WO1981000856A1 - Production d'acides carboxyliques et de leurs esters - Google Patents

Production d'acides carboxyliques et de leurs esters Download PDF

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Publication number
WO1981000856A1
WO1981000856A1 PCT/US1980/001276 US8001276W WO8100856A1 WO 1981000856 A1 WO1981000856 A1 WO 1981000856A1 US 8001276 W US8001276 W US 8001276W WO 8100856 A1 WO8100856 A1 WO 8100856A1
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ruthenium
methanol
aliphatic
iodide
halogen
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PCT/US1980/001276
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English (en)
Inventor
S Vanderpool
E Buinicky
J Knifton
J Estes
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Texaco Development Corp
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Publication date
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Publication of WO1981000856A1 publication Critical patent/WO1981000856A1/fr

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    • 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 concerns a process for the preparation of carboxylic acids and their ester derivatives by reaction of alcohols and their derivatives with carbon monoxide. More specifically, the inventive process concerns the selective synthesis of aliphatic carboxylic acids and their esters from aliphatic alcohols by reaction with carbon monoxide in the presence of a supported ruthenium-containing catalyst component and a halogen-containing promoter.
  • Eq. 1 is illustrative of this process, where R is a linear, branchedchain or cyclic saturated hydrocarbyl radical containing 1 to 12 carbon atoms. Methanol carbonylation to acetic acid is a specific illustration of this general synthesis.
  • acetic acid A wide variety of aliphatic carboxylic acids of differing carbon numbers and structures are presently important articles of commerce.
  • the production of acetic acid for example, now exceeds 2 billion lbs. per annum in the United States*; important applications for this acid include the production of cellulose acetate and vinyl acetate.
  • acetic acid manufacture* There are several commercially proven routes to acetic acid manufacture*, including oxidation of ethylene via acetaldhyde, liquid-phase oxidation of saturated hydro-carbons, n-butene oxidation and methanol carbonylation. To the extent that methanol is currently produced from
  • Carbonylation processes for the preparation of carboxylic acids from alcohols are well known in the art. These have been directed especially to the production of acetic acid by the carbonylation of methanol.
  • a variety of soluble and supported forms of cobalt, nickel, iron, iridium and rhodium have been patented in recent years as catalysts for methanol carbonylation to acetic acid.
  • the process of this invention is primarily directed to the synthesis of acetic acid from methanol.
  • the ruthenium-based process is characterized by selectivities to acetic acid exceeding
  • the preferred ruthenium catalysts of this process are those which minimize the formation of carbon dioxide, due to competing water-gas shift, and methane due to methanation (Eqs. 2 and 3).
  • Other products, particularly the formation of methyl acetate (Eq. 4), are equilibrium controlled and will ultimately yield acetic acid.
  • carboxylic acids and their ester derivatives are prepared from alcohol reactants and their ester derivatives by contacting said reactants with carbon monoxide in the presence of one or more supported ruthenium catalyst precursors and a halgen-containing promoter, and heating said reaction mixture under superatmospheric pressures until the desired acid products are formed.
  • aliphatic carboxylic acids and their ester derivatives containing 2 or more carbon atoms are prepared from aliphatic alcohol reactants containing 1 to 12 carbon atoms by a process comprising the following steps: a) Contacting said aliphatic alcohol with at least a catalytic quantity of a supported ruthenium-containing catalyst component in the presence of a halogen-containing promoter in which the halogen is either bromide or iodine.
  • Catalyst Composition -
  • the catalyst precursors that are suitable in the practice of this invention essentially include a ruthenium component and a halogen component in which the halogen is either bromine or Iodine.
  • a wide range of ruthenium catalyst compositions may be employed.
  • the ruthenium component is dispersed on one or more solid carriers or supports.
  • Suitable supports for the ruthenium may include, but are not limited to, activated and inactivated carbons, alumina, silica-alumina, zeolites, as well as zeolite molecular sieves, magnesia, diatomaceous earth, bauxite, titania, zirconia, clays, lime, magnesium silicate, silicon carbide, as well as various organic polymers.
  • the supports may be in the form of powders, pellets, spheres, shapes and extrudates.
  • the ruthenium component to be dispersed upon the solid support phase may be added to said supports in the form of a ruthenium oxide, as in the case of, for example, ruthenium( IV) dioxide, hydrate, anhydrous ruthenium(IV) dioxide and ruthenium(VIII) tetraoxide, or as the salt of a mineral acid, as in the case of ruthenium(II) chloride, hydrate, ruthenium(III) bromide, anhydrous ruthenium(II) chloride and ruthenium nitrate.
  • ruthenium oxide as in the case of, for example, ruthenium( IV) dioxide, hydrate, anhydrous ruthenium(IV) dioxide and ruthenium(VIII) tetraoxide
  • salt of a mineral acid as in the case of ruthenium(II) chloride, hydrate, ruthenium(III) bromide, anhydrous ruthenium(II) chloride and ruthen
  • the ruthenium may be added as the salt of a suitable organic carboxylic acid.
  • a suitable organic carboxylic acid examples include ruthenium(III) acetate, ruthenium(III) propionate, ruthenium hexafluoroacetylacetonate, ruthenium(III) trifluoroacetate, ruthenium octanoate, ruthenium naphthenate, ruthenium valerate and ruthenium(III) acetylacetonate.
  • This invention also contemplates the use of iodide-containing ruthenium salts such as ruthenium(III) triiodide, ruthenium(II) dioxide and tricarbonylruthenium(II) dioxide, as well as ruthenium carbonyl or hydrocarbonyl derivatives such as triruthenium dodecacarbonyl, H 2 Ru 4 (CO) 13 and H 4 Ru 4 (CO) 12 , and substituted carbonyl species such as the tricarbonylruthenium(II) dimer, [Ru(CO) 3 C 1 2 ].
  • iodide-containing ruthenium salts such as ruthenium(III) triiodide, ruthenium(II) dioxide and tricarbonylruthenium(II) dioxide
  • ruthenium carbonyl or hydrocarbonyl derivatives such as triruthenium dodecacarbonyl, H 2 Ru 4 (CO) 13 and H 4 Ru 4 (CO) 12
  • substituted carbonyl species such as the tri
  • the solid phase of said ruthenium-containing catalyst system is prepared by first dissolving or slurrying the selected ruthenium oxide, salt etc, eg
  • the impregnated support is then maintained at a temperature sufficient to volatize the solvent component, eg. at a temperature between 150°C and 325°C, to permit drying of the composite solid catalyst.
  • a vacuum may also be applied to the catalyst in order to volatalize the solvent, although use of vacuum is not essential.
  • the volatile solvent evaporates from the solid catalytic product, and the ruthenium component remains on the support.
  • this ruthenium impregnated solid then may be treated with hydrogen or carbon monoxide/hydrogen mixtures at elevated temperatures in order to cause at least partial reduction of the ruthenium component to ruthenium metal or a low valency form of ruthenium such as ruthenium(1).
  • the solvent which may be used to dissolve the ruthenium oxide or salt compound prior to impregnation onto the support should be a liquid of relatively low boiling point ( 150°C).
  • a preferrable group of solvents include mineral acid solutions such as hydrochloric acid and nitric acid, carboxylic acids such as acetic acid, propionic acid, and halogenated solvents like chloroform and carbon tetrachloride, ketones such as acetone and methyl isobutyl ketone, alcohols such as methanol, isopropanol and tert-butanol, aromatics such as benzene, tolune and xylene, as well as certain heterocyclic solvents like pyridine and N-methylpyrrolidone.
  • the choice of solvent is dependent optionally upon the nature of the ruthenium oxide or salt to be used for impregnation.
  • the catalytically active ruthenium species of this invention during the alcohol carbonylation is in the form of a coordination complex of ruthenium and an iodide or bromide-containing halogen component that may or may not, contain carbon monoxide ligands.
  • the ruthenium may be introduced into the reaction zone as a coordination complex of ruthenium containing these halogen ligands, as for example, when the halogen is impregnated onto the catalyst.
  • the ruthenium compound and the halogen component may be introduced separately into the reaction zone.
  • halogen component of said catalyst system may be in combined form with the ruthenium, as for instance in ruthenium(III) iodide and Ru(CO) 3 I 2 , it is generally preferred to have an excess of halogen present in the catalyst system as a promoting agent. By excess is meant an amount of halogen greater than three atoms of halogen per atom of ruthenium in the catalyst system.
  • This promoting component of the catalyst system may consist of a halogen, and/or a halogen compound, that may be introduced into the reaction zone in a gaseous or liquid- form, or saturated in a suitable solvent or reactant.
  • Satisfactory halogen promoters include hydrogen halides, such as hydrogen iodide and gaseous hydriodic acid, alkyl and aryl halides containing 1 to 2 carbon atoms such as methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane, 1-iodobutane, ethyl bromide, iodobenzene and benzyl iodide as well as acyl iodides such as acetyl iodide.
  • halogen coreactants are the alkali and alkaline earth halides, and ammonium and phosphonium halides.
  • Suitable examples include sodium iodide, cesium iodide, potassium iodide, tetramethyl-ammonium iodide, tetrabutylphosphonium iodide and potassium bromide.
  • Iodide-containing promoters are the preferred coreactants for the ruthenium catalyzed carbonylation reaction of this invention, particularly those alkyl iodide containing 1 to 12 carbon atoms wherein the alkyl radical corresponds in carbon number and structure to the alkyl radical of the aliphatic alcohol reactant.
  • Alcohol Composition - Suitable alcohol reactants for the ruthenium-catalyzed carbonylations of this invention include saturated, aliphatic, hydrocarbyl alcohols, ROH, and their ester derivatives.
  • the saturated hydrocarbylradicals (R) may include straight-chain, branched-chain and cyclic saturated radicals containing 1 to 12 carbon atoms. Generally these radicals contain one carbon less than that of the desired acid.
  • alcohols that may be readily carbonylated to the corresponding aliphatic carboxylic acids by the process of this invention include methanol, ethanol, n-propanol, iso-propanol, the butanols, pentanols, heptanols, including n-heptanol, the decanols, dodecanols, as well as the cyclohexanol and cyclopentanols.
  • esters are also suitable as reactants for the carbonylation process of this invention. These esters will have the general formula:
  • R and R' are saturated hydrocarbyl radicals that may be straight-chain, branched-chain or cyclic, and contain 1 to 12 carbon atoms.
  • Suitable examples of these esters include methyl acetate, ethyl acetate, propyl acetate, propyl propionate, ethyl propionate, pentyl acetate and the like.
  • the preferred feedstocks for this carboxylation process are alcohols of 1 to 12 carbon atoms.
  • Methanol is a particularly preferred feed, but where it is desirable to produce high proportions of carboxylic acid product, the liquid charge may also include by-products or co-products which are recycled along with the aliphatic alcohol.
  • a further embodiment of the process is when the liquid phase components, prior to carbonylation, consist of mixtures of the aforementioned aliphatic alcohols together with the corresponding ethers, alkyl halides and carbonylic acid ester.
  • the feedstock may consist of methanol in combination with derivatives thereof, such as dimethyl ether, methyl acetate and methyl iodide.
  • the alcohol reactants may be mixtures of one or more aliphatic alcohol reactancts, and these may be in combination with one or more aliphatic ethers, or aliphatic carboxylic acid esters.
  • a further class of suitable feedstocks for this process are liquid-phase components which contain substantial quantities of carboxylic acid product, aqueous coproduct and/or inert diluent.
  • the initial addition of various proportions of alcohol, acid and ester and water can substantially alter and control the final product distribution.
  • Illustrative examples include those cases where the liquid feed comprises mixtures of an aliphatic alcohol, an acid having a carbon atom more than the alcohol, and the ester of said acid and said alcohol.
  • Example 25 provides exemplifi cation of this embodiment.
  • the liquid feed comprises methanol, methyl acetate, methyl iodide and acetic acid.
  • the liquid feed comprises methanol, water and acetic acid.
  • Ruthenium-catalyzed alcohol carbonylation may also be conducted in the presence of one or more inert diluents.
  • these diluents should have boiling points higher than that of the product acids and/or esters.
  • Suitable inert diluents that may aid in the desired carbonylation process include aromatic hydrocarbons of from 6 to 20 carbon atoms, higher-boiling organic carboxylic acids and the esters composed of the aforementioned acids in combination with the feedstocks undergoing carbonylation.
  • the quantity of ruthenium catalyst employed in the instant invention is not critical and may vary over a wide range.
  • the carbonylation process is desirably conducted in the presence of a catalytically effective quantity of the active ruthenium species which gives the desired acid and/or ester products in reasonable yields.
  • the reaction proceeds when employing concentrations of ruthenium on the support of between 0.01 wt. % and 10 wt. %. This is the range normally employed, with the preferred range being 0.1 wt. % to 5 wt. %. Higher concentrations of ruthenium may be used to the extent of 20 wt. %.
  • the temperature range which can usefully be employed in these acid/ester syntheses is a variable, dependent upon other experimental factors including the choice of alcohol reactant, the pressure, and the concentration and particular choice of catalyst, among other things. Again using ruthenium as the active metal, the range of operability is from about 30° to at least 400°C, when superatmospheric pressures of syngas are employed. A narrower range of 180° - 350°C represents the preferred temperature range when the major products are aliphatic carboxylic acids and their ester derivatives. Table I is evidency of how the narrower range is derived.
  • a preferred operating range for solutions of ruthenium (III) acetylacetonate in methanol is from 500 psi (34.47 bar) to 4000 psi (275.79 bar), although pressures above 4000 psi (274.79 bar) also provide useful yields of desired ester.
  • Table I is evidence of this preferred, narrower range of operating pressures.
  • the pressures referred to here represent the total pressure generated by all the reactants, although they are substantially due to the carbon monoxide fraction in these examples.
  • the carbon monoxide may also be used in conjunction with up to 50% by volume of one or more other gases.
  • gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO carbonylation conditions such as carbon dioxide, hydrogen, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ether, alkanols such as methanol and acid esters such as methyl acetate.
  • the first class of primary products is carboxylic acids, preferably aliphatic carboxylic acids containing two or more carbon atoms.
  • the second class of primary products are ester derivatives of these carboxylic acids.
  • methanol is the alcoholic reactant
  • the principal products are acetic acid and methyl acetate.
  • Minor by-products detected in the liquid product fraction include small amounts of water, ethyl acetate and dimethyl ether. Carbon dioxide, methane and dimethyl ether may be detected in the off-gas together with unreacted carbon monoxide.
  • the process of this invention can be conducted in a batch, semi-continuous or continuous fashion.
  • the solid catalyst may be employed as a fixed or fluid bed; the reactor may consist of a series of catalyst beds or the catalyst may be placed in tubes with a heat exchange medium around the tubes. So as to provide certain operating advantages, the metal content of the catalyst may be varied through the reactor bed, and the reactants may be passed up-flow or down-flow through the reactor.
  • a second, alternative method is to have the carbonylation reactor lined with some other inert materials, such as by using a silver-lined reactor, prior to effecting the alcohol carbonylation.
  • Further alternatives include the use of titanium-lined pressure reactors, tantalum-lined reactors, and reactors having Hastelloy alloy or copper-nickel alloy surfaces.
  • This example illustrates a method of preparation of a solid catalyst, comprising 1% of ruthenium dispersed upon a carbon-containing support.
  • a sample of Columbia grade SXZ activated carbon material is first pretreated to remove metal impurities in the following manner: 900cc of carbon support is heated to 55°C overnight in 2700cc of 10% nitric acid. The acid is decanted and the support is washed with distilled water to approximately a pH of 4. Drying is accomplished in a vacuum oven at 100°C overnight.
  • a 1% ruthenium on carbon catalyst 1.28g of ruthenium chloride hydrate (36.5%Ru) is first dissolved in 5cc HCl and 5cc HNO 3 with heating. This solution is diluted to 30cc with water and added to 50g of the pretreated carbon support material. The volume of the ruthenium solution is adjusted to bring the support to incipient wetness.
  • the ruthenium-treated carbon is then prereduced by flowing the sample in a quartz tube and purging with hydrogen for 30 minutes at a H 2 flow of 12 P/hr.
  • the sample is then heated to 315°C for 1 hour and at 490°C for 2.5 hr. under the same H 2 flow conditions, upon cooling to 70°C it is purged with nitrogen until reaching ambient temperature and stored under N 2 .
  • This example illustrates the utility of a typical supported ruthenium catalyst for the production of acetic acid from methanol.
  • a typical composition of the liquid product effluent (determined by glc) is detailed below; acetic acid : 92.2wt% methyl iodide/methyl acetate : 4.6wt% methanol : 0.1wt% water : 2.8wt% As can be seen from this data the conversion of the methanol feed is 99% per pass and the majority of the product is acetic acid. In particular, chromatographic analysis of this liquid product indicates no substantial production of by-products such as aldehydes, higher boiling carboxylic acids and/or alcohols.
  • samples of the standard, 1% ruthenium-on-carbon catalyst, prepared by the procedure in Example 1 have been evaluated for the carbonyation of methanol to acetic acid over a range of operating temperatures and pressures.
  • the operating procedures are those illustrated in Example 2; the feed rates are methanol (0.13 mole/hr.), methyl iodide (0.01 mole/hr.) and carbon monoxide (0.13 mole/hr.).
  • Typical components of the liquid product effluents under steady state conditions are shown in Table 1.
  • This example illustrates the use of different reactant feed rates upon the performance of a typical 1% ruthenium-on- carbon catalyst prepared by the method of Example 1.
  • Example 2 To the 23 ml capacity continuous reactor of Example 2 filled with 1% ruthenium-on-carbon catalyst is fed a mixture of methanol (0.13 mole/hr), methyl iodide (0.005 mole/hr.) and carbon monoxide (0.16 mole/hr.). The reactor temperature is maintained at 250°C, the pressure within the reactor is 3000 psi(206.84 bar). Under steady state conditions, a typical composition of the liquid product effluent (determined by glc) is as follows: acetic acid : 67.2 st% methyl iodide/methyl acetate : 17.7 wt% methanol : 1.9 wt% water : 12..5 wt%
  • This example illustrates a method of catalyst preparation using ruthenium (IV) oxide, hydrate (Ru0 2 x H 2 O as the souce of ruthenium.
  • the ruthenium-treated carbon is then placed in a quartz tube and purged with hydrogen for 30 minutes at a H 2 flow rate of 12 1/hr.
  • the sample is next heated to 315°C. for 1 hr and 480°C for 2.5 hr under the same H 2 flow conditions. After cooling to 70°C it is purged with nitrogen before reaching ambient temperature.
  • Example 19 A supported ruthenium-on-carbon catalyst prepared from ruthenium(IV) oxide and activated carbon according to the procedure of Example 19 (see Example 23). a Methanol carbonylations carried out under the conditions of Example 2. b Prepared from ruthenium(III) chloride and activated carbon according to the procedure of Example 1. c Prepared from ruthenium( IV) oxide and activated carbon according to the procedure of Example 19.
  • This example illustrates the use of a liquid feedstock comprising a mixture of methanol, methyl acetate and methyl iodide.
  • the carbonylation process is conducted by feeding to said reactor a mixture of methanol (.10 mole/hr), methyl acetate (.03 mole/hr), methyl iodide (.01 mole/hr) and carbon monoxide (.16 mole/hr).
  • the pressure within the reactor is held at 3000 psi (206.84 bar) and the temperature is 250°C.
  • the composition of the liquid effluent is as follows: acetic acid : 34.5 wt% methyl iodide/methyl acetate : 35..6 wt% methanol : 8.5 wt% water : 21.4 wt%
  • This example illustrates the recycle of a liquid product effluent to the carbonylation reactor wherein said liquid product comprises a mixture of unreacted methanol, methyl acetate and acetic acid.
  • the carbonylation process is conducted by feeding to said reactor the liquid product from Example 2 (0.05 mole/hr), methanol (0.13 mole/hr), methyl iodide (0.01 mole/hr) and carbon monoxide (0.16 mole/hr).
  • the pressure within the reactor is held at 3000 psi (206.84 bar), and the temperature is 250°C. Under steady state conditions the majority of the product is acetic acid.
  • This example illustrates another method of catalyst preparation using an organic solvent to solubilize the ruthenium(III) chloride prior to loading onto the carbon support.
  • a sample of ruthenium(III) chloride hydrate (1.28 g) is dissolved in a minimal amount of acetone (30 ml). Thissolution is added dropwise to the carbon support, and pretreated according to the procedure of Example 1, until insipient wetness. Excess acetone is removed under vacuo, and solution addition repeated until all the ruthenium has been added to the carbon support. The ruthenium-treated carbon is then prereduced under a flow of hydrogen according to the procedure of Example 1, and stored under a nitrogen atmosphere.
  • Example 26 A catalyst prepared from a carbon support treated with a solution of .ruthenium chloride hydrate in an organic solvent (acetone).
  • Example 26 is illustrative of this catalyst preparative technique.
  • Example 2 a Methanol carbonylations carried out in accordance with the procedure and conditions of Example 2.
  • Methanol carbonylation is carried out at 3500 psi pressure.
  • Methyl iodide feed rate 0.01 mole/hr Carbon monoxide feed rate - 0.16 mole/hr
  • Operating pressure - 3000 psi (206.84 bar)
  • Operating temperature 300°C
  • Example 2 The operating procedure is similar to that outlined in Example 2. Under steady state conditions, a typical composition of the liquid product effluent is as follows: acetic acid 90.2 wt% methyl iodide/methyl acetate 3.8 wt% methanol 0.1 wt% water 5.8 wt%
  • composition of the off-gas under these same steady state conditions is as follows: carbon monoxide : 72.0% carbon dioxide : 10.4% methane : 8.1% methyl iodide : 5.8% methyl acetate : 0.8%

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  • 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)

Abstract

Production d'acides carboxyliques et de leurs esters par reaction d'alcools et de leur derive avec de l'oxyde de carbone en presence d'une ou de plusieurs compositions de catalyseurs au ruthenium et un activateur contenant un halogene.
PCT/US1980/001276 1979-10-01 1980-09-29 Production d'acides carboxyliques et de leurs esters WO1981000856A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0063105A1 (fr) * 1981-04-06 1982-10-20 Consiglio Nazionale Delle Ricerche Procédé de production d'acétate d'éthyle par homologation d'acétate de méthyle
EP0072055A1 (fr) * 1981-08-06 1983-02-16 Shell Internationale Researchmaatschappij B.V. Procédé de coproduction d'acides carboxyliques et d'esters d'acides carboxyliques
EP0075335A1 (fr) * 1981-09-22 1983-03-30 Shell Internationale Researchmaatschappij B.V. Procédé de coproduction d'acides carboxyliques et d'esters d'acides carboxyliques
EP0120631A1 (fr) * 1983-03-25 1984-10-03 Texaco Development Corporation Procédé de production d'acides carboxyliques par carbonylation en présence d'un catalyseur au carbone
US4790963A (en) * 1984-08-20 1988-12-13 The Standard Oil Company Process for synthesis of esters from gaseous reactants containing organic hydroxy compounds and mixtures of hydrogen and carbon monoxide
WO1989004295A1 (fr) * 1987-11-02 1989-05-18 Eastman Kodak Company Procede de coproduction de carboxylates aromatiques et de iodures d'alkyle
WO1997002091A1 (fr) * 1995-07-05 1997-01-23 Dsm N.V. Catalyseur de carbonylation porte par un support

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2053233A (en) * 1933-06-24 1936-09-01 Du Pont Catalyst and catalytic process
US3655745A (en) * 1968-09-06 1972-04-11 Union Oil Co Preparation of methacrylic acid
US3769324A (en) * 1972-06-15 1973-10-30 Monsanto Co Production of carboxylic acids and esters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2053233A (en) * 1933-06-24 1936-09-01 Du Pont Catalyst and catalytic process
US3655745A (en) * 1968-09-06 1972-04-11 Union Oil Co Preparation of methacrylic acid
US3769324A (en) * 1972-06-15 1973-10-30 Monsanto Co Production of carboxylic acids and esters

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0063105A1 (fr) * 1981-04-06 1982-10-20 Consiglio Nazionale Delle Ricerche Procédé de production d'acétate d'éthyle par homologation d'acétate de méthyle
EP0072055A1 (fr) * 1981-08-06 1983-02-16 Shell Internationale Researchmaatschappij B.V. Procédé de coproduction d'acides carboxyliques et d'esters d'acides carboxyliques
EP0075335A1 (fr) * 1981-09-22 1983-03-30 Shell Internationale Researchmaatschappij B.V. Procédé de coproduction d'acides carboxyliques et d'esters d'acides carboxyliques
EP0120631A1 (fr) * 1983-03-25 1984-10-03 Texaco Development Corporation Procédé de production d'acides carboxyliques par carbonylation en présence d'un catalyseur au carbone
US4790963A (en) * 1984-08-20 1988-12-13 The Standard Oil Company Process for synthesis of esters from gaseous reactants containing organic hydroxy compounds and mixtures of hydrogen and carbon monoxide
WO1989004295A1 (fr) * 1987-11-02 1989-05-18 Eastman Kodak Company Procede de coproduction de carboxylates aromatiques et de iodures d'alkyle
WO1997002091A1 (fr) * 1995-07-05 1997-01-23 Dsm N.V. Catalyseur de carbonylation porte par un support

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