US20060252959A1 - Process for carbonylation of alkyl ethers - Google Patents

Process for carbonylation of alkyl ethers Download PDF

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Publication number
US20060252959A1
US20060252959A1 US11/123,581 US12358105A US2006252959A1 US 20060252959 A1 US20060252959 A1 US 20060252959A1 US 12358105 A US12358105 A US 12358105A US 2006252959 A1 US2006252959 A1 US 2006252959A1
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United States
Prior art keywords
process according
catalyst
alkyl groups
methyl acetate
mordenite
Prior art date
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Abandoned
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US11/123,581
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English (en)
Inventor
Patricia Cheung
Enrique Iglesia
John Sunley
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BP Chemicals Ltd
University of California
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BP Chemicals Ltd
University of California
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Priority to US11/123,581 priority Critical patent/US20060252959A1/en
Assigned to BP CHEMICALS LIMITED reassignment BP CHEMICALS LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUNLEY, JOHN GLENN
Assigned to THE REGENTS OF THE UNIVERSITY OF CALIFORNIA reassignment THE REGENTS OF THE UNIVERSITY OF CALIFORNIA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEUNG, PATRICIA, INGLESIA, ENRIQUE
Priority to KR1020137015131A priority patent/KR20130079649A/ko
Priority to PCT/US2006/017219 priority patent/WO2006121778A1/fr
Priority to US11/417,415 priority patent/US7309798B2/en
Priority to EP06752246.6A priority patent/EP1877361B1/fr
Priority to BRPI0611385A priority patent/BRPI0611385B1/pt
Priority to RU2007145050/04A priority patent/RU2411232C2/ru
Priority to JP2008510219A priority patent/JP4796134B2/ja
Priority to CN2006800152239A priority patent/CN101203479B/zh
Priority to UAA200713604A priority patent/UA89674C2/ru
Priority to KR1020077028345A priority patent/KR101300895B1/ko
Priority to CA2605017A priority patent/CA2605017C/fr
Priority to TW095115878A priority patent/TWI304806B/zh
Priority to MYPI20062083A priority patent/MY137639A/en
Publication of US20060252959A1 publication Critical patent/US20060252959A1/en
Priority to US11/639,420 priority patent/US7465822B2/en
Priority to NO20075595A priority patent/NO20075595L/no
Abandoned legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds

Definitions

  • This invention 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.
  • methanol is reacted with carbon monoxide or a carbon monoxide-containing gas in the presence of a rhodium- or iridium-containing catalyst, in the additional presence of a halogen (usually iodine)-containing promoter.
  • Methyl acetate is an important compound used industrially in petrochemical processes, particularly as a feed for the production of acetic anhydride and/or acetic acid. Methyl acetate can also be used for the production of ethylidene diacetate, a precursor to vinyl acetate and polyvinyl acetate. Dimethyl ether may be readily produced from synthesis gas, and the cost of its production can be lower than that of methanol.
  • a number of patents describe processes in which methanol or a mixture of methanol and dimethyl ether is carbonylated in the presence of a catalyst.
  • the products are a mixture of acetic acid and methyl acetate, sometimes also including acetic anhydride.
  • one of the reactions that may occur is the carbonylation of dimethyl ether to form methyl acetate.
  • dimethyl ether is not used as the sole or even as the primary component of the feed, but as a minor component in methanol streams.
  • German OLS 3,606,169 of BASF AG discloses carbonylation of a mixture of methanol, methyl acetate and/or dimethyl ether to produce a product containing acetic acid, methyl acetate and/or dimethyl ether in the presence of a cobalt-containing zeolite catalyst.
  • the preferred zeolites are those of the 10-ring pentasil type with pore sizes intermediate between those of 8-ring zeolite A and those of 12-ring zeolites X and Y.
  • J Wegman (U.S. Pat. No. 5,218,140) experimented primarily with the carbonylation of methanol to produce acetic acid using heteropolyacid catalysts.
  • the patent contains a group of experiments in which the feed was dimethyl ether (Examples 28-33); however, in those experiments the conversion to methyl acetate was relatively low.
  • Sardesai et al. ( Energy Sources 2002, 24:301) also carried out carbonylation of dimethyl ether with a number of heteropoly acid catalysts, which gave results that varied widely in terms of conversion and selectivity to methyl acetate.
  • Bagno et al. ( J. Org. Chem. 1990, 55:4284) ran such a reaction with so-called “super-acid” catalysts including BF 3 and triflic acid, again with varying results as to selectively to methyl acetate.
  • this invention comprises a process for producing a product comprising a lower alkyl ester of a lower aliphatic carboxylic acid comprising reacting a lower alkyl ether with carbon monoxide in the presence of a catalyst comprising mordenite and/or ferrierite under substantially anhydrous conditions.
  • the invention herein comprises a process for producing methyl acetate by reaction of dimethyl ether with carbon monoxide in the presence of a catalyst comprising mordenite and/or ferrierite, under substantially anhydrous conditions.
  • FIG. 1 depicts formation rates of methyl acetate using various zeolites as catalyst candidates for the process of this invention.
  • FIG. 2 depicts the formation rate of acetic acid using an H-mordenite zeolite catalyst for the process of this invention.
  • FIG. 3 depicts the formation rate of methanol using an H-mordenite zeolite catalyst for the process of this invention.
  • FIG. 4 depicts the formation rate of hydrocarbons using an H-mordenite zeolite catalyst for the process of this invention.
  • FIG. 5 depicts calculated product selectivities.
  • FIG. 6 depicts the formation rate of methyl acetate using H-mordenite zeolite catalyst in the presence (and absence) of hydrogen in the reactant mixture.
  • this invention comprises a process for producing a product comprising a lower alkyl ester of a lower aliphatic carboxylic acid comprising reacting a lower alkyl ether with carbon monoxide in the presence of a catalyst comprising mordenite or ferrierite, under substantially anhydrous conditions.
  • the invention herein comprises a process for producing methyl acetate by reaction of dimethyl ether with carbon monoxide in the presence of a catalyst comprising mordenite or ferrierite, under substantially anhydrous conditions.
  • One component of the feed to the process comprises (primarily) a lower 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 6 alkyl groups or R 1 +R 2 together form a C 2 -C 6 alkylene group.
  • the total number of carbon atoms in groups R 1 and R 2 if R 1 and R 2 are alkyl groups, is from 2 to 12, preferably from 2 to 8, most preferably from 2 to 6.
  • R 1 and R 2 are straight-chain alkyl groups, most preferably straight-chain alkyl groups having from 1 to 3 carbon atoms each. If R 1 +R 2 form an alkylene group (i.e., the ether is a cyclic ether), the total number of carbon atoms is preferably from 2 to 4.
  • reaction overall can be depicted as R 1 —O—R 2 +CO ⁇ R 1 COOR 2
  • alkyl as used herein means a straight or branched chain, or cyclic, saturated aliphatic group, or a combination thereof, that has the number of carbon atoms designated (i.e. C 3 means three carbon atoms).
  • acyclic alkyl groups include groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, and the various pentyl and hexyl isomers.
  • Examples of cyclical alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Combinations of cyclical and acyclic alkyl groups include, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopropylethyl, etc.
  • alkylene refers to saturated aliphatic moieties that may form two single bonds with other moieties. This group includes, for example, methylene (—CH 2 —), ethylene (—CH 2 CH 2 —) and hexylene [(—CH 2 —) 6 ]. While alkylene groups may be straight or branched chain groups, straight-chain alkylene groups are preferred for use in the processes of this invention.
  • 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.
  • 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 fee 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 ability to use synthesis gas provides another advantage over processes for producing acetic acid from methanol, namely the option of using a less expensive carbon monoxide feed. In methanol-to-acetic acid processes, the inclusion of hydrogen in the feed can result in production of unwanted hydrogenation byproducts; accordingly the feed should be high-purity carbon monoxide.
  • the catalyst is composed of mordenite or ferrierite, or mixtures or combinations of the two, either per se (i.e., in the acid form, generally referred to as H-mordenite and H-ferrierite), or optionally ion-exchanged or loaded with one or more metals such as copper, nickel, iridium, rhodium, platinum, palladium, or cobalt.
  • Mordenite (sometimes referred to as H-mordenite) is a member of the aluminosilicate zeolite class of minerals. Its formula is usually given as Na(AlSi 5 O 12 ).3H 2 O or (Na 2 ,Ca,K 2 )Al 2 Si 10 O 24 .7H 2 O. It is available from a number of commercial sources of such materials. Ferrierite is another member of the aluminosilicate zeolite class of minerals, with a formula generally given as Na 0.8 K 0.2 MgSi 15 Al 3 O 36 .9H 2 O or (Mg,Na 2 ,K 2 ,Ca) 3-5 Mg[Al 5-7 Si 27.5-31 O 72 ].18H 2 O. It, too, is available from various commercial sources. Additional information on these materials can be found on the website of the International Zeolite Association, www.iza-online.org.
  • the catalyst should be dried before beginning the operation, for example, by preheating to 400-500° C.
  • the process is run at temperatures at or below about 250° C., that is, at temperatures of from about 100 to about 250° C., preferably from about 150 to about 180° C.
  • One feature of the process is that, surprisingly, the carbonylation of dimethyl ether (DME) to methyl acetate using mordenite zeolite based catalysts and in the substantial absence of water can be performed with very high selectivities at temperatures significantly lower than those cited in the prior art for methanol carbonylation. Additionally, under these conditions the mordenite is essentially inactive for the carbonylation of methanol. Reaction temperatures are kept within the above range also to minimize the dehydration of any methanol that may be present to form hydrocarbons and water, because the presence of water strongly inhibits the carbonylation of dimethyl ether to methyl acetate.
  • Typical operating pressures are from about 1 bar to about 100 bar, preferably with carbon monoxide pressures greater than 10 bar and dimethyl ether pressures below 5 bar.
  • the process is run under substantially anhydrous conditions, i.e. in the substantial absence of water.
  • Water has been found to inhibit the carbonylation of dimethyl ether to form methyl acetate. This is in comparison to prior art processes in which dimethyl ether was a co-feed, and in which water was also fed to the reaction. Water is thus kept as low as feasible, in order to allow the desired reaction to proceed best.
  • the ether and carbon monoxide reactants and the catalyst are preferably dried prior to introduction into the process.
  • 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 methyl acetate may be recovered and sold as such, or may be forwarded to other chemical process units as desired. If desired, the entire reaction product may be sent to a chemical process unit for conversion of the methyl acetate and optionally other components to other useful products.
  • the methyl acetate is 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.
  • alcohols produced in the hydrolysis reactor 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 the 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 dimethyl ether to methyl acetate, and removes the requirement for a separate hydrolysis reactor.
  • the mordenite or ferrierite catalyst thus may also function as the acid catalyst for the hydrolysis of the ester product to give a carboxylic acid. If the reactor is a fluidized bed reactor, with back-mixing, then the reactor and catalyst will then have to be thoroughly dried before they are again used for the main process. If, on the other hand, the reactor is a tubular reactor, with staged introduction of water downstream of the main reaction zone, such drying should not be necessary.
  • conversions can be up to 100%, preferably from about 10% to about 100%, depending on the space velocity and reactant pressures used.
  • Selectivity to methyl acetate has been shown to be constant, at values greater than 99% at 165° C. for over 10 hours. At 190° C., selectivities to methyl acetate ate initially 96%, but decrease with time on stream.
  • Such results are unexpected with the use of mordenite, and maintenance of a substantially anhydrous environment, as the prior art indicates that mordenite typically must be used for the conversion of methanol to acetic acid at temperatures substantially higher than 250° C. Such temperatures also can lead to deactivation of methanol carbonylation die to the formation of hydrocarbons, which can block catalyst pores and/or active sites.
  • experiments with other zeolites under similar conditions do not show the desired conversion and/or selectivity as mordenite and ferrierite.
  • Catalysts were obtained commercially in the ammonium or acid form and pretreated in flowing dry air at 773 K for 3 hours.
  • Dimethyl ether carbonylation reactions were carried out in a fixed-bed stainless steel microreactor using 0.15-0.5 g catalyst. Catalysts were activated at 773 K in flowing dry air for 2 hours, cooled to reaction temperatures (150-240° C.), flushed with flowing dry helium, and pressurized to 10 bar before introducing reactants.
  • Heat-traced lines (200-250° C.) were used to transfer the reactants and products to an on-line gas chromatograph (Agilent 6890) equipped with flame ionization and thermal conductivity detectors with methyl siloxane and Porapak® Q columns, respectively.
  • FIGS. 2 and 3 show acetic acid and methanol formation rates on H-MOR.
  • Acetic acid forms via methyl acetate hydrolysis or methanol carbonylation at temperatures ⁇ 490 K on H-MOR.
  • Methanol cannot form from dimethyl ether in the absence of water, which may be formed, however, as a by-product of MTG (methane-to-gasoline) reactions.
  • the initial methanol formation rates reflect reactions of either residual water or of water formed from hydroxyl groups remaining in zeolites after catalyst pre-treatment (drying) at 500° C. Therefore, when detectable steady-state methanol rates are observed above 463 K, hydrocarbons are presumably being formed, even if they are not detected in the effluent by gas chromatography.
  • Hydrocarbon formation rates (calculated as the dimethyl ether converted to products other than methyl acetate, acetic acid, or methanol) on H-MOR are shown in FIG. 4 . No acetic acid was observed on the other zeolites. Product selectivities are shown in FIG. 5 .
  • the lower carbonylation activity (per Al) is not completely unexpected for this material because it shows higher hydrocarbon formation rates.
  • Methanol (and DME)-to-hydrocarbon reactions form water in stoichiometric amounts; our studies have shown the requirement of anhydrous conditions for carbonylation activity. A dry environment is not possible in the presence of concurrent reactions that form hydrocarbons.
  • H-Mordenite was evaluated for dimethyl ether carbonylation in the presence of hydrogen. Carbonylation rates are essentially unaffected by the presence of hydrogen as one-half of the total reactant feedstock ( FIG. 6 ). Synthesis gas of various hydrogen:carbon monoxide ratios can be utilized without affecting dimethyl ether carbonylation rates.
US11/123,581 2005-05-05 2005-05-05 Process for carbonylation of alkyl ethers Abandoned US20060252959A1 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US11/123,581 US20060252959A1 (en) 2005-05-05 2005-05-05 Process for carbonylation of alkyl ethers
CA2605017A CA2605017C (fr) 2005-05-05 2006-05-03 Procede de carbonylation d'ethers alcoyliques
PCT/US2006/017219 WO2006121778A1 (fr) 2005-05-05 2006-05-03 Procede de carbonylation d'ethers alcoyliques
JP2008510219A JP4796134B2 (ja) 2005-05-05 2006-05-03 アルキルエーテルのカルボニル化のための方法
KR1020077028345A KR101300895B1 (ko) 2005-05-05 2006-05-03 알킬 에테르의 카보닐화 방법
US11/417,415 US7309798B2 (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers
EP06752246.6A EP1877361B1 (fr) 2005-05-05 2006-05-03 Procede de carbonylation d'ethers alcoyliques
BRPI0611385A BRPI0611385B1 (pt) 2005-05-05 2006-05-03 processo para carbonilação de éteres de alquila
RU2007145050/04A RU2411232C2 (ru) 2005-05-05 2006-05-03 Способ карбонилирования простых алкиловых эфиров
KR1020137015131A KR20130079649A (ko) 2005-05-05 2006-05-03 알킬 에테르의 카보닐화 방법
CN2006800152239A CN101203479B (zh) 2005-05-05 2006-05-03 烷基醚羰基化方法
UAA200713604A UA89674C2 (ru) 2005-05-05 2006-05-03 Способ получения продукта, который содержит эстер низшего алкила и низшей карбоновой кислоты
TW095115878A TWI304806B (en) 2005-05-05 2006-05-04 Process for carbonylation of alkyl ethers
MYPI20062083A MY137639A (en) 2005-05-05 2006-05-05 Process for carbonylation of alkyl ethers
US11/639,420 US7465822B2 (en) 2005-05-05 2006-12-15 Process for carbonylation of alkyl ethers
NO20075595A NO20075595L (no) 2005-05-05 2007-11-05 Fremgangsmate for karbonylering av alkyletere

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US11/417,415 Active US7309798B2 (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers

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EP (1) EP1877361B1 (fr)
JP (1) JP4796134B2 (fr)
KR (2) KR20130079649A (fr)
CN (1) CN101203479B (fr)
BR (1) BRPI0611385B1 (fr)
CA (1) CA2605017C (fr)
MY (1) MY137639A (fr)
NO (1) NO20075595L (fr)
RU (1) RU2411232C2 (fr)
TW (1) TWI304806B (fr)
UA (1) UA89674C2 (fr)
WO (1) WO2006121778A1 (fr)

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WO2008073096A1 (fr) 2006-12-15 2008-06-19 The Regents Of The University Of California Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs
EP2072491A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'alcool(s) en alcool(s) avec une chaîne de carbone prolongée
EP2072492A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'hydrocarbure en éthanol
EP2072490A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'hydrocarbure en alcool
US20100063315A1 (en) * 2007-04-26 2010-03-11 Evert Jan Ditzel Process for the carbonylation of dimethyl ether
US20100130771A1 (en) * 2007-04-26 2010-05-27 Bp Chemicals Limited Process for the carbonylation of dimethyl ether
WO2010061169A1 (fr) * 2008-11-27 2010-06-03 Bp Chemicals Limited Procédé de carbonylation pour la production d'acétate de méthyle
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RU2478609C2 (ru) * 2007-04-26 2013-04-10 Бп Кемикэлз Лимитед Способ карбонилирования диметилового эфира
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WO2014096249A1 (fr) * 2012-12-21 2014-06-26 Bp Chemicals Limited Procédé intégré pour la production de méthanol et d'acétate de méthyle
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SG11201507102VA (en) * 2013-03-08 2015-10-29 Bp Chem Int Ltd Process for the carbonylation of dimethyl ether
JP5918190B2 (ja) * 2013-10-05 2016-05-18 ザ レジェンツ オブ ザ ユニバーシティ オブ カリフォルニア 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
CN106365995B (zh) * 2015-07-20 2018-06-05 中国科学院大连化学物理研究所 一种乙酸甲酯的生产方法
WO2017102284A1 (fr) 2015-12-18 2017-06-22 Bp Chemicals Limited Procédé de carbonylation faisant appel à un catalyseur zéolite prétraité
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ES2718747T3 (es) 2016-07-19 2019-07-04 Evonik Degussa Gmbh Procedimiento para la alcoxicarbonilación de éteres
CN106311336B (zh) * 2016-08-11 2019-02-15 西南化工研究设计院有限公司 二甲醚羰基化制醋酸甲酯的方法及其改性分子筛催化剂和改性方法
GB201705882D0 (en) 2017-04-12 2017-05-24 Bp Chem Int Ltd Process
CN111822041B (zh) * 2019-04-15 2021-11-09 中国科学院大连化学物理研究所 一种复合催化剂、其制备方法及其应用
WO2022132843A1 (fr) * 2020-12-16 2022-06-23 The Regents Of The University Of California Prétraitement de catalyseurs d'oxyde métallique pour la déshydrogénation d'alcanes
KR102536204B1 (ko) 2023-02-14 2023-05-30 고등기술연구원연구조합 무포집형 저농도 이산화탄소 활용 플랫폼화합물 생산 기술

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689533A (en) * 1971-03-15 1972-09-05 Monsanto Co Production of carboxylic acids and esters
US4612387A (en) * 1982-01-04 1986-09-16 Air Products And Chemicals, Inc. Production of carboxylic acids and esters
US5189203A (en) * 1987-06-30 1993-02-23 Haldor Topsoe A/S Process for preparing acetic acid, methyl acetate, acetic anhydride or mixtures thereof
US5218140A (en) * 1988-08-02 1993-06-08 Union Carbide Chemicals & Plastics Technology Corporation Carbonylation reaction and catalyst therefor
US5728871A (en) * 1996-04-10 1998-03-17 Haldor Topsoe A/S Process for the preparation of acetic acid
US5763654A (en) * 1995-10-20 1998-06-09 Bp Chemicals Limited Process for the production of acetic acid by the carbonylation of dimethyl ether
US6130355A (en) * 1998-01-31 2000-10-10 Bp Chemicals Limited Anhydrous carbonylation process for the production of acetic acid
US6353132B1 (en) * 1999-08-25 2002-03-05 Eastman Chemical Company Vapor phase carbonylation process using group 5 metal promoted iridium catalyst
US6355837B1 (en) * 1999-08-25 2002-03-12 Eastman Chemical Company Vapor phase carbonylation process using group 4 metal promoted iridium catalyst
US6387842B1 (en) * 1998-01-29 2002-05-14 Union Carbide Chemicals & Plastics Technology Corporation Process for preparing oxygenates and catalysts therefor
US6521783B1 (en) * 1998-01-29 2003-02-18 Union Carbide Chemicals & Plastics Technology Corporation Processes for preparing oxygenates
US20030054951A1 (en) * 2001-06-20 2003-03-20 Joseph Zoeller Tin promoted iridium catalyst for carbonylation of lower alkyl alcohols

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3031007A (en) * 1960-08-29 1962-04-24 Mine Safety Appliances Co Pipe flaring tool
US3130007A (en) 1961-05-12 1964-04-21 Union Carbide Corp Crystalline zeolite y
GB1185453A (en) 1967-02-20 1970-03-25 Monsanto Co Multiphase Catalysis.
US3717670A (en) 1968-08-02 1973-02-20 Monsanto Co Production of carboxylic acids and esters
CA1064890A (fr) * 1975-06-10 1979-10-23 Mae K. Rubin Synthese et utilisation de la zeolite cristalline
NZ195461A (en) 1979-11-27 1983-06-14 British Petroleum Co Producing oxygenated hydrocarbon product containing ethanol
DE3606169A1 (de) 1986-02-26 1987-08-27 Basf Ag Verfahren zur herstellung von essigsaeure, methylacetat und/oder dimethylether
GB9008038D0 (en) 1990-04-09 1990-06-06 Univ Manchester Gallium zeolites
CA2093752C (fr) 1992-04-15 1999-06-15 David W. Studer Procede integre pour la preparation de composes acetyles oxygenes a partir de gaz de synthese via l'oxyde de dimethyle
CA2093747C (fr) 1992-04-15 1999-06-15 Francis J. Waller Methode pour convertir de l'oxyde de dimethyle en diacetate d'ethylidene
GB9223170D0 (en) 1992-11-05 1992-12-16 British Petroleum Co Plc Process for preparing carboxylic acids
GB0404793D0 (en) 2004-03-03 2004-04-07 Bp Chem Int Ltd Process
GB0409490D0 (en) * 2004-04-28 2004-06-02 Bp Chem Int Ltd Process

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689533A (en) * 1971-03-15 1972-09-05 Monsanto Co Production of carboxylic acids and esters
US4612387A (en) * 1982-01-04 1986-09-16 Air Products And Chemicals, Inc. Production of carboxylic acids and esters
US5189203A (en) * 1987-06-30 1993-02-23 Haldor Topsoe A/S Process for preparing acetic acid, methyl acetate, acetic anhydride or mixtures thereof
US5286900A (en) * 1987-06-30 1994-02-15 Haldor Topsoe A/S Process for preparing acetic acid, methyl acetate, acetic anhydride or mixtures thereof
US5218140A (en) * 1988-08-02 1993-06-08 Union Carbide Chemicals & Plastics Technology Corporation Carbonylation reaction and catalyst therefor
US5763654A (en) * 1995-10-20 1998-06-09 Bp Chemicals Limited Process for the production of acetic acid by the carbonylation of dimethyl ether
US5728871A (en) * 1996-04-10 1998-03-17 Haldor Topsoe A/S Process for the preparation of acetic acid
US6387842B1 (en) * 1998-01-29 2002-05-14 Union Carbide Chemicals & Plastics Technology Corporation Process for preparing oxygenates and catalysts therefor
US6521783B1 (en) * 1998-01-29 2003-02-18 Union Carbide Chemicals & Plastics Technology Corporation Processes for preparing oxygenates
US6130355A (en) * 1998-01-31 2000-10-10 Bp Chemicals Limited Anhydrous carbonylation process for the production of acetic acid
US6353132B1 (en) * 1999-08-25 2002-03-05 Eastman Chemical Company Vapor phase carbonylation process using group 5 metal promoted iridium catalyst
US6355837B1 (en) * 1999-08-25 2002-03-12 Eastman Chemical Company Vapor phase carbonylation process using group 4 metal promoted iridium catalyst
US20030054951A1 (en) * 2001-06-20 2003-03-20 Joseph Zoeller Tin promoted iridium catalyst for carbonylation of lower alkyl alcohols

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008073096A1 (fr) 2006-12-15 2008-06-19 The Regents Of The University Of California Procédé de carbonylation d'alcools aliphatiques et/ou de leurs dérivés réactifs
RU2458909C2 (ru) * 2006-12-15 2012-08-20 Дзе Риджентс Оф Дзе Юниверсити Оф Калифорния Способ карбонилирования алифатических спиртов и/или их реакционноспособных производных
CN101600678B (zh) * 2006-12-15 2012-08-15 加州大学评议会 脂肪醇和/或其反应性衍生物羰基化的方法
US20100130771A1 (en) * 2007-04-26 2010-05-27 Bp Chemicals Limited Process for the carbonylation of dimethyl ether
US8283490B2 (en) * 2007-04-26 2012-10-09 Bp Chemicals Limited Process for the carbonylation of dimethyl ether
US8536369B2 (en) 2007-04-26 2013-09-17 Bp Chemicals Limited Process for the carbonylation of dimethyl ether
RU2478609C2 (ru) * 2007-04-26 2013-04-10 Бп Кемикэлз Лимитед Способ карбонилирования диметилового эфира
US20100063315A1 (en) * 2007-04-26 2010-03-11 Evert Jan Ditzel Process for the carbonylation of dimethyl ether
US8394983B2 (en) * 2007-04-26 2013-03-12 Bp Chemicals Limited Process for the carbonylation of dimethyl ether
RU2473535C2 (ru) * 2007-04-26 2013-01-27 Бп Кемикэлз Лимитед Способ карбонилирования диметилового эфира
RU2469018C2 (ru) * 2007-04-26 2012-12-10 Бп Кемикэлз Лимитед Способ карбонилирования диметилового эфира
EA016785B1 (ru) * 2007-12-17 2012-07-30 Бп П.Л.К. Способ превращения спирта (спиртов) в спирт (спирты) с более длинной углеродной цепью
EP2072490A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'hydrocarbure en alcool
US20100317900A1 (en) * 2007-12-17 2010-12-16 Berian John Daniel Process for the conversion of alcohol (s) into alcohol (s) with increased carbon-chain
WO2009077726A1 (fr) 2007-12-17 2009-06-25 Bp P.L.C. Procédé permettant de convertir des alcools en des alcools possédant une chaîne à nombre de carbones augmenté
EP2072492A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'hydrocarbure en éthanol
EP2072491A1 (fr) * 2007-12-17 2009-06-24 BP p.l.c. Processus de conversion d'alcool(s) en alcool(s) avec une chaîne de carbone prolongée
WO2009077720A1 (fr) * 2007-12-17 2009-06-25 Bp P.L.C. Processus de production d'alcool à partir d'une charge carbonée
WO2009077730A1 (fr) * 2007-12-17 2009-06-25 Bp P.L.C. Procédé permettant de produire des alcools à partir d'une charge d'alimentation carbonée
US8378156B2 (en) 2007-12-17 2013-02-19 Bp P.L.C. Process for the conversion of alcohol (s) into alcohol (s) with increased carbon-chain
US20100274045A1 (en) * 2007-12-19 2010-10-28 Bp Chemicals Limited Carbonylation process for the production of methyl acetate
US8431732B2 (en) * 2007-12-19 2013-04-30 Bp Chemicals Limited Carbonylation process for the production of methyl acetate
WO2010061169A1 (fr) * 2008-11-27 2010-06-03 Bp Chemicals Limited Procédé de carbonylation pour la production d'acétate de méthyle
EP2199272A1 (fr) * 2008-11-27 2010-06-23 BP Chemicals Limited Procédé de carbonylation
US8624054B2 (en) 2008-11-27 2014-01-07 Bp Chemicals Limited Carbonylation process for the production of methyl acetate
US20100170319A1 (en) * 2009-01-06 2010-07-08 Soren Wiberg Method for press hardening of metals
KR101431328B1 (ko) 2012-10-08 2014-08-20 성균관대학교산학협력단 페리어라이트 촉매를 사용하는 합성가스로부터 에탄올의 제조방법
WO2014096249A1 (fr) * 2012-12-21 2014-06-26 Bp Chemicals Limited Procédé intégré pour la production de méthanol et d'acétate de méthyle
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US9469591B2 (en) 2012-12-21 2016-10-18 Bp Chemicals Limited Integrated process for the production of methanol and methyl acetate
US9546120B2 (en) 2012-12-21 2017-01-17 Bp Chemicals Limited Integrated process for the production of methanol and methyl acetate
RU2686734C2 (ru) * 2012-12-21 2019-04-30 Бп Кемикэлз Лимитед Объединенный способ получения метилацетата и метанола из синтез-газа и диметилового эфира
RU2686701C2 (ru) * 2012-12-21 2019-04-30 Бп Кемикэлз Лимитед Объединенный способ получения метанола и метилацетата
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BRPI0611385A2 (pt) 2010-09-08
EP1877361B1 (fr) 2015-09-09
KR20130079649A (ko) 2013-07-10
TW200706532A (en) 2007-02-16
KR20090004395A (ko) 2009-01-12
UA89674C2 (ru) 2010-02-25
CN101203479A (zh) 2008-06-18
CN101203479B (zh) 2011-06-15
MY137639A (en) 2009-02-27
US7309798B2 (en) 2007-12-18
RU2411232C2 (ru) 2011-02-10
TWI304806B (en) 2009-01-01
JP2008540444A (ja) 2008-11-20
WO2006121778A1 (fr) 2006-11-16
BRPI0611385B1 (pt) 2016-02-10
CA2605017C (fr) 2013-07-23
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JP4796134B2 (ja) 2011-10-19
US20060287551A1 (en) 2006-12-21

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