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
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Abandoned
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US11/123,581
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English (en)
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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 EP06752246.6A priority patent/EP1877361B1/en
Priority to BRPI0611385A priority patent/BRPI0611385B1/pt
Priority to JP2008510219A priority patent/JP4796134B2/ja
Priority to CA2605017A priority patent/CA2605017C/en
Priority to KR1020077028345A priority patent/KR101300895B1/ko
Priority to CN2006800152239A priority patent/CN101203479B/zh
Priority to KR1020137015131A priority patent/KR20130079649A/ko
Priority to US11/417,415 priority patent/US7309798B2/en
Priority to UAA200713604A priority patent/UA89674C2/ru
Priority to RU2007145050/04A priority patent/RU2411232C2/ru
Priority to PCT/US2006/017219 priority patent/WO2006121778A1/en
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.

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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
PCT/US2006/017219 WO2006121778A1 (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers
BRPI0611385A BRPI0611385B1 (pt) 2005-05-05 2006-05-03 processo para carbonilação de éteres de alquila
KR1020137015131A KR20130079649A (ko) 2005-05-05 2006-05-03 알킬 에테르의 카보닐화 방법
RU2007145050/04A RU2411232C2 (ru) 2005-05-05 2006-05-03 Способ карбонилирования простых алкиловых эфиров
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
CA2605017A CA2605017C (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers
KR1020077028345A KR101300895B1 (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
EP06752246.6A EP1877361B1 (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers
US11/417,415 US7309798B2 (en) 2005-05-05 2006-05-03 Process for carbonylation of alkyl ethers
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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EP (1) EP1877361B1 (zh)
JP (1) JP4796134B2 (zh)
KR (2) KR20130079649A (zh)
CN (1) CN101203479B (zh)
BR (1) BRPI0611385B1 (zh)
CA (1) CA2605017C (zh)
MY (1) MY137639A (zh)
NO (1) NO20075595L (zh)
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WO2008073096A1 (en) 2006-12-15 2008-06-19 The Regents Of The University Of California Process for carbonylation of aliphatic alcohols and/or reactive derivatives thereof
EP2072491A1 (en) * 2007-12-17 2009-06-24 BP p.l.c. Process for the conversion of alcohol(s) into alcohol(s) with increased carbon-chain
EP2072492A1 (en) * 2007-12-17 2009-06-24 BP p.l.c. Process for the conversion of hydrocarbons to ethanol
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US20100063315A1 (en) * 2007-04-26 2010-03-11 Evert Jan Ditzel Process for the carbonylation of dimethyl ether
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