JP2010513270A - Method for carbonylation of aliphatic alcohol and / or reactive derivative thereof - Google Patents

Abstract

C ₁ -C ₃ aliphatic carboxylic acid or product containing the corresponding ester in the presence of a zeolite catalyst having a 8-membered ring channels channel interconnected with that defined by the above 8-membered rings, C ₁ - It produced a C ₃ aliphatic alcohol or reactive derivative thereof by a process comprising the step of reacting with carbon monoxide, and 8-membered rings, at least 2.5 angstroms × least 3.6 angstroms area size and at least one The zeolite has a Bronsted acid site and the zeolite has a ratio of at least 5 silica: X ₂ O ₃ (where X is selected from aluminum, boron, iron, gallium and mixtures thereof) and the zeolite Is not mordenite or ferrierite.
[Selection figure] None

Description

  The present invention relates to a process for the selective preparation of lower aliphatic carboxylic acids and / or their corresponding esters by carbonylation of the corresponding lower aliphatic alcohols and / or their ester or ether derivatives, in particular methanol and The present invention relates to a method for selectively producing acetic acid and / or methyl acetate by carbonylation of an ester or ether derivative thereof. The present invention also relates to an improved method for producing methyl acetate from dimethyl ether, and more particularly to an improved method for producing an alkyl ester of an aliphatic carboxylic acid by carbonylation of an alkyl ether. In another embodiment, the present invention relates to a process for producing a lower aliphatic carboxylic acid by first producing an alkyl ester from a lower alkyl ether and then hydrolyzing the ester to an acid. In this illustration, acetic acid is produced by carbonylation of dimethyl ether to form methyl acetate, and then the ester is hydrolyzed to produce acetic acid.

  The most widely used industrial method for producing acetic acid is methanol carbonylation, generally described in, for example, GB 1185453 and GB 1277242 and US Pat. No. 3,688,533. Has been. In this type of process, methanol is reacted with carbon monoxide or a carbon monoxide containing gas in the presence of a rhodium or iridium containing catalyst, and further in the presence of a halogen (usually iodine) containing promoter. Although widely used, such methods still require the use of expensive corrosion resistant alloys due to the presence of iodide, which makes it difficult to remove from acetic acid by conventional distillation. Leading to the production of a level of iodine-containing by-products. For such reactions, non-halide based catalyst systems have been studied, but none have been commercialized, mainly due to catalyst lifetime and selectivity issues.

  Many patents describe a process for carbonylating methanol or a mixture of methanol and dimethyl ether in the presence of a catalyst. In general, the product is a mixture of acetic acid and methyl acetate, which may contain acetic anhydride. In these patents it is disclosed that one of the reactions that can occur is carbonylation of dimethyl ether to form methyl acetate.

  In EP 0596632, an aliphatic alcohol or a reactive derivative thereof is reacted with carbon monoxide in the presence of a copper, nickel, iridium, rhodium or cobalt filled mordenite zeolite catalyst under high temperature and pressure conditions. A method for producing an aliphatic carboxylic acid by contacting is disclosed.

  In WO 2005/105720, copper, nickel, iridium having aliphatic alcohol and / or reactive derivative thereof as a skeletal element having silicon, aluminum, and further one or more kinds of gallium, boron and iron. Discloses a process for producing an aliphatic carboxylic acid, ester or anhydride thereof by contacting with carbon monoxide in the presence of a rhodium or cobalt filled mordenite catalyst.

  US Pat. No. 6,387,842 discloses the reaction of alcohol, ether and / or ether alcohol raw materials with carbon monoxide in the presence of a catalyst comprising solid superacid, clay, zeolite or molecular sieve under temperature and pressure conditions. Discloses a process for converting to oxygenated products and a catalyst used for such conversion.

  Cheung et al. (Angew, Chem. Int. Ed 2006, 45, (10), 1617) perform carbonylation of dimethyl ether using zeolite mordenite, ferrierite, and also zeolite ZSM-5, BEA and USY. It was. The latter three zeolite types do not contain 8-membered ring channels.

British Patent No. 1185453 British Patent No. 1277242 US Pat. No. 3,688,533 European Patent Application No. 0596632 Specification International Publication No. 2005/105720 Pamphlet US Pat. No. 6,387,842

Cheung et al. (Angew, Chem. Int. Ed 2006, 45, (10), 1617)

The present invention provides for the oxidation of the corresponding C ₁ -C ₃ aliphatic alcohol, such as methanol and / or its ester or ether derivative, such as dimethyl ether, in the presence of a catalyst comprising a zeolite having at least one 8-membered ring channel. A process for the selective production of C ₁ -C ₃ aliphatic carboxylic acids, eg acetic acid and / or the corresponding C ₁ -C ₃ ester, eg methyl acetate, by carbonylation with carbon, comprising an 8-membered ring channel Interconnected with a channel defined by an eight or more member ring, and the eight member ring has a region size of at least 2.5 Angstroms × at least 3.6 Angstroms and at least one Bronsted acid site; zeolite, at least 5 of _silica: X 2 _{O 3} (where, X is aluminum, boron, iron, gully Is selected from the arm, and mixtures thereof.) Has a ratio, and zeolite, C ₁ -C ₃ aliphatic carboxylic acids and / or method of manufacture corresponding ester, wherein the non-mordenite or ferrierite including.

Further, the present invention is the presence of a catalyst comprising a zeolite having at least one 8-member ring channel, substantially C ₁ -C ₃ alkyl ether under anhydrous conditions, for example, dimethyl ether is carbonylated with carbon monoxide C ₁ -C ₃ alkyl esters of C ₁ -C ₃ aliphatic carboxylic acid comprising the step, for example, a method for producing a product comprising methyl acetate, a 8-membered ring channels is defined by the above 8-membered ring Interconnected with the channel and the 8-membered ring has a region size of at least 2.5 Angstroms × at least 3.6 Angstroms and at least one Bronsted acid site, and the zeolite is at least 5 silica: X ₂ O 3 _(where, X is aluminum, boron, iron,. is selected from gallium and mixtures thereof) has a ratio, and Ze Lights, including manufacturing method characterized by not mordenite or ferrierite.

The present invention provides for the oxidation of the corresponding C ₁ -C ₃ aliphatic alcohol, such as methanol and / or its ester or ether derivative, such as dimethyl ether, in the presence of a catalyst comprising a zeolite having at least one 8-membered ring channel. A process for the selective production of C ₁ -C ₃ aliphatic carboxylic acids, eg acetic acid and / or the corresponding ester, eg methyl acetate, by carbonylation with carbon, wherein an 8-membered ring channel Interconnected with a channel defined by the ring, and the 8-membered ring has a region size of at least 2.5 Angstroms × at least 3.6 Angstroms and at least one Bronsted acid site, and the zeolite is at least 5 _silica: X 2 _{O 3} (where, X is aluminum, boron, iron, gallium and this Mixtures of the.) Has a ratio, and zeolite, including C ₁ -C ₃ production method of aliphatic carboxylic acids and / or the corresponding ester, wherein the non-mordenite or ferrierite.

Further, the present invention is the presence of a catalyst comprising a zeolite having at least one 8-member ring channel, substantially C ₁ -C ₃ alkyl ether under anhydrous conditions, for example, dimethyl ether is carbonylated with carbon monoxide C ₁ -C ₃ alkyl esters of C ₁ -C ₃ aliphatic carboxylic acid comprising the step, for example, a method for producing a product comprising methyl acetate, a 8-membered ring channels is defined by the above 8-membered ring Interconnected with the channel and the 8-membered ring has a region size of at least 2.5 Angstroms × at least 3.6 Angstroms and at least one Bronsted acid site, and the zeolite is at least 5 silica: X ₂ O 3 _(where, X is aluminum, boron, iron,. is selected from gallium and mixtures thereof) has a ratio, and Ze Lights, including manufacturing method characterized by not mordenite or ferrierite.

In one embodiment of the present invention, one component of the feed to the process of the present invention may be a C ₁ -C ₃ aliphatic alcohol. The method of the present invention is particularly applicable to alcohols such as methanol, ethanol and n-propanol. A preferred alcohol is methanol. Instead of alcohol, or a reactive derivative of a good alcohol be used in addition to alcohols, esters and C ₁ -C ₃ alcohol ether derivatives of alcohol. Suitable reactive derivatives of methanol include methyl acetate and dimethyl ether. Mixtures of alcohol and its reactive derivatives may be used, for example a mixture of methanol and methyl acetate.

  When alcohol is used as a feed to the process of the present invention, the product will vary depending on the degree of alcohol conversion. If the conversion is 100%, the product will be the corresponding carboxylic acid. Thus, if methanol is the alcohol feed, the product will contain acetic acid. If the conversion is less than 100%, the alcohol will be converted to a mixture of the corresponding carboxylic acid and carboxylic ester. If the ester used as feed is a symmetric ester, for example methyl acetate, the main product in the carbonylation process will be the corresponding carboxylic acid (in this case acetic acid). If the ester is asymmetric, the product will contain a mixture of carboxylic acids formed from each alkyl group in the ester.

［但し、Ｒ_１及びＲ_２が独立してＣ_１−Ｃ_３アルキル基である。］
を有する化合物を含む。Ｒ_１及びＲ_２がアルキル基である場合、基Ｒ_１及びＲ_２における炭素原子の合計数は、２〜６個である。Ｒ_１及びＲ_２は、直鎖のアルキル基であるのが好ましく、１〜３個の炭素原子を有する直鎖のアルキル基、例えばメチル、エチル及びｎ−プロピルであるのが最も好ましい。 In another embodiment of the present invention, one component of the feed to the process of the present invention, C ₁ -C ₃ alkyl ether, i.e., the formula:

[However, R ₁ and R ₂ are independently a C ₁ -C ₃ alkyl group. ]
A compound having When R ₁ and R ₂ are alkyl groups, the total number of carbon atoms in the groups R ₁ and R ₂ is 2-6. R ₁ and R ₂ are preferably straight-chain alkyl groups, most preferably straight-chain alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl and n-propyl.

If the ether is a symmetric ether, such as dimethyl ether, the main product will be the corresponding alkyl ester of an aliphatic acid (in this case methyl acetate). If the ether is asymmetric, the product will contain one or both of the two possible carboxylic esters, depending on whether the two C—O bonds were cleaved in the reaction. For example, if the feed is methyl ethyl ether (R ₁ = methyl; R ₂ = ethyl), the product will contain ethyl acetate and / or methyl propionate.

  The second component in the method of the present invention is a feed comprising carbon monoxide. The feed may include substantially pure carbon monoxide (CO), such as carbon monoxide commonly provided by industrial gas suppliers, or the feed may be a desired ester of an alkyl ether. Impurities that do not interfere with the conversion to hydrogen, such as hydrogen, nitrogen, helium, argon, methane and / or carbon dioxide may be included. For example, the feed may include CO, which is typically made commercially by removing hydrogen from synthesis gas via cryogenic separation and / or using a membrane.

  The carbon monoxide feed may contain a substantial amount of hydrogen. For example, the feed may be what is commonly known as synthesis gas, i.e. many gaseous mixtures used for the synthesis of various organic or inorganic compounds, in particular the synthesis of ammonia. good. Syngas is generally obtained by reacting a carbon-rich substance with steam (a method known as steam reforming) or steam and oxygen (partial oxidation process). Such a gas mainly contains carbon monoxide and hydrogen, and may further contain small amounts of carbon dioxide and nitrogen. Suitably, the ratio of carbon monoxide: hydrogen may be in the range of 1: 3 to 15: 1 on a molar basis, for example in the range of 1: 1 to 10: 1. The ability to use synthesis gas provides another advantage over the process for producing acetic acid from methanol, namely the choice of an inexpensive carbon monoxide feed. In methanol-to-acetic acid processes, the inclusion of hydrogen in the feedstock can lead to the production of unwanted hydrogenation.

The catalyst used in the process of the present invention is zeolite excluding mordenite and ferrierite. Zeolites, both natural and synthetic, are microporous crystalline aluminosilicate materials that have a well-defined crystalline structure as measured by X-ray diffraction. Although the chemical composition of the zeolite can be widely changed, it is generally composed of SiO ₂ , and a part of the Si atom is converted into a tetravalent atom such as Ti or Ge, a trivalent atom such as Al, B, etc. , Ga, Fe, or a divalent atom such as Be, or a combination thereof. Zeolites are comprised of other channel systems or channel systems that may be interconnected with cavities such as side pockets or cages. A channel system is uniform in size within a particular zeolite and may be three-dimensional, but not necessarily so, and may be two-dimensional or one-dimensional. It is common to contact the zeolite channel system via a 12-membered, 10-membered or 8-membered ring. The zeolite used in the present invention contains at least one channel defined by an 8-membered ring. Preferred zeolites are those that do not have side pockets or cages within the zeolite structure. Atlas of Zeolite Framework Types (C. Baerlocher, WM Meier, DH Olson, 5th edition. Elsevier, Amsterdam, 2001) and web-based version (http: / ww: / ww databases /) is a summary of the topological and structural details of the zeolite framework including the types of ring structures present in the zeolite and the dimensions of the channels defined by each ring type. In the context of the present invention, the term 'zeolite' also includes materials having a zeolite-type structure, such as flaky porous crystalline oxide material and columnar layered oxide material, such as ITQ-36.

The method of the present invention uses a zeolite having at least one channel defined by an 8-membered ring of tetrahedral coordination atoms (tetrahedra) in a region dimension having a minimum dimension of 2.5 Angstroms × 3.6 Angstroms. . An 8-membered ring channel is interconnected with at least one channel defined by an 8-membered or more, eg, 10-membered and / or 12-membered ring. Interconnected 8-membered, 10-membered and 12-membered ring channels contact the Bronsted acid sites contained in the 8-membered ring channel to effect carbonylation of C ₁ -C ₃ alcohols or derivatives thereof such as methanol and dimethyl ether. It is possible to start at an acceptable speed.

  The zeolite used in the process of the present invention may consist of interconnected channels defined only by eight-membered rings, for example framework type CHA zeolites such as chabazite and framework type ITE such as ITQ- 3. However, the zeolite preferably has at least one channel formed by an 8-membered ring and at least one interconnected channel defined by more than 8 members, such as 10 and / or 12 members. Non-limiting examples of zeolites having an 8-membered ring channel and a larger interconnected ring channel system include framework type OFF zeolites such as, for example, fluorite, GME, such as gmelinite, MFS, such as ZSM-57, EON, such as ECR. -1 and ETR, such as ECR-34. The zeolite used in the method of the present invention has at least one 8-membered ring channel interconnected with at least one 12-membered ring channel, for example, framework type OFF and GME zeolites, such as offretite and It is gmelinite.

  However, the mere presence of interconnected 8-membered ring channels in zeolite is not sufficient to develop an effective carbonylation process. It is also necessary to control the region dimensions of the channel system so that the reaction material molecules can freely diffuse in and out of the zeolite framework. It has now been found that effective carbonylation can be achieved if the opening (pore width) in the 8-membered ring channel of the zeolite has a minimum dimension of 2.5 × 3.6 angstroms. Zeolite framework-type channel dimensions can be found, for example, in Atlas of Zeolite Framework Types. In addition, M.M. D. Foster, I.D. Rivin, M.M. M.M. J. et al. Treacy and O.I. Delgado Friedrichs uses “A geometric solution to the large-free-sphere program in zeolitic frameworks”. And tabulates the largest free-sphere diameters for diffusion along three important crystallographic directions in the case of the 165 zeolite framework generally listed in Atlas of Zeolite Framework Types. It was. The ring dimension region can be altered by suitable atomic substitutions that change the bond lengths and bond angles of tetrahedrally coordinated atoms and bridge oxygens.

A partial listing of the framework types of zeolites with at least one interconnected 8-membered ring channel with a minimum dimension of 2.5 × 3.6 angstroms used by Atlas of Zeolite Framework Types is given below:

  Zeolites are commercially available. Alternatively, the zeolite can be synthesized using known techniques. In general, synthetic zeolites are prepared from aqueous reaction mixtures containing a suitable source of oxide. In order to influence the production of zeolite having a desired structure, an organic directing agent may be included in the reaction mixture. After properly mixing the components of the reaction mixture with each other, the reaction mixture is subjected to appropriate crystallization conditions. After completing the crystallization of the reaction mixture, the crystalline product can be recovered from the residue of the reaction mixture. Such recovery may require the crystals to be filtered, washed with water, and then calcined under high temperature conditions. The synthesis of zeolite has been described in many documents. For example, zeolite Y and its synthesis are described in US Pat. No. 3,313,0007 and zeolite ZSM-23 is described in US Pat. No. 4,076,842 and J. Pat. Phys. Chem. B, 109, pages 652-661 (2005), Zones, S .; I. Darton, R.D. J. et al. , Morris, R and Hwany, SJ; ECR-18 is available from Microporous Mesoporous Mat. 28, pp. 233-239 (1999), Vaughan D. et al. E. W & Strommeier, K.M. G. Theta-1 is described in Nature, 312, 533-534 (1984), Barri, S .; A. I, Smith W. G. , White, D and Young, D. Mazite is described in Microporous Mesoporous Mat. 63, pages 33-42 (2003), Martucci, A, Alberti, A, Guzmar-Castillo, M .; D. , Di Renzo, F and Fajula, F. Zeolite L is available from Microporous Mesoporous Mat. 76, pp. 81-99 (2004), Bhat, S .; D. Niphadkair, P .; S. , Gaydharker, T .; R. , Await, S. V. Belhekar, A .; A. and Joshi, P .; N and even J. Ind. Eng. Chem. Vol. 10, no. 4 (2004), 633-644, Ko Y. et al. S, Ahn W. S, and offretite is described in Zeolites 255-264, Vol. 7, 1987 Howden M. et al. G. It is described in.

The zeolite catalyst used in the process of the present invention is generally used in the 'H' form of the zeolite, for example in the form of an acid called H-offretite. It is possible to convert other forms of the zeolite, for example the NH ₄ form, to the H-form, for example by calcining the NH ₄ form under high temperature conditions. The acid form of the zeolite will have Bronsted acid (H ⁺ ) sites that are located in the various channel systems in the zeolite. For example, H-offlet zeolite has an H ⁺ site located in a 12-membered ring channel, particularly an 8-membered ring channel. The number or concentration of H ⁺ species present in a particular channel system can be measured by known techniques such as infrared NMR spectroscopy. Quantification of Bronsted acidity by FTIR and NMR spectroscopy is described, for example, by Makalova; A. Wilson, A .; E. , Van Liemt, B.M. J. et al. , Masters, C.I. de Winter, A.D. W. Williams, C .; Journal of Catalysis 1997, 172, (1), 170. The two types of channels in H-offlet zeolite (defined by 12-membered and 8-membered rings) give rise to at least two bands that are bound to the hydroxyl region of H-offlet zeolite, and one band is Corresponds to vibrations in large pores, the other corresponds to vibrations in small pores under lower frequency conditions. While the inventors of the present application have shown that there is a correlation between the number of H ⁺ sites arranged in the 8-membered ring channel and the rate of carbonylation, the case of the 12-membered ring channel Was observed to have no correlation. The rate of carbonylation was found to increase in parallel with the number of H ⁺ sites in the 8-membered ring channel. In contrast, the correlation with the number of H ⁺ sites within the 12-membered ring channel is not clear. The number of H ⁺ sites in the 8-membered ring channel can be controlled by substituting H ⁺ with metal cations such as Na ⁺ or Co ²⁺ using known ion exchange techniques.

［但し、Ｘが３価の元素、例えばアルミニウム、ホウ素、鉄及び／又はガリウムであり、好ましくはアルミニウムである。］
に関連すると表されても良い。所定のゼオライトにおけるＳｉＯ_２：Ｘ_２Ｏ_３比は、屡々、変化する。例えば、オフレット沸石を、６〜９０以上のＳｉＯ_２：Ａｌ_２Ｏ_３比にて合成可能であり、ゼオライトＹを約１〜約６にて合成可能であり、菱沸石を約２〜２０００にて合成可能であり、そしてグメリン沸石を、４を超えるＳｉＯ_２：Ａｌ_２Ｏ_３比にて合成可能であることが知られている。一般に、ＳｉＯ_２：Ｘ_２Ｏ_３比の上限は、制限されず、例えばゼオライトＺＳＭ−５である。本発明で使用するゼオライトは、少なくとも５、好ましくは７〜４０の範囲、例えば１０〜３０の範囲のＳｉＯ_２：Ｘ_２Ｏ_３モル比を有する。好適には、ＳｉＯ_２：Ｘ_２Ｏ_３モル比は、１００以下である。特定のＳｉＯ_２：Ｘ_２Ｏ_３比を、高温の水蒸気処理又は酸洗浄を用いる標準的な技術での脱アルミニウム化（但し、ＸがＡｌである）によって多くのゼオライトに関して得ることが可能である。 The chemical composition of the zeolite has the following molar relationship:

[However, X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum. ]
It may be expressed as related to The SiO ₂ : X ₂ O ₃ ratio in a given zeolite often varies. For example, offretite can be synthesized at a SiO ₂ : Al ₂ O ₃ ratio of 6 to 90 or more, zeolite Y can be synthesized at about 1 to about 6, and chabazite at about 2 to 2000. It is known that gmelinite can be synthesized and that it is possible to synthesize gmelinite at a SiO ₂ : Al ₂ O ₃ ratio of greater than 4. In general, the upper limit of the SiO ₂ : X ₂ O ₃ ratio is not limited, for example, zeolite ZSM-5. The zeolite used in the present invention has a SiO ₂ : X ₂ O ₃ molar ratio of at least 5, preferably in the range of 7-40, for example in the range of 10-30. Preferably, the SiO ₂ : X ₂ O ₃ molar ratio is 100 or less. A specific SiO ₂ : X ₂ O ₃ ratio can be obtained for many zeolites by dealumination with standard techniques using high temperature steaming or acid cleaning (where X is Al). .

Depending on the nature of the feed, water may be generated in situ. For example, when alcohol is used as a feedstock, water is produced by dimerizing alcohol into ether. Water may also be generated by esterification of an alcohol and a carboxylic acid product. Water can be fed separately or together with the alcohol or ester feed components or mixtures thereof. Water may be present in liquid or vapor form. If the process of the invention is carried out under hydrating conditions and the feed is an aliphatic alcohol or an aliphatic ester, the carbonylation reaction product will be the corresponding carboxylic acid and / or ester. For example, if the feed is methanol or methyl acetate, the reaction product will be acetic acid and / or methyl acetate. If the feed is a C ₁ -C ₃ alkyl ethers, such as dimethyl ether, carbonylation reaction is preferably carried out in a substantially anhydrous conditions. In the substantial absence of water, the carbonylation of dimethyl ether is selective for the methyl acetate product.

  If the reaction is carried out substantially in the absence of water, the operation is started after the catalyst and preferably the feed components have been dried, for example by preheating to 400-500 ° C.

  Generally, when the feedstock is an ether, such as dimethyl ether, the process operates under a temperature condition of about 250 ° C. or less, ie, about 100 to about 250 ° C., preferably about 150 to about 180 ° C. When the feed is an alcohol or ester, such as methanol or methyl acetate, the reaction operates under temperature conditions above 250 ° C., ie from about 250 to about 400 ° C., preferably from about 275 to about 350 ° C. To do.

  Typical total operating pressures are from about 1 to about 100 bar, preferably using a carbon monoxide pressure greater than 10 bar and a reactant pressure less than 5 bar.

  The process may operate as a continuous process or a batch process, and generally a continuous process is preferred. In essence, the process is gas phase operation and the reactants are introduced into the liquid or gas phase and the product is removed as a gas. If desired, the reaction product may be subsequently cooled and condensed. The catalyst may suitably be used in a fixed bed or a fluidized bed. In the operation of the process, unreacted starting material may be recovered and recycled to the reactor. If the product is methyl acetate, it can be recovered and sold as such or sent to other chemical process equipment as desired. If desired, the entire reaction product can be sent to chemical process equipment to convert methyl acetate or acetic acid and optionally other components to other useful products.

  In one preferred embodiment of the invention, when methyl acetate is the product, it can be recovered from the reaction product and contacted with water to form acetic acid via a hydrolysis reaction. Alternatively, the entire product may be transferred to a hydrolysis step, followed by separation of acetic acid. The hydrolysis step may be performed in the presence of an acid catalyst and can take the form of reactive distillation methods well known in the art.

  After separation, the alcohol produced in the reaction can be sent to a dehydration reactor to produce ether, which can be separated from water and recycled to the carbonylation unit as a new feed for the carbonylation reactor. is there.

  In another embodiment, when hydrolysis of the ester product to alcohol and carboxylic acid is carried out by injecting water into the catalyst bed in one or several portions, a sufficient amount of ester is obtained by carbonylation. To manufacture. Water injection in such a process, for example, essentially stops the conversion of dimethyl ether to methyl acetate and eliminates the need for a separate hydrolysis reactor.

  The following examples are given as illustrations of the present invention. However, this is not meant to limit the scope of the invention.

General Procedure 1) Catalyst Preparation Catalyst samples in ammonium or acid form are compressed under conditions of 12 tons in a 33 mm die set using Specac Press, then ground to 212-335 micron granules Sieve into diameter. The catalyst (typically 1 g) was then calcined to convert the NH ₄ ⁺ form to the H ⁺ form in a muffle furnace (furnace volume = 30 L) in a static atmosphere of air. The temperature was raised from room temperature to 450 ° C. at a ramp rate of 5 ° C./min and then maintained for 12 hours under such temperature conditions. Details of the zeolite are shown in Table 1 below.

The sodium form of zeolite A was converted to the NH ₄ ⁺ form by stirring 1 g of material in a 10 ml solution of 1 molar ammonium nitrate for 3 hours and then filtering the solution. This was repeated three times, the solid was dried in air at 100 ° C., then pressed and sieved. NH ₄ ⁺ exchanged NaA was not calcined before use.

Carbonylation reaction of dimethyl ether The carbonylation reaction of dimethyl ether was carried out in a pressure flow reactor apparatus consisting of 60 identical parallel isothermal cocurrent vertical reactors. In each tube, 50 microliters of catalyst was packed into a metal sinter having a pore size of 20 μm. All catalyst samples were heated to 100 ° C. at a ramp rate of 5 ° C./min under N ₂ at atmospheric pressure under a flow rate condition of 3.33 mL / hour and maintained under such temperature conditions for 1 hour. The reactor was then depressurized to 70 bar with N ₂ and the system was maintained under such conditions for 1 hour. The nitrogen gas feed was then changed to a mixture containing 64 mol% carbon monoxide, 16 mol% hydrogen and 20 mol% nitrogen under a gas flow rate of 3.33 mL / hr and the system was changed to 3 Heated to a temperature of 300 ° C. at a ramp rate of ° C./min. The system was then maintained for 3 hours under such conditions. Thereafter, the temperature was reduced to 180 and stabilized for 10 minutes. At this stage, the activation of the catalyst is considered complete, and the gaseous feed is subjected to 64 mol% carbon monoxide, 16 mol% hydrogen, 15 mol% under gas flow conditions of 3.33 mL / hr. And a mixture containing 5 mol% dimethyl ether. The reaction was continued for 27.8 hours, after which the temperature was raised to 250 ° C. Varian 4900 micro gas chromatography (molecular sieve 5A, Porapak® Q and CP-Wax-52) having 3 columns of water vapor coming from the reactor, each column being equipped with a thermal conductivity detector Micro gas chromatography and Interscience Trace gas chromatography having two columns, each column having a flame ionization detector. The results of the carbonylation reaction are shown in Table 2.

  In the above experiments, the offretite, chabazite, and ECR-18 zeolites are at least 5 silica: alumina molar ratio, at least 2.5 x at least 3.6 angstrom region range 8-membered ring channel and at least one. And an 8-membered ring channel was interconnected with a channel defined by a ring of 8 or more members. These experiments have shown that significant carbonylation activity can be achieved with these zeolites. However, carbonylation activity was hardly found to occur in carbonylation reactions using zeolites, ie ZSM-23, Theta-1, Zeolite-A, Zeolite-L, Mazite and Beta-18. ZSM-23 and Theta-1 have only 10-membered ring channels and no 8-membered ring channels; Beta-18 and zeolite-L have only 12-membered ring channels and 8-membered ring channels Zeolite-A has an 8-membered ring channel but its silica / alumina ratio is less than 5; Mazite has both an 8-membered and 12-membered ring channel, The member ring channel did not cross the 8-member ring channel or the 12-member ring channel.

General procedure B
In order to investigate the catalytic activity of the zeolite when methanol was non-iodinated carbonylated to acetic acid, it was possible to test the zeolite in a pressure flow reactor according to the following procedure. Zeolite pellets with dimensions of 500-1000 μm were packed into a pressure flow reactor. A catalyst pre-bed was also used to ensure thorough mixing / heating of the reaction materials. The preliminary bed was γ-alumina, which can form a methanol / dimethyl ether / water equilibrium with methanol. The catalyst was activated under flowing nitrogen conditions at 350 ° C. (100 cm ³ / min) for 16 hours and then reduced under carbon monoxide at 350 ° C. (200 cm ³ / min) for 2 hours. The system was then depressurized to 30 bar using a back pressure regulator. The carbon monoxide flow rate was adjusted to 400 cm ³ / min (GHSV = 2200) and methanol was pumped into the reactor (rate + 0.15 ml / min). Liquid product and unconverted reaction material were collected in a cooled trap, while gaseous product and unreacted feed were sampled downstream by on-line gas chromatography. The reaction was frequently sampled and the liquid product was analyzed off-line by gas chromatography. It is expected that sufficient amounts of methyl acetate and acetic acid will be found in the liquid product using zeolite H-offlet zeolite (molar ratio of 10 silica: alumina) as catalyst in the methanol carbonylation described above. Would be. Similarly, when the zeolite H-gmelinite (8 silica: alumina molar ratio) was used as a catalyst in the methanol carbonylation described above, sufficient amounts of methyl acetate and acetic acid were found in the liquid product. Would have been expected. Both offretite and gmelinite had an 8-membered ring channel that intersected the 12-membered ring channel. In contrast, zeolite H-ZSM-5 (23 silica: alumina ratio; 10-membered ring channel only) or zeolite HY (12 silica: alumina ratio; 12-membered ring channel only) was used as the catalyst. In some cases, only trace amounts of acetic acid would be found in the liquid product.

  All publications and patent applications cited in the specification of the present application are hereby incorporated by reference into the content of the present application, specifically and individually as indicated by reference to each publication or patent application.

  Although the foregoing invention has been described in detail by way of illustration and example for purposes of clarity of understanding, those skilled in the art will appreciate the teachings of the invention and from the spirit or scope of the appended claims. It will be readily apparent that certain changes and modifications can be made without departing.

Claims (42)

In the presence of a catalyst comprising a zeolite having at least one 8-membered ring channels, a C ₁ -C ₃ aliphatic alcohols and / or esters or ether derivatives corresponding due to carbonylation with carbon monoxide C ₁ - a C ₃ aliphatic carboxylic acids and / or manufacturing process of the corresponding ester,
An 8-membered ring channel is interconnected with a channel defined by a ring of 8 or more members, and the 8-membered ring has a region size of at least 2.5 Angstroms × at least 3.6 Angstroms and at least one Bronsted acid site And the zeolite has a molar ratio of at least 5 silica: X ₂ O ₃ where X is selected from aluminum, boron, iron, gallium and mixtures thereof, and the zeolite has C ₁ -C ₃ aliphatic carboxylic acids and / or manufacturing process of the corresponding ester, wherein the non-mordenite or ferrierite. The method of claim 1 C ₁ -C ₃ carboxylic acid is acetic acid. The method of claim 1 esters of C ₁ -C ₃ carboxylic acid is methyl acetate. The method of claim 1 C ₁ -C ₃ alcohol is methanol or ethanol.   The process according to claim 4, wherein the alcohol is methanol.   The process of claim 1 wherein the ether is carbonylated.   The process according to claim 6, wherein the ether is dimethyl ether.   The process of claim 1, wherein the ether is carbonylated under temperature conditions of about 100C to about 250C.   The process of claim 1, wherein the ether is carbonylated under temperature conditions of about 150C to about 180C.   The method according to claim 8 or 9, wherein the ether is dimethyl ether.   The process of claim 1, wherein the alcohol or ester derivative thereof is carbonylated under temperature conditions of about 250C to about 400C.   The method of claim 1, wherein the alcohol or ester derivative thereof is carbonylated under temperature conditions of about 275C to about 350C.   13. A process according to claim 11 or 12, wherein the alcohol is methanol and the ester derivative is methyl acetate.   The process of claim 1 wherein the catalyst comprises a fixed bed of catalyst.   The process of claim 1 wherein the catalyst comprises a fluidized bed of catalyst.   The continuous method according to claim 1.   The batch method according to claim 1.   The method of claim 1, wherein the carbon monoxide-containing feedstock further comprises hydrogen.   The method of claim 18, wherein the carbon monoxide containing feed comprises synthesis gas. Derivatives of alcohol is C ₁ -C ₃ ethers, the method is substantially carried out under anhydrous conditions, and the product A method according to claim 1 which is corresponding ester.   21. A process according to claim 20, wherein the ether is dimethyl ether, the process is carried out under substantially anhydrous conditions and the product is methyl acetate.   21. The method of claim 20, further comprising hydrolyzing the ester to produce the corresponding carboxylic acid.   The method according to claim 21, further comprising hydrolyzing methyl acetate to produce acetic acid.   The process according to claim 22 or 23, wherein the hydrolysis is carried out in a reactor separate from the ester production reaction.   The process according to claim 22 or 23, wherein the hydrolysis is carried out in the same reactor as the ester production reaction.   The process according to claim 1, wherein the zeolite catalyst is selected from the group consisting of zeolites of framework type OFF, CHA, ITE, GME, ETR, EON and MFS.   27. The method of claim 26, wherein the catalyst is selected from the group consisting of offretite, gmelinite, ZSM-57 and ECR-18.   28. A process according to claim 27, wherein the zeolite is offretite.   2. A process according to claim 1 wherein the catalyst consists of channels defined only by 8-membered rings.   The method of claim 1, wherein a channel defined by an 8-membered ring is interconnected with at least one channel defined by an 8-membered or greater ring.   32. The method of claim 30, wherein at least one channel defined by a ring having more than 8 members is defined by a 10-membered ring or a 12-membered ring.   32. The method of claim 31, wherein at least one channel defined by more than 8 membered rings is defined by a 12 membered ring.   The method of claim 1, wherein the method is performed under hydrating conditions.   34. The method of claim 33, wherein water is supplied separately or together with the alcohol and / or ester thereof. The method of claim 1, wherein the silica: X ₂ O ₃ ratio is 100 or less. _Silica: The method of claim 1 X 2 _{O 3} ratio is in the range of 7 to 40. The method of claim 1, wherein the silica: X ₂ O ₃ ratio is in the range of 10-30.   The method of claim 1, wherein X is selected from aluminum, gallium, and mixtures thereof.   The method of claim 1, wherein X is aluminum. The method of claim 1, wherein X is aluminum and the silica: Al ₂ O ₃ ratio is 100 or less. Silica: The method of claim 40 _Al 2 _{O 3} ratio is in the range of 7 to 40. Silica: The method of claim 40 _Al 2 _{O 3} ratio is in the range of 10 to 30.