably having from 1 to 6 carbon atoms, alkane polyols having 2 to 6 carbon atoms, alkyl alkylene polyethers having 3 to 20 carbon atoms and alkoxyalkanols having from 3 to 10 carbon atoms.
• the most preferred reactant is methanol.
• methanol is the preferred feedstock to use with the solid supported catalyst ofthe present invention and is normally fed as methanol, it can be supplied in the form of a combination of materials which generate methanol. Examples of such 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 converted to acetic acid. Accordingly, one skilled in the art will further recognize that it is possible to utilize the catalyst ofthe present invention to produce a carboxylic acid from an ester feed material.
• the presence of water in the gaseous feed mixture is not essential when using methanol, the presence of some water does serve to suppress formation of methyl acetate and/or dimethyl ether. Therefore, when using methanol to generate acetic acid, 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 ofthe methanol alternative. Accordingly, 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.
• 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.
• a gaseous mixture having at least one of lower alkyl alcohol, ether and ester-alcohol mixture, either alone or in combination; carbon monoxide; and a halide are fed to a carbonylation reactor containing the gold supported catalyst described above.
• the reactant, in the vapor phase, is allowed to contact the solid supported catalyst.
• the reactor is maintained under carbonylation conditions of temperature and pressure. If acetic acid is the desired product, the feedstock may consist of methyl alcohol, dimethyl ether, methyl acetate, a methyl halide or any combination thereof. If it is desired to increase the proportion of acid produced, the ester may be recycled to the reactor together with water or introduced into a separate reactor with water to produce the acid in a separate zone.
• the carbon monoxide can be a purified carbon monoxide or include other gases.
• the carbon monoxide need not be of a high purity and may contain from about 1 % by volume to about 99 % by volume carbon monoxide, and preferably from about 70 % by volume to about 99 % by volume carbon monoxide.
• the remainder ofthe gas mixture may include such gases as nitrogen, hydrogen, carbon dioxide, water and paraffinic hydrocarbons having from one to four carbon atoms.
• hydrogen is not part ofthe reaction stoichiometry, hydrogen may be useful in maintaining optimal catalyst activity.
• the preferred ratio of carbon monoxide to hydrogen generally ranges from about 99: 1 to about 2:1, but ranges with even higher hydrogen levels are also likely to be useful.
• the amount of halide present in the gaseous feed to produce an effective carbonylation is based on the amount of alcohol or alcohol equivalents.
• the molar ratio of alcohol to halide ranges from about 1:1 to about 10,000:1, with the preferred range being from about 5:1 to about 1000:1.
• the vapor-phase carbonylation catalyst ofthe present invention may be used for making acetic acid, methyl acetate or a mixture thereof.
• the process includes the steps of contacting a gaseous mixture comprising methanol and carbon monoxide with the gold catalyst described above in a carbonylation zone and recovering a gaseous product from the carbonylation zone.
• the main gaseous products recovered include methyl acetate, acetic acid, unreacted methanol, and methyl iodide.
• CATALYST 1 (Au on Carbon): Hydrogen tetrachloroaurate (HI) hydrate (50.11% Au, 0.458 grams, 1.16 mmol) was dissolved in 30 mL of distilled water. The solution was then added to 20 grams of 12 X 40 mesh activated carbon granules (20.0 g, obtained from Calgon) having a BET surface area in excess of 800 m 2 /g contained in an evaporating dish. The mixture was heated on the steam bath with continuous stirring until it became free flowing and then transferred to a quartz tube measuring 106 cm long by 25 mm outer diameter. The quartz tube containing the mixture was placed in a three-element electric tube furnace so that the mixture was located in the approximate center ofthe 61 cm long heated zone ofthe furnace. Nitrogen (100 standard cubic centimeters per minute) was continuously passed through the catalyst bed, and the tube was heated from ambient temperature to 300°C over a 2 hour period, held at 300°C for 2 hours and then allowed to cool back to ambient temperature.
• HI
• Iridium (III) chloride hydrate (418 mg, 1.17 mmol of Ir) was dissolved in distilled water (30 mL) and then added to 12 X 40 mesh activated carbon granules (20.0 g, obtained from Calgon) having a BET surface area in excess of 800 m 2 /g contained in an evaporating dish.
• the mixture was heated on the steam bath with continuous stirring until it became free flowing and then transferred to a quartz tube measuring 106 cm long by 25 mm outer diameter.
• the quartz tube containing the mixture was placed in a three-element electric tube furnace so that the mixture was located in the approximate center ofthe 61 cm long heated zone ofthe furnace. Nitrogen (100 standard cubic centimeters per minute) was continuously passed through the catalyst bed, and the tube was heated from ambient temperature to 300°C over a 2 hour period, held at 300°C for 2 hours and then allowed to cool back to ambient temperature.
• the catalyst prepared in this manner contained 1.10% Ir and had a density of 0.57 g per mL.
• the reactor system consisted of a 800 to 950 mm (31.5 and 37 inch) section of 6.35 mm ( l ⁇ inch) diameter tubing constructed of Hastelloy alloy.
• the upper portion ofthe tube constituted the preheat and reaction (carbonylation) zones which were assembled by inserting a quartz wool pad 410 mm from the top ofthe 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 ofthe 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 Tescom
• 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).
• the flow rate of hydrogen was set at 25 standard cubic cm. per minute (cc/min) and the carbon monoxide flow rate was set at 100 cc/min.
• the reactor section was maintained under these conditions for 1 hour or until the temperature and pressure had stabilized (whichever was longer.)
• the high pressure liquid chromatography pump was then started, feeding a mixture consisting of 70 weight percent methanol and 30 weight percent methyl iodide at a rate of 12 ml/hr (The solution had a density of 1 g/mL.) Samples ofthe liquid product were collected and analyzed periodically using gas chromatographic techniques.
• Catalyst 1 the gold-on-carbon catalyst, was used in the Carbonylation of Methanol procedure described above.
• the composition and weight ofthe samples taken periodically during the carbonylation are set forth in Table 1.
• “Time” is the total time of operation (in hours) ofthe carbonylation, commencing with the feeding ofthe methanol until a particular sample aliquot was withdrawn.
• the values set forth below “Mel” (methyl iodide), “MeOAc” (methyl acetate), “MeOH” (methanol) and “HOAc” (acetic acid) are the weight percentages of each of those compounds present in the sample. The weight of each sample is given in grams.
• “Production Rate” is the moles of Acetyl Produced per liter of catalyst volume per hour during each increment of Time (Time Increment), i.e., the time of operation between samples.
• the formula for determining moles of Acetyl Produced per liter of catalyst volume per hour is:
• Example 1 was repeated twice to verify the results.
• Each ofthe two repeat examples demonstrated the same behavior observed above in that they were characterized by: a) an induction period of very low activity lasting 18-28 hours followed by, b) an period of increasing activity lasting approximately an additional 20-30 hours, and c) finally achieving a final steady state rate of approximately 45 mol of acetyl/L cat -h (80 mol ofacetyl/kg cat -h). In each case, even higher (>99%) selectivity for acetyls was observed upon reaching the final steady state rate.
• Example 1 was repeated using Comparative Catalyst C-1 (Ag on carbon). The results are shown below in Table 3 and Table 4. The calculations used to generate the information in Tables 3 and 4 are identical to those used in Example 1.
• silver is a very poor catalyst for the carbonylation of methanol when compared to gold.
• Carbonylation Example 1 was repeated using Comparative Catalyst 2 (Ir on carbon) instead ofthe gold on carbon catalyst. There was no induction period and the catalyst produced 8.65 mol of acetyl product over a period of 178 hours with a selectivity toward acetyl products of

Landscapes

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

Applications Claiming Priority (1)

Publications (1)

Family

ID=21742752

Family Applications (1)

Country Status (3)

Families Citing this family (2)

Family Cites Families (3)

• 2001
  • 2001-08-03 CN CNA018236790A patent/CN1556783A/zh active Pending
  • 2001-08-03 CN CNA018236774A patent/CN1555353A/zh active Pending
  • 2001-08-03 EP EP01957441A patent/EP1414776A1/en not_active Withdrawn
  • 2001-08-03 WO PCT/US2001/024483 patent/WO2003014054A1/en not_active Application Discontinuation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events