WO2008073096A1 - Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs - Google Patents

Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs Download PDF

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Publication number
WO2008073096A1
WO2008073096A1 PCT/US2006/047718 US2006047718W WO2008073096A1 WO 2008073096 A1 WO2008073096 A1 WO 2008073096A1 US 2006047718 W US2006047718 W US 2006047718W WO 2008073096 A1 WO2008073096 A1 WO 2008073096A1
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process according
zeolite
ester
ether
catalyst
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PCT/US2006/047718
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English (en)
Inventor
Enrique Iglesia
John Glenn Sunley
David John Law
Aditya Bhan
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The Regents Of The University Of California
Bp Chemicals Ltd.
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Application filed by The Regents Of The University Of California, Bp Chemicals Ltd. filed Critical The Regents Of The University Of California
Priority to EP06845427A priority Critical patent/EP2114850A4/fr
Priority to CA2671361A priority patent/CA2671361C/fr
Priority to UAA200907279A priority patent/UA95663C2/uk
Priority to PCT/US2006/047718 priority patent/WO2008073096A1/fr
Priority to CN2006800566291A priority patent/CN101600678B/zh
Priority to KR1020097012298A priority patent/KR20090092280A/ko
Priority to KR1020147009999A priority patent/KR20140054448A/ko
Priority to JP2009541278A priority patent/JP2010513270A/ja
Priority to BRPI0622186-6A priority patent/BRPI0622186A2/pt
Publication of WO2008073096A1 publication Critical patent/WO2008073096A1/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
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • 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
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide

Definitions

  • This invention relates to a process for the selective production of lower aliphatic carboxylic acids and/or their corresponding esters by the carbonylation of the corresponding lower aliphatic alcohol and/or ester or ether derivatives thereof, and, in particular- to the selective production of acetic acid and/or methyl acetate by the carbonylation of methanol and/or ester or ether derivatives thereof.
  • This invention also relates to an improved process for the production of methyl acetate from dimethyl ether, and more generally to the production of alkyl esters of aliphatic carboxylic acids, by the carbonylation of alkyl ethers.
  • this invention relates to the production of lower aliphatic carboxylic acids by first producing an alkyl ester from a lower alkyl ether, followed by hydrolysis of the ester to the acid.
  • An example of this is the production of acetic acid by carbonylation of dimethyl ether, to form methyl acetate, followed by hydrolysis of the ester to produce acetic acid.
  • EP-A- 0 596 632 discloses the preparation of an aliphatic carboxylic acid by contacting an aliphatic alcohol or a reactive derivative thereof with carbon monoxide in the presence of a copper, nickel, indium, rhodium or cobalt loaded mordenite zeolite catalyst at high temperatures and pressures.
  • WO 2005/105720 discloses a process for the preparation of an aliphatic carboxylic acid, ester or anhydride thereof by contacting an aliphatic alcohol and/or a reactive derivative thereof with carbon monoxide in the presence of a copper, nickel, iridium, rhodium or cobalt loaded mordenite catalyst which has as framework elements, silicon, aluminium and also one or more of gallium, boron and iron.
  • US 6,387,842 discloses processes and catalysts for converting an alcohol, ether and/or ether alcohol feedstock to oxygenated products by reaction with carbon monoxide in the presence of a catalyst comprising a solid super acid, clay, zeolite or molecular sieve under conditions of temperature and pressure.
  • Cheung et al (Angew. Chem. Int. Ed 2006, 45, (10), 1617) carried out carbonylation of dimethyl ether with the zeolites mordenite, ferrierite and also with the zeolites ZSM-5, BEA and USY. These latter three zeolite types do not contain 8-member ring channels.
  • This invention comprises a process for the selective production of a C1-C 3 aliphatic carboxylic acid such as acetic acid and/or the corresponding C 1 -C 3 ester, such as methyl acetate by carbonylating the corresponding C 1 -C 3 aliphatic alcohol, such as methanol and/or an ester or ether derivative thereof, such as dimethyl ether with carbon monoxide in the presence of a catalyst comprising a zeolite, having at least one 8-member ring channel, said 8-member ring channel being interconnected with a channel defined by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Br ⁇ nsted acid site and wherein the zeolite has a silica : X 2 O 3 ratio of at least 5, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof, with the proviso that the
  • This invention also comprises a process for producing a product comprising a C 1 -C 3 alkyl ester of a C 1 -C 3 aliphatic carboxylic acid, such as methyl acetate comprising carbonylating a C 1 -C 3 alkyl ether, such as dimethyl ether with carbon monoxide under substantially anhydrous conditions in the presence of a catalyst comprising a zeolite having at least one 8-member ring channel, said 8-member ring channel being interconnected with a channel defined by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Br ⁇ nsted acid site and wherein the zeolite has a silica : X 2 O 3 ratio of at least 5, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof, with the proviso that the zeolite is not mordenite or fer
  • This invention comprises a process for the selective production of a C1-C 3 aliphatic carboxylic acid such as acetic acid and/or the corresponding ester, such as methyl acetate by carbonylating the corresponding Cj-C 3 aliphatic alcohol, such as methanol and/or an ester or ether derivative thereof, such as dimethyl ether with carbon monoxide in the presence of a catalyst comprising a zeolite having at least one 8-member ring channel, said 8-member ring channel being interconnected with a channel defined by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Br ⁇ nsted acid site and wherein the zeolite has a silica : X 2 O 3 ratio of at least 5, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof, with the proviso that the zeolite is not morde
  • This invention also comprises a process for producing a product comprising a C1-C3 alkyl ester of a C 1 -C 3 aliphatic carboxylic acid, such as methyl acetate comprising carbonylating a C 1 -C 3 alkyl ether, such as dimethyl ether with carbon monoxide under substantially anhydrous conditions in the presence of a catalyst comprising a zeolite having at least one 8-member ring channel, said 8-member ring channel being interconnected with a channel defined by a ring with greater than or equal to 8 members, said 8-member ring having a window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Br ⁇ nsted acid site and wherein the zeolite has a silica : X 2 O 3 ratio of at least 5, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof, with the proviso that the zeolite is not mordenite or ferrierite.
  • one component of the feed to the process may be a Ci- C 3 aliphatic alcohol.
  • the process is particularly applicable to alcohols such as methanol, ethanol and n-propanol.
  • a preferred alcohol is methanol.
  • Reactive derivatives of the alcohol which may be used as an alternative to, or in addition to the alcohol, include esters of the alcohol and ether derivatives of a C 1 -C 3 alcohol. Suitable reactive derivatives of methanol include methyl acetate and dimethyl ether. A mixture of the alcohol and a reactive derivative thereof may also be employed, such as a mixture of methanol and methyl acetate.
  • the product will be dependent upon the degree of conversion of the alcohol. If the conversion is 100% then the product will be the corresponding carboxylic acid. Thus where methanol is the alcohol feed, the product will comprise acetic acid. If the conversion is less than 100%, the alcohol will be converted to a mixture of the corresponding carboxylic acid and carboxylic acid ester. If the ester employed as the feed, is a symmetrical ester, for example, methyl acetate, the main product of the carbonylation process will be the corresponding carboxylic acid (in this case, acetic acid). If the ester is asymmetrical, then the product will comprise a mixture of carboxylic acids formed from each of the alkyl groups of the ester.
  • one component of the feed to the process comprises a C 1 -C 3 alkyl ether, that is, a compound having the formula
  • R 1 -O-R 2 in which R 1 and R 2 are independently C 1 -C 3 alkyl groups.
  • Ri and R 2 are straight-chain alkyl groups, most preferably straight-chain alkyl groups having from 1 to 3 carbon atoms each, such as methyl, ethyl and n-propyl.
  • the main product will be the corresponding alkyl ester of an aliphatic acid (in this case, methyl acetate).
  • a second component of the process is a feed comprising carbon monoxide.
  • the feed may comprise substantially pure carbon monoxide (CO), for example, carbon monoxide typically provided by suppliers of industrial gases, or the feed may contain impurities that do not interfere with the conversion of the alkyl ether to the desired ester, such as hydrogen, nitrogen, helium, argon, methane and/or carbon dioxide.
  • CO carbon monoxide
  • the feed may comprise CO that is typically made commercially by removing hydrogen from synthesis gas via a cryogenic separation and/or use of a membrane.
  • the carbon monoxide feed may contain substantial amounts of hydrogen.
  • the feed may be what is commonly known as synthesis gas, i.e. any of a number of gaseous mixtures that are used for synthesizing a variety of organic or inorganic compounds, and particularly for ammonia synthesis.
  • Synthesis gas typically results from reacting carbon- rich substances with steam (in a process known as steam reforming) or with steam and oxygen (a partial oxidation process).
  • These gases contain mainly carbon monoxide and hydrogen, and may also contain smaller quantities of carbon dioxide and nitrogen.
  • the ratio of carbon monoxide : hydrogen may be in the range 1 : 3 to 15 : 1 on a molar basis, such as 1 : 1 to 10 : 1.
  • synthesis gas provides another advantage over processes for producing acetic acid from methanol, namely the option of using a less expensive carbon monoxide feed.
  • methanol-to-acetic acid processes the inclusion of hydrogen in the feed can result in production of unwanted hydrogenation.
  • the catalyst for use in the process of the invention is a zeolite, excluding mordenite and ferrierite.
  • Zeolites both natural and synthetic are microporous crystalline aluminosilicate materials having a definite crystalline structure as determined by X-ray diffraction.
  • the chemical composition of zeolites can vary widely but they typically consist of SiO 2 in which some of the Si atoms may be replaced by tetravalent atoms such as Ti or Ge, by trivalent atoms such as Al, B, Ga, Fe or by bivalent atoms such as Be, or by a combination thereof.
  • a zeolite is comprised of a system of channels which may be interconnected with other channel systems or cavities such as side-pockets or cages.
  • the channel systems are uniform in size within a specific zeolite and may be three-dimensional but are not necessarily so and may be two-dimensional or one-dimensional.
  • the channel systems of a zeolite are typically accessed via 12-member rings, 10-member rings or 8 member rings.
  • the zeolites for use in the present invention contain at least one channel which is defined by an 8-member ring.
  • Preferred zeolites are those which do not have side-pockets or cages within the zeolite structure.
  • the Atlas of Zeolite Framework Types C. Baerlocher, W. M. Meier, D. H. Olson, 5 th ed.
  • zeolite' also includes materials having a zeolite-type structure such as delaminated porous crystalline oxide materials and pillared layered oxide materials such as ITQ-36.
  • the process of the present invention employs a zeolite having at least one channel defined by an 8-member ring of tetrahedrally co-ordinated atoms (tetrahedra) with a window size having a minimum dimension of 2.5 Angstroms x 3.6 Angstroms.
  • the 8-member ring channel is interconnected with at least one channel defined by a ring with equal to or greater than 8 members, such as 10 and/or 12 members.
  • the interconnected 8-, 10, and 12- member ring channels provide access to Br ⁇ nsted acid sites contained in the 8-member ring channels to enable the carbonylation of the C 1 -C 3 alcohol or derivative thereof, such as methanol and dimethyl ether to proceed at acceptable rates.
  • the zeolite for use in the present invention may consist of interconnected channels defined solely by 8-member rings, such as zeolites of framework type CHA, for example, chabazite and framework type ITE, for example ITQ-3.
  • the zeolite has at least one channel formed by an 8-member ring and at least one interconnecting channel defined by a ring with greater than 8 members, such as a 10, and/or 12 member ring.
  • Non- limiting examples of zeolites having 8- member ring channels and interconnecting larger ring channel systems include zeolites of framework type OFF, for example, offretite, GME, for example Gmelinite, MFS, such as ZSM-57, EON such as ECR-I and ETR such as ECR-34.
  • the zeolites for use in the process of the present invention have at least one 8- member ring channel interconnected with at least one 12-member ring channel, such as those of framework type OFF and GME, for example, offretite and gmelinite.
  • Zeolites are available from commercial sources. Alternatively they may be synthesized using known techniques. In general, synthetic zeolites are prepared from aqueous reaction mixtures comprising sources of appropriate oxides. Organic directing agents may also be included in the reaction mixture for the purpose of influencing the production of a zeolite having the desired structure. After the components of the reaction mixture are properly mixed with one another, the reaction mixture is subjected to appropriate crystallization conditions. After crystallization of the reaction mixture is complete, the crystalline product may be recovered from the remainder of the reaction mixture. Such recovery may involve filtering the crystals, washing with water followed by a calcination treatment at high temperature. The synthesis of zeolites is described in numerous references.
  • zeolite Y and its synthesis is described in US 3,130,007
  • zeolite ZSM-23 is described in US 4,076,842 and J.Phys. Chem. B, 109, 652-661 (2005), Zones, S.I. Darton, R. J., Morris, R and Hwany, S-J
  • ECR- 18 is described in Microporous Mesoporous Mat., 28, 233-239 (1999), Vaughan D.E.W. & Strohmaier, K.G.
  • Theta-1 is described in Nature, 312, 533-534 (1984).
  • the zeolite catalyst for use in the process of the present invention is used in the acid form, generally referred to as the ⁇ ' form of the zeolite, for example, H-rissatite.
  • Other forms of the zeolite, such as the NH 4 form can be converted to the H-form, for example, by calcining the NH 4 form at elevated temperature.
  • the acid form of a zeolite will possess Br ⁇ nsted acid (H + ) sites which are distributed among the various channel systems in the zeolite.
  • H-offretite has H + sites located in the 12 member ring channels and in the 8 member ring channels.
  • the number or concentration of H + species residing in any particular channel system can be determined by known techniques such.
  • SiO 2 : X 2 O 3 wherein X is a trivalent element, such as aluminium, boron, iron and/or gallium, preferably aluminium.
  • the SiO 2 : X 2 O 3 ratio of a given zeolite is often variable.
  • the upper limit of the SiO 2 : X 2 O 3 ratio is unbounded, for example, the zeolite ZSM-5.
  • the zeolites for use in the present invention have a SiO 2 : X2O3 molar ratio of at least 5, preferably in the range 7 to 40, such as 10 to 30.
  • the SiO 2 : X 2 O 3 molar ratio is less than or equal to 100.
  • Particular SiO 2 : X 2 O 3 ratios can be obtained for many zeolites by dealumination (where X is Al), by standard techniques using high temperature steam treatment or acid washing.
  • water may be generated in-situ.
  • water is generated by the dimerisation of the alcohol to an ether
  • Water may also be generated by the esterification of the alcohol with the carboxylic acid product.
  • Water may be fed separately or together with the alcohol or ester feed component or a mixture thereof.
  • the water may be present in liquid or vapour form.
  • the process of the present invention is carried out under hydrous conditions and the feed is an aliphatic alcohol or an aliphatic ester, the carbonylation reaction products will be the corresponding carboxylic acid and/or ester.
  • the reaction products will be acetic acid and/or methyl acetate.
  • the feed is a C 1 -C 3 alkyl ether, such as dimethyl ether
  • the carbonylation reaction is preferably carried out under substantially anhydrous conditions. In the substantial absence of water, the carbonylation of dimethyl ether is selective to methyl acetate product.
  • the catalyst and preferably, the feed components should be dried before beginning the operation, for example, by preheating to 400- 500 0 C.
  • the process is run at temperatures at or below about 250 0 C, that is, at temperatures of from about 100 to about 250 °C, preferably from about 150 to about 180 °C .
  • the process is run at temperatures above 250 0 C, that is, at temperatures of from about 250 to about 400 0 C, preferably from about 275 to about 350 0 C .
  • Typical total operating pressures are from about 1 bar to about 100 bar, preferably with carbon monoxide pressures greater than 10 bar and reactant pressures below 5 bar.
  • the process may be run as either a continuous or a batch process, with continuous processes typically preferred.
  • the process is a gas-phase operation, with reactants being introduced in either liquid or gaseous phase and products withdrawn as gases.
  • the reaction products may subsequently be cooled and condensed.
  • the catalyst may be used as convenient, in either a fixed bed or a fluidized bed.
  • unreacted starting materials may be recovered and recycled to the reactor.
  • the product is methyl acetate it may be recovered and sold as such, or may be forwarded to other chemical process units as desired.
  • the entire reaction product may be sent to a chemical process unit for conversion of the methyl acetate or acetic acid and optionally other components to other useful products.
  • methyl acetate is a product
  • it may be recovered from the reaction products and contacted with water to form acetic acid via hydrolysis reactions.
  • the entire product may be passed to a hydrolysis step, and acetic acid separated thereafter.
  • the hydrolysis step may be carried out in the presence of an acid catalyst, and may take the form of a reactive distillation process, well known in the art.
  • any alcohols produced in the reaction may be sent to a dehydration reactor to produce an ether, which can be separated from water and recycled to the carbonylation unit as fresh feed for the carbonylation reactor.
  • the hydrolysis of an ester product to alcohol and carboxylic acid is performed by injecting water at one or more points in the catalyst bed, once a significant amount of ester has been produced by carbonylation. Injection of water in this manner essentially stops the conversion of, for example, dimethyl ether to methyl acetate, and removes the requirement for a separate hydrolysis reactor.
  • a catalyst sample in the ammonium or acid form was compacted at 12 tonnes in a 33 mm die set using a Specac Press, then crushed and sieved to a particle size fraction of 212 to 335 microns.
  • the catalyst typically Ig
  • the temperature was increased from room temperature to 450 C C at a ramp rate of 5°C/min and then held at this temperature for 12 hours. Details of the zeolites are given in Table 1 below. Table 1
  • the sodium form of zeolite A was converted to the NH4 + form by stirring 1 gram of material in a 10 ml solution of 1 molar ammonium nitrate for three hours and then filtering off the solution. This was repeated three times and the solid dried at 100 0 C in air before pressing and sieving. The NH 4 + exchanged NaA was not calcined prior to use. Dimethyl Ether Carbonylation Reaction
  • the nitrogen gas feed was then changed to a mixture comprising 64 mole % carbon monoxide, 16 mole % hydrogen and 20 mole % nitrogen at a gas flow rate of 3.33 ml/ hour, and the system were heated at a ramp rate 3 0 C/ min. to a temperature of 300 0 C. The system was then held at this condition for 3 hours. After this the temperature was reduced to 180 0 C and allowed to stabilise for 10 minutes. At this point catalyst activation is considered complete and the gas feed was changed to a mixture comprising 64 mole % carbon monoxide, 16 mole % hydrogen, 15 mole % nitrogen and 5 mole % dimethyl ether at a gas flow rate of 3.33 ml/ hour.
  • the reaction was allowed to continue for 27.8 hours after which the temperature was increased to 250 0 C.
  • the exit stream from the reactor was passed to a Varian 4900 micro gas chromatograph with three columns (Molecular Sieve 5A, Porapak® Q and CP-Wax-52) each column being equipped with a thermal conductivity detector; and an Interscience Trace gas chromatograph having two columns (CP-SiI 5 and CP- Wax 52) each equipped with a flame ionization detector.
  • Table 2 The results of the carbonylation reactions are given in Table 2.
  • the offretite, chabazite, and ECR-18 zeolites have a silica : alumina molar ratio of at least 5, an 8-member ring channel of window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Bronsted acid site, and.the 8-member ring channel is interconnected with a channel defined by a ring with greater than or equal to 8 members.
  • ZSM-23, Theta-1, Zeolite-A, Zeolite-L, Mazzite and Beta-18 little, if any carbonylation activity was found to occur.
  • ZSM-23, and Theta-1 possess 10-member ring channels only and do not have 8-member ring channels; Beta-18 and Zeolite-L have 12-member ring channels only and does not have 8-member ring channels; the Zeolite-A has 8- member ring channels but its silica/alumina ratio is below 5;
  • Mazzite has both 8- and 12-member ring channels but the 8-member ring channels do not intersect with either 8-member ring channels or 12- member ring channels.
  • zeolites can be tested in a pressure flow reactor in accordance with the following procedure.
  • Zeolite pellets of size 500-lOOOum are loaded into a pressure flow reactor.
  • a catalyst pre-bed is also employed to ensure efficient mixing/heating of the reactants.
  • the pre-bed is gamma-alumina which allows methanol to form a methanol/dimethylether/water equilibrium.
  • the catalysts are activated under flowing nitrogen (100cm3/min) at 350 0 C for 16hrs and then reduced under carbon monoxide (200cm3/min) at 350 0 C for 2 hours.
  • the system is then pressurised up to 30barg using a back pressure regulator.
  • the liquid products and unconverted reactants are collected in a cooled trap, while gaseous products and un-reacted feeds are sampled downstream by an online gas chromatograph.
  • the reaction is sampled at frequent intervals and the liquid products analysed off line using gas-chromatography.
  • zeolite H-Offretite (silica : alumina molar ratio of 10) as the catalyst in the above described carbonylation of methanol, it would be expected that significant amounts of both methyl acetate and acetic acid would be seen in the liquid products.
  • zeolite H-Gmelinite (silica : alumina molar ratio of 8) was employed as the catalyst in the above described carbonylation of methanol, it would be expected that significant amounts of both methyl acetate and acetic acid would be seen in the liquid products.
  • Both offretite and gmelinite zeolites have 8-member ring channels intersecting with 12-member ring channels.

Abstract

Un produit comprenant un acide carboxylique aliphatique en C1 à C3 ou un ester correspondant est produit par un procédé comprenant la réaction d'un alcool aliphatique en C1 à C3 ou de l'un de ses dérivés réactifs avec du monoxyde de carbone en présence d'un catalyseur de zéolite présentant un canal cyclique à 8 chaînons qui est interconnecté avec un canal défini par un cycle à 8 chaînons ou plus, le cycle à 8 chaînons présentant une taille de fenêtre d'au moins 2,5 Angströms x, au moins 3,6 Angströms et au moins un site d'acide de Bronsted et la zéolite présentant un rapport de silice / X2O3 d'au moins 5, X étant choisi parmi l'aluminium, le bore, le fer, le gallium et leurs mélanges à condition que la zéolite ne soit pas de la mordénite ou de la ferriérite.
PCT/US2006/047718 2006-12-15 2006-12-15 Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs WO2008073096A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP06845427A EP2114850A4 (fr) 2006-12-15 2006-12-15 Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs
CA2671361A CA2671361C (fr) 2006-12-15 2006-12-15 Procede de carbonylation d'alcools aliphatiques et/ou de leurs derives reactifs
UAA200907279A UA95663C2 (uk) 2006-12-15 2006-12-15 Спосіб одержання с1-с3-аліфатичної карбонової кислоти й/або відповідного складного ефіру шляхом карбонілювання
PCT/US2006/047718 WO2008073096A1 (fr) 2006-12-15 2006-12-15 Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs
CN2006800566291A CN101600678B (zh) 2006-12-15 2006-12-15 脂肪醇和/或其反应性衍生物羰基化的方法
KR1020097012298A KR20090092280A (ko) 2006-12-15 2006-12-15 지방족 알코올 및/또는 이의 반응성 유도체의 카르보닐화 방법
KR1020147009999A KR20140054448A (ko) 2006-12-15 2006-12-15 지방족 알코올 및/또는 이의 반응성 유도체의 카르보닐화 방법
JP2009541278A JP2010513270A (ja) 2006-12-15 2006-12-15 脂肪族アルコール及び／又はその反応性誘導体のカルボニル化方法
BRPI0622186-6A BRPI0622186A2 (pt) 2006-12-15 2006-12-15 processo para carbonilaÇço de alcoàis alifÁticos e/ou de derivados reativos dos mesmos

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KR (2) KR20090092280A (fr)
CN (1) CN101600678B (fr)
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CA (1) CA2671361C (fr)
UA (1) UA95663C2 (fr)
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RU2658005C2 (ru) * 2013-03-08 2018-06-19 Бп Кемикэлз Лимитед Способ карбонилирования
US20180201567A1 (en) * 2015-07-20 2018-07-19 Dallian Institute of Chemical Phisics, Chinese Academy of Sciences Method for preparing acetal carbonyl compound
EP3326994A4 (fr) * 2015-07-20 2018-08-01 Dalian Institute of Chemical Physics, Chinese Academy of Sciences Procédé de production d'ester d'alkyle d'acide carboxylique gras inférieur
US11427524B2 (en) 2017-08-24 2022-08-30 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product
US11673851B2 (en) 2017-08-24 2023-06-13 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product

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RU2658005C2 (ru) * 2013-03-08 2018-06-19 Бп Кемикэлз Лимитед Способ карбонилирования
US20180201567A1 (en) * 2015-07-20 2018-07-19 Dallian Institute of Chemical Phisics, Chinese Academy of Sciences Method for preparing acetal carbonyl compound
EP3326994A4 (fr) * 2015-07-20 2018-08-01 Dalian Institute of Chemical Physics, Chinese Academy of Sciences Procédé de production d'ester d'alkyle d'acide carboxylique gras inférieur
US10087135B2 (en) * 2015-07-20 2018-10-02 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Lower fatty carboxylic acid alkyl ester production method
US10508073B2 (en) * 2015-07-20 2019-12-17 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing acetal carbonyl compound
US11427524B2 (en) 2017-08-24 2022-08-30 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product
US11673851B2 (en) 2017-08-24 2023-06-13 Bp P.L.C. Process for dehydrating methanol to dimethyl ether product

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EP2114850A1 (fr) 2009-11-11
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BRPI0622186A2 (pt) 2011-12-27
CN101600678B (zh) 2012-08-15
KR20090092280A (ko) 2009-08-31
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JP2010513270A (ja) 2010-04-30
CA2671361C (fr) 2014-10-21
CA2671361A1 (fr) 2008-06-19
CN101600678A (zh) 2009-12-09

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