WO2024083048A1 - 用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂及其用途 - Google Patents

用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂及其用途 Download PDF

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WO2024083048A1
WO2024083048A1 PCT/CN2023/124541 CN2023124541W WO2024083048A1 WO 2024083048 A1 WO2024083048 A1 WO 2024083048A1 CN 2023124541 W CN2023124541 W CN 2023124541W WO 2024083048 A1 WO2024083048 A1 WO 2024083048A1
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catalyst
catalyst layer
methyl acetate
carbonylation
dimethyl ether
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French (fr)
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高裕一
杨国辉
椿大輝
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高化学株式会社
株式会社模范
高裕一
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Publication of WO2024083048A1 publication Critical patent/WO2024083048A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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

  • the present invention relates to a catalyst, in particular to a catalyst for preparing methyl acetate by carbonylation of dimethyl ether and/or methanol; and a method for preparing methyl acetate by carbonylation of dimethyl ether and/or methanol using the catalyst.
  • Methyl acetate is widely used in the fragrance, coating, adhesive and pharmaceutical industries. It is not only a good environmentally friendly solvent that can be used to replace acetone, butanone, ethyl acetate, cyclopentane, etc., but also an important organic raw material intermediate. Its downstream products mainly include acetic acid, ethanol, acetic anhydride, methyl acrylate, vinyl acetate, acetamide, etc. The demand for methyl acetate at home and abroad is increasing. In recent years, methyl acetate has developed some new applications, such as hydrogenation synthesis of ethanol.
  • methyl acetate is usually prepared from dimethyl ether and/or methanol by carbonylation reaction.
  • the acid sites of the molecular sieve are increased and the distribution of the acid sites is regulated by introducing metal elements or loading a certain amount of metal elements, so as to achieve the purpose of improving the activity of the molecular sieve in catalyzing the carbonylation of dimethyl ether.
  • the mainstream mechanism in the carbonylation of dimethyl ether believes that the activation of CO or dimethyl ether/methanol requires the assistance of the metal functional sites of the molecular sieve and the Bronsted acid sites of the molecular sieve.
  • MOR after metal ion exchange has problems such as unstable skeleton and easy internal metal aggregation, and the space-time yield and selectivity of the product methyl acetate still need to be improved.
  • molecular sieves loaded with metals by impregnation method also have similar problems.
  • the inventors have conducted extensive and in-depth research on molecular sieve catalysts for preparing methyl acetate and/or acetic acid by carbonylation of dimethyl ether and/or methanol, in order to discover a catalyst with a completely new structure having stable carbonylation activity.
  • the inventors have found that by isolating the metal from the molecular sieve in space, the space-time yield of methyl acetate can be significantly improved, and the selectivity is considerable.
  • the present invention relates to a catalyst comprising a first catalyst layer comprising a metal supported on a support material and a second catalyst layer comprising an H-type molecular sieve, wherein the first catalyst layer and the second catalyst layer are spatially isolated.
  • the metal in the first catalyst layer may be those metals in the metal-modified MOR commonly used in the art for carbonylation reactions, such as one or more of Ca, Ag, Ce, Pt, Pd, Ga, Zn, Mg, Au, Co, Fe, Zr, Ni or Cu, preferably one or more of Cu, Pd, Ag, Ce, Co, Ga, Zr, Zn or Fe, most preferably one or both of Cu or Pd.
  • the support material in the first catalyst layer may be a conventional inert support, such as silica, zirconia, titania, ceria, activated carbon, graphene, carbon nanotubes or a combination thereof, preferably silica, activated carbon, graphene, carbon nanotubes or a combination thereof.
  • the metal loading of the support material in the first catalyst layer can be 0.001 to 30% by weight, preferably 0.01 to 25% by weight, more preferably 0.1 to 20% by weight, most preferably 0.5 to 15% by weight, in each case based on the total weight of metal and support material in the first catalyst layer.
  • the specific surface area of the metal-loaded support material in the first catalyst layer can be 300-700 m 2 /g, preferably 400-600 m 2 /g, in each case determined by mercury porosimetry using N 2. Surprisingly, it has been found that when the specific surface area of the support material is within the above range, the resulting catalyst has a high space-time yield and selectivity.
  • the pore volume of the metal-loaded support material in the first catalyst layer can be 0.10-1.50 mL/g, preferably 0.20-0.70 mL/g, in each case determined according to the nitrogen adsorption-desorption BET method. Surprisingly, it has been found that when the pore volume of the support material is within the above range, the resulting catalyst has a high space-time yield and selectivity.
  • the pore size of the metal-loaded support material in the first catalyst layer may be 3.0-50.0 nm, preferably 7.0-10 nm.
  • the particle size of the support material may be 10-10000 ⁇ m, preferably 20-5000 ⁇ m, more preferably 40-1000 ⁇ m, more preferably 50-500 ⁇ m, most preferably 60-250 ⁇ m.
  • the loading of the metal on the support material can be achieved by methods known in the art, such as impregnation, in particular incipient wetness impregnation.
  • Incipient wetness impregnation also known as capillary impregnation or dry impregnation, is commonly used to synthesize heterogeneous materials, i.e., catalysts.
  • the precursor is dissolved in water or an organic solvent and the resulting solution is added to a catalyst support having a pore volume approximately the same as the volume of solution added. Capillary action draws the solution into the support pores.
  • the catalyst can then be dried and calcined to remove volatile components to deposit the metal on the support material.
  • the support material Prior to impregnation, the support material may be subjected to a vacuum degassing treatment.
  • the treatment is carried out at a temperature of 80-150° C., and the treatment time may be 0.5-10 hours.
  • the vacuum degassed support is immersed in a solution of a soluble salt of the metal.
  • the soluble salt may be a nitrate, a sulfate, a carboxylate or a halide, especially a chloride.
  • its soluble salt may be copper nitrate, copper sulfate, copper acetate, copper oxalate or a copper halide, wherein the copper halide may be selected from copper chloride or copper bromide, including hydrate and non-hydrate forms.
  • the water-soluble copper salt is copper nitrate, copper sulfate or copper chloride.
  • copper complexes such as copper ammonia complexes, may also be used.
  • the support material can be stirred to ensure uniform metal loading.
  • the stirring can be performed with a stirrer or ultrasound assistance, preferably ultrasound assistance.
  • the resulting wet solid can be vacuum degassed, then dried, and finally calcined.
  • Vacuum degassing can be carried out at a temperature of 80-150°C, and the treatment time can be 0.5-72 hours, preferably 10-50 hours.
  • Drying can be carried out at a temperature of 80-150°C, and the drying time can be 0.5-24 hours.
  • Calcination can be carried out at a temperature of 200-700°C, preferably 300-600°C, and the calcination time can be 0.5-24 hours.
  • the H-type molecular sieve in the second catalyst layer can be H-type ZSM-34, ZSM-35, MOR, CHA, OFF, EU-12, Al-RUB-41 or HSUZ-4, preferably H-type OFF, EU-12, Al-RUB-41, ZSM-34 or MOR, and more preferably H-type MOR (H-MOR).
  • the H-type molecular sieve can be commercially available or prepared by a method known in the art, such as a solvent thermal method, preferably a hydrothermal method.
  • the hydrothermal method comprises the following steps: mixing an aluminum source, a silicon source, an alkali source, an optional template agent and water, and performing a hydrothermal crystallization reaction to obtain a crystallization reaction material; drying the crystallization reaction material, then calcining it, and finally reducing it to obtain the H-type molecular sieve.
  • the aluminum source can be selected from one or more of sodium aluminate, aluminum nitrate, aluminum isopropoxide, and aluminum chloride;
  • the alkali source can be selected from one or more of sodium hydroxide, sodium carbonate, and potassium hydroxide;
  • the silicon source can be selected from one or more of silicon dioxide, silica sol, water glass, and organic silane; when used, the template can be selected from one or more of choline chloride, tetraethylammonium hydroxide, and tetramethylammonium chloride.
  • the amounts of the aluminum source, alkali source, silicon source, optional template agent (SDA) and water are known in the art.
  • the hydrothermal crystallization can be carried out in a closed container (e.g., autoclave) under the autogenous pressure of the reaction system.
  • the crystallization temperature can range from 100-300°C, preferably 150-300°C; the crystallization time can range from 1 hour to 10 days, preferably 4 hours to 5 days.
  • a slow-release agent may be added.
  • Suitable slow-release agents include, but are not limited to, urea, ammonium acetate, ammonium oxalate or ammonium carbonate.
  • the amount of the slow-release agent may be 0-2.0% by weight, preferably 0.01-1.5% by weight, and more preferably 0.1-1.0% by weight, based on the total weight of the reaction mixture.
  • the reaction mixture can be filtered and washed with distilled water several times (e.g., 1-10 times, preferably 1-3 times) until the washing liquid is neutral. Then, the filtrate is dried. Drying can be carried out by various drying methods known in the prior art, such as ordinary heating drying, microwave drying and/or spray drying. In the case of heating drying, the drying temperature can be 50-200° C., preferably 80-150° C., and the drying time can be 1-24 hours, more preferably 4-20 hours, more preferably 8-15 hours.
  • the resulting product can be shaped, and the shaping can be carried out in a manner known in the prior art, such as tableting, ball rolling or extrusion.
  • the shaping can be carried out under the addition of a lubricant.
  • the lubricant is, for example, graphite.
  • the amount of lubricant used can be 1-10%, preferably 1-5%, based on the total weight of the lubricant and the dried product.
  • the resulting shaped body can be crushed and sieved through a 40-60 mesh sieve.
  • the obtained product is calcined.
  • the calcination can be carried out in various ways known in the prior art, such as in a muffle furnace.
  • the calcination temperature can be 300-800°C, preferably 350-600°C, more preferably 350-500°C; the calcination time can be 1-24 hours, preferably 1-12 hours, more preferably 1-5 hours.
  • the "first catalyst layer” and the “second catalyst layer” are relative to the flow direction of the reaction materials (such as dimethyl ether and CO, etc.), that is, relative to the flow direction of the reaction materials, the first catalyst layer is located upstream of the second catalyst layer.
  • the reaction materials such as dimethyl ether and CO, etc.
  • isolated in space means that the first catalyst layer and the second catalyst are spatially separated by a macroscopically discernible distance, such as centimeter level, such as 0.5-100 cm, preferably 1-100 cm, more preferably 1-50 cm, more preferably 1-20 cm, most preferably 1-10 cm.
  • the first catalyst layer and the second catalyst layer can be isolated by an inert material mesh, such as quartz wool, quartz sand, activated carbon, silicon dioxide, graphite, glass beads or ceramic rings.
  • the weight ratio of the first catalyst layer to the second catalyst layer may be 1:10 to 10:1, preferably 1:5 To 5:1, more preferably 1:2 to 2:1.
  • the catalyst of the invention can be used as a catalyst for preparing methyl acetate by carbonylation of dimethyl ether and/or methanol, and can significantly improve the space-time yield of methyl acetate and has considerable selectivity.
  • the present invention relates to a process for preparing methyl acetate by carbonylation of dimethyl ether and/or methanol, wherein the catalyst of the present invention is used.
  • the carbonylation reaction can be carried out batchwise or continuously.
  • the catalyst of the present invention may be in any conventional form, preferably in the form of a fixed bed.
  • the reaction gas may be passed over the catalyst.
  • the carbonylation reaction temperature may be 180-330° C., preferably 200-280° C., for example 210-240° C., such as 220° C. or 230° C.
  • the carbonylation reaction pressure may be 0.1-40 MPa, preferably 0.5-30 MPa.
  • the gas flow rate of the carbonylation reaction may be 0.1-2000 mL/min, preferably 0.5-200 mL/min, more preferably 5-100 mL/min, and most preferably 10-50 mL/min.
  • CO in the carbonylation reaction, CO is used in a molar excess relative to dimethyl ether and/or methanol.
  • the molar ratio of CO to dimethyl ether and/or methanol is 100:1-5:1, such as 80:1-8:1, 50:1-10:1, 40:1-12:1, 30:1-12:1, 20:1-14:1, more preferably 50:1-10:1, and even more preferably 25:1-12:1.
  • At least one inert gas is used in the carbonylation reaction.
  • DME is dimethyl ether and MeOH is methanol.
  • the methanol can be passed into a gasification device for preheating and gasification.
  • the gasification device can be a stainless steel tubular fixed bed reactor, which is filled with a material that does not have an adsorption function and has good thermal conductivity, preferably quartz sand or glass beads.
  • the preheating gasification temperature is 70-400°C, preferably 80-300°C.
  • the preheated methanol is then passed through a catalyst together with CO and an inert gas.
  • the methanol is carbonylated to produce acetic acid, and the acetic acid is esterified with methanol to finally produce methyl acetate.
  • methanol is first dehydrated to produce dimethyl ether, and dimethyl ether is carbonylated to produce methyl acetate.
  • the catalyst of the present invention may be loaded into a reactor and then reduced.
  • a hydrogen-containing gas may be used, such as pure H2 or a mixture of H2 and N2 ( H2 / N2 ).
  • the volume content of H2 may be 1-20%, more preferably 2-10%.
  • the flow rate of the hydrogen-containing gas may be 5-500 ml/min, preferably 10-400 ml/min, more preferably 10-300 ml/min, and most preferably 80-200 ml/min.
  • the reduction temperature may be 100-500°C, preferably 150-450°C, more preferably 200-400°C.
  • the reduction time may be 0.5-50 hours, preferably 1-20 hours, and more preferably 2-10 hours.
  • a catalyst comprising a first catalyst layer comprising a metal supported on a support material and a second catalyst layer comprising an H-type molecular sieve, wherein the first catalyst layer and the second catalyst layer are spatially isolated.
  • H-type molecular sieve is H-type ZSM-34, ZSM-35, MOR, CHA, OFF, EU-12, Al-RUB-41 or HSUZ-4, preferably H-type OFF, EU-12, Al-RUB-41, ZSM-34 or MOR, more preferably H-MOR.
  • Cu/ SiO2 was prepared by incipient wetness impregnation.
  • SiO2 (CARiACT Q series, Q3, particle size 75-150 ⁇ m, pore volume 0.30 mL/g, specific surface area 550 m3 /g) obtained from Fujisilysia, Japan was used as the carrier, and the Cu source was Cu( NO3 ) 2 ⁇ 3H2O .
  • 5 g of SiO2 was vacuum degassed at 120°C for 6 hours, then placed in a glass beaker, and 10 mL of an aqueous solution containing 2.27 g of Cu( NO3 ) 2 ⁇ 3H2O was slowly impregnated into SiO2 for 30 minutes under the assistance of ultrasound.
  • the catalyst was pretreated in flowing 20 mL/min high purity H2 at 400°C for 3 hours.
  • the reaction was carried out at 2.0 MPa and a constant temperature of 220°C, with the reaction gas Ar/DME/CO (3.1 mol% Ar, 5.2 mol% DME, the balance CO, obtained from Sumitomo Chemical) flowing through the catalyst layer at a flow rate of 20 mL/min.
  • Ar/DME/CO 3.1 mol% Ar, 5.2 mol% DME, the balance CO, obtained from Sumitomo Chemical
  • Example 1 The procedure of Example 1 was repeated, except that the copper content of the Cu(NO 3 ) 2 ⁇ 3H 2 O aqueous solution was 1.14 g Cu(NO 3 ) 2 ⁇ 3H 2 O, thereby preparing Cu/SiO 2 with a Cu loading of 6 wt %.
  • Example 1 The procedure of Example 1 was repeated, except that the copper content of the Cu(NO 3 ) 2 ⁇ 3H 2 O aqueous solution was 0.57 g Cu(NO 3 ) 2 ⁇ 3H 2 O, thereby preparing Cu/SiO 2 with a Cu loading of 3 wt %.
  • Example 1 The procedure of Example 1 was repeated, except that the copper content of the Cu(NO 3 ) 2 ⁇ 3H 2 O aqueous solution was 0.29 g Cu(NO 3 ) 2 ⁇ 3H 2 O, thereby preparing Cu/SiO 2 with a Cu loading of 1.5 wt %.
  • Example 1 The procedure of Example 1 was repeated, except that the copper content of the Cu(NO 3 ) 2 ⁇ 3H 2 O aqueous solution was 0.15 g Cu(NO 3 ) 2 ⁇ 3H 2 O, thereby preparing Cu/SiO 2 with a Cu loading of 0.75 wt %.
  • Example 1 The procedure of Example 1 was repeated, except that the copper content of the Cu(NO 3 ) 2 ⁇ 3H 2 O aqueous solution was 0.11 g Cu(NO 3 ) 2 ⁇ 3H 2 O, thereby preparing Cu/SiO 2 with a Cu loading of 0.6 wt %.
  • Example 1 The procedure of Example 1 was repeated except that 10 mL of an aqueous solution containing 1.48 g of Pd(NO 3 ) 2 was used to prepare Pd/SiO 2 with a Pd loading of 12 wt %.
  • Example 1 The procedure of Example 1 was repeated, except that 0.5 g of H-type ZSM-34 (second catalyst layer) synthesized by the method of DOI https://doi.org/10.1039/C2JM31479G literature was used instead of H-MOR.
  • Example 1 The procedure of Example 1 was repeated except that 0.5 g of H-CHA (second catalyst layer) from Clariant was used instead of H-MOR.
  • H-CHA second catalyst layer
  • Example 1 The same as Example 1, except that H-MOR is used as the first catalyst layer, and Cu/ SiO2 prepared in Example 1 is used as the second catalyst layer.
  • Example 2 The same as Example 1, except that only Cu-MOR was used as the catalyst.
  • the preparation of Cu-MOR was the same as Example 1, except that H-MOR was used instead of SiO 2 used therein.
  • the catalyst of the present invention has a significantly improved space-time yield of methyl acetate and has considerable selectivity. Compared with Comparative Example 1 using pure H-MOR, the space-time yield of methyl acetate of the catalyst of the present invention is increased by up to 170%.

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Abstract

本发明涉及一种由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂，其包括包含负载在载体材料上的金属的第一催化剂层以及包含H型分子筛的第二催化剂层，其中第一催化剂层和第二催化剂层在空间上隔离。本发明的催化剂具有显著提高的乙酸甲酯的产率且具有相当的选择性。此外，本发明还涉及使用所述催化剂由二甲醚和/或甲醇羰基化制备乙酸甲酯的方法。

Description

用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂及其用途 技术领域
本发明涉及一种催化剂，特别是用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂；以及一种使用所述催化剂由二甲醚和/或甲醇羰基化制备乙酸甲酯的方法。
背景技术
乙酸甲酯广泛用于香料、涂料、胶黏剂和医药等行业。它不仅是一种良好的环保溶剂，可用于替代丙酮、丁酮、醋酸乙酯、环戊烷等，而且是一种重要的有机原料中间体，其下游产品主要有乙酸、乙醇、醋酐、丙烯酸甲酯和乙酸乙烯酯、乙酰胺等。国内外对乙酸甲酯的需求量不断增加。近年来，乙酸甲酯又开拓了一些新的应用，如加氢合成乙醇等。
在工业上，乙酸甲酯通常由二甲醚和/或甲醇通过羰基化反应制备。
二甲醚和/或甲醇羰基化制乙酸甲酯的传统生产工艺多采用均相催化法。然而，该方法存在产物与催化剂难以分离的问题；此外，使用了贵金属，增加了生产成本；而且还使用了碘化物，对设备腐蚀较大且对操作环境不利。Wegman等人(J Chem Soc Chem Comm 1994，(8)，947-948)开发了以杂多酸RhW12PO4/SiO2为催化剂进行二甲醚羰基化反应，获得16％的乙酸甲酯产率。Volkova等人(Catalyst Letters 2002，80(3-4)，175-179)应用Rh/CsxH3-xPW12O40研究了二甲醚羰基化反应，获得了比RhW12P(VSiO2)高一个数量级的反应速率。但是，上述催化剂体系均使用了贵金属，因而提高了生产乙酸甲酯的成本。此外，这些催化剂体系在二甲醚羰基化反应过程中易生成大量的烃类和积碳，使得乙酸甲酯的生产需要频繁停车以更换催化剂。
2006年Iglesia等人(Angew.Chem，Int.Ed.，2006，(10)，1617-1620)报道了丝光沸石(MOR)和ZSM-35分子筛具有良好的二甲醚羰基化活性。由于分子筛具有不需要负载贵金属，易于再生的特点，有效地降低了制备乙酸甲酯或乙酸的成本，使得分子筛催化剂成为研究二甲醚羰基化制备乙酸 甲酯的热点。
大量的研究工作集中在沸石拓扑结构、酸强度和密度、形貌控制和金属改性对二甲醚羰基化催化剂性能的影响上。
在金属改性MOR的羰基化反应研究工作中，通过引入金属元素或负载一定量的金属元素等实验方法，增加分子筛酸性位点以及调控酸性位点的分布，达到提高分子筛催化二甲醚羰基化的活性的目的。迄今为止，二甲醚羰基化中的主流机理认为，CO或二甲醚/甲醇的活化需要分子筛的金属功能位点和分子筛的布朗斯台德酸位点的辅助。因为Weisz的亲密度准则认为金属活性位点和酸性活性位点之间的距离越短，就越能促进它们之间的交流，也就是说“越近越好”。大多数相关工作还证明，通过在纳米尺度上调整和缩短两个活性位点之间的距离，可以提高双功能催化剂的催化性能。
然而，金属离子交换后的MOR存在骨架不稳定、内部金属容易聚集等问题，而且产物乙酸甲酯的时空产率和选择性仍存在提高的空间。此外，通过浸渍法负载金属的分子筛也存在类似的问题。
因此，本领域需要一种用于由二甲醚羰基化制备乙酸甲酯的催化剂，其能显著提高乙酸甲酯的时空产率，并且具有相当的选择性。
发明内容
鉴于现有技术的上述状况，本发明人在二甲醚和/或甲醇羰基化制备乙酸甲酯和/或乙酸的分子筛催化剂方面进行了广泛而深入的研究，以期发现一种具有稳定羰基化活性的全新结构的催化剂。本发明人发现，通过将金属与分子筛在空间上隔离，能够显著提高乙酸甲酯的时空产率，并且具有相当的选择性。考虑到上文所述的本领域的一般见解，即金属活性位点和酸性活性位点之间的距离越近越好，本发明的这一发现—即，将金属与分子筛在空间上隔离能够显著提高乙酸甲酯的时空产率且具有相当的选择性—是令人惊讶的和出乎意料的。
因此，在本发明的第一方面中，本发明涉及一种催化剂，其包括包含负载在载体材料上的金属的第一催化剂层以及包含H型分子筛的第二催化剂层，其中第一催化剂层和第二催化剂层在空间上隔离。
第一催化剂层中的金属可为本领域中通常用于羰基化反应的金属改性MOR中的那些金属，例如Ca、Ag、Ce、Pt、Pd、Ga、Zn、Mg、Au、Co、Fe、Zr、Ni或Cu中的一种或多种，优选为Cu、Pd、Ag、Ce、Co、Ga、Zr、Zn或Fe中的一种或多种，最优选为Cu或Pd中的一种或两种。
第一催化剂层中的载体材料可为常规的惰性载体，例如二氧化硅、氧化锆、二氧化钛、二氧化铈、活性炭、石墨烯、碳纳米管或其组合，优选为二氧化硅、活性炭、石墨烯、碳纳米管或其组合。
第一催化剂层中的载体材料的金属负载量可为0.001-30重量％，优选为0.01-25重量％，更优选为0.1-20重量％，最优选为0.5-15重量％，在每种情况下基于第一催化剂层中金属和载体材料的总重量。
第一催化剂层中负载有金属的载体材料的比表面积可为300-700m2/g，优选为400-600m2/g，在每种情况下根据汞孔隙率法使用N2测定。令人惊讶地发现，当载体材料的比表面积处于上述范围内时，所得的催化剂具有高时空产率和选择性。
第一催化剂层中负载有金属的载体材料的孔体积可为0.10-1.50mL/g，优选为0.20-0.70mL/g，在每种情况下根据氮气吸脱附BET法测定。令人惊讶地发现，当载体材料的孔体积处于上述范围内时，所得的催化剂具有高时空产率和选择性。
第一催化剂层中负载有金属的载体材料的孔径可为3.0-50.0nm，优选为7.0-10nm。
载体材料的粒径可为10-10000μm，优选为20-5000μm，更优选为40-1000μm，更优选50-500μm，最优选为60-250μm。
金属在载体材料上的负载可通过本领域已知的方法实现，例如浸渍法，特别是初湿含浸法。初湿含浸法，也称为毛细浸渍或干法浸渍，常用于合成非均质材料，即催化剂。通常，将前体溶解在水或有机溶剂中，然后将所得溶液添加到具有与添加的溶液体积大致相同的孔隙体积的催化剂载体中。毛细作用将溶液吸入载体孔隙。然后可以干燥和煅烧催化剂以除去挥发性组分，以将金属沉积在载体材料上。
在浸渍之前，可对载体材料进行真空脱气处理。真空脱气处理可在 80-150℃下的温度下进行，处理时间可为0.5-10小时。然后，将真空脱气处理的载体浸入所述金属的可溶性盐的溶液中。所述可溶性盐可为硝酸盐、硫酸盐、羧酸盐或卤化物，尤其是氯化物。例如，对铜而言，其可溶性盐可为硝酸铜、硫酸铜、醋酸铜、草酸铜或卤化铜，其中卤化铜可选自氯化铜或溴化铜，包括水合物形式和非水合物形式。优选地，所述水溶性铜盐为硝酸铜、硫酸铜或氯化铜。此外，还可以使用铜络合物，例如铜氨络合物。
在浸渍过程中，可对载体材料进行搅拌以使金属负载均匀。搅拌可采用搅拌器或超声辅助进行，优选采用超声辅助。
在浸渍后，可将得到的潮湿固体真空脱气，然后干燥，最后煅烧。真空脱气可在80-150℃的温度下进行，处理时间可为0.5-72小时，优选为10-50小时。干燥可在80-150℃的温度下进行，干燥时间可为0.5-24小时。煅烧可在200-700℃，优选300-600℃的温度下进行，煅烧时间可为0.5-24小时。
第二催化剂层中的H型分子筛可为H型ZSM-34、ZSM-35、MOR、CHA、OFF、EU-12、Al-RUB-41或HSUZ-4，优选为H型OFF、EU-12、Al-RUB-41、ZSM-34或MOR，更优选为H型MOR(H-MOR)。
所述H型分子筛可商购获得，或者可通过本领域公知的方法制备，例如溶剂热法，优选水热法。水热法包括以下步骤：将铝源、硅源、碱源、任选的模板剂以及水混合，进行水热晶化反应，得到晶化反应物料；将所述晶化反应物料干燥，然后焙烧，最后进行还原，从而得到H型分子筛。
所述铝源可选自偏铝酸钠、硝酸铝、异丙醇铝、氯化铝中的一种或多种；所述碱源可选自氢氧化钠、碳酸钠、氢氧化钾中的一种或多种；所述硅源可选自二氧化硅、硅溶胶、水玻璃、有机硅烷中的一种或多种；当使用时，所述模板剂可选自氯化胆碱，四乙基氢氧化铵，四甲基氯化铵中的一种或多种。
所述铝源、碱源、硅源、任选的模板剂(SDA)和水的用量是本领域所已知的，例如当制备H-MOR时，其摩尔比可为n(Al2O3):n(Na2O):n(K2O):n(SiO2):n(H2O):n(SDA)＝1:(2.5-5.1):(0.76-9.13):(10.54-30):(130-216):(0-1.3)。
水热晶化可在密闭容器(例如高压釜)中在反应体系的自生压力下进行。晶化温度范围可为100-300℃，优选150-300℃；晶化时间可为1小时至10天，优选4小时至5天。
在水热晶化时，可加入缓释剂。合适的缓释剂例如为但不限于尿素、醋酸铵、草酸铵或碳酸铵。缓释剂的用量可为0-2.0重量％，优选为0.01-1.5重量％，更优选为0.1-1.0重量％，基于反应混合物的总重量。
在反应后，可将反应混合物过滤，并用蒸馏水洗涤数次(例如1-10次，优选1-3次)，直到洗液呈中性。然后，将滤出物干燥。干燥可采用现有技术中已知的各种干燥方式进行，例如普通加热干燥、微波干燥和/或喷雾干燥。在加热干燥的情况下，干燥温度可为50-200℃，优选为80-150℃，干燥时间可为1-24小时，更优选为4-20小时，更优选为8-15小时。
在干燥后，可将所得产物成型，成型可采用现有技术中已知的方式进行，例如压片成型、滚球成型或挤出成型。成型可在加入润滑剂下进行。所述润滑剂例如为石墨等。润滑剂的用量可为1-10％，优选为1-5％，基于润滑剂和干燥后产物的总重量。在成型后，可将所得成型体破碎并经40-60目筛筛分。
在筛分后，将所得产物焙烧。焙烧可采用现有技术已知的各种方式进行，例如在马弗炉中进行。焙烧温度可为300-800℃，优选为350-600℃，更优选为350-500℃；焙烧时间可为1-24小时，优选为1-12小时，更优选为1-5小时。
在本发明的催化剂中，“第一催化剂层”和“第二催化剂层”是相对于反应物料(例如二甲醚和CO等)的流动方向而言的，即相对于反应物料的流动方向，第一催化剂层位于第二催化剂层的上游。
在本发明的催化剂中，“空间上隔离”意指第一催化剂层和第二催化剂在空间上相距达宏观上可辨的距离，例如厘米级，例如0.5-100cm，优选1-100cm，更优选1-50cm，更优选1-20cm，最优选1-10cm。第一催化剂层和第二催化剂层可通过惰性材料网隔离，例如石英棉、石英砂、活性炭、二氧化硅、石墨、玻璃珠或陶瓷环。
第一催化剂层与第二催化剂层的重量比可为1:10至10:1，优选为1:5 至5:1，更优选为1:2至2:1。
本发明的催化剂可用作由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂，其能显著提高乙酸甲酯的时空产率，并且具有相当的选择性。
因此，在本发明的另一个方面中，本发明涉及一种由二甲醚和/或甲醇羰基化制备乙酸甲酯的方法，其中使用本发明的催化剂。
根据本发明，所述羰基化反应可以间歇进行，也可连续进行。
本发明的催化剂可以采用任何常规形式，优选以固定床的形式使用。在羰基化反应中，可以使反应气体通过催化剂。
根据本发明的优选实施方案，羰基化反应温度可为180-330℃，优选200-280℃，例如210-240℃，如220℃或230℃。羰基化反应的压力可为0.1-40MPa，优选0.5-30MPa。羰基化反应的气体流速可为0.1-2000mL/分钟，优选0.5-200mL/分钟，更优选5-100mL/分钟，最优选10-50mL/分钟。
根据本发明，在羰基化反应中，CO相对于二甲醚和/或甲醇以摩尔过量使用。优选CO与二甲醚和/或甲醇的摩尔比为100:1-5:1，例如80:1-8:1，50:1-10:1，40:1-12:1，30:1-12:1，20:1-14:1，更优选50:1-10:1，还更优选25:1-12:1。
在本发明的一个实施方案中，在羰基化反应中使用至少一种惰性气体，优选氩气。当使用二甲醚和甲醇作为原料时，反应气体的摩尔比为Ar:DME:MeOH:CO＝1:(0.1-20):(0.1-50):(1-50)，优选为1:(0.1-50):(0.1-50):(10-50)。当使用二甲醚或甲醇作为原料时，反应气体的摩尔比为Ar:DME/MeOH:CO＝1:(0.1-50):(1-50)，优选为1:(0.1-50):(10-50)。其中DME为二甲醚，MeOH为甲醇。
当使用甲醇时，可以将甲醇通入气化装置预热气化。气化装置可以为不锈钢管式固定床反应器，其中填充不具有吸附功能且导热良好的物质，优选为石英砂或玻璃珠。预热气化温度为70-400℃，优选为80-300℃。然后使预热的甲醇与CO和惰性气体一起通过催化剂。当经过催化床时，甲醇被羰基化生成乙酸，乙酸通过和甲醇的酯化反应最后生产乙酸甲酯。或者，甲醇先脱水生成二甲醚，二甲醚经由羰基化反应生产乙酸甲酯。
在反应前，可将本发明的催化剂装入反应器中，然后进行还原。还原 可使用含氢气体进行，例如纯H2或H2和N2的混合物(H2/N2)。在使用H2/N2的情况下，H2的体积含量可为1-20％，更优选为2-10％。含氢气体流速可为5-500ml/分钟，优选为10-400ml/分钟，更优选为10-300ml/分钟，最优选为80-200ml/分钟。还原温度可为100-500℃，优选为150-450℃，更优选为200-400℃。还原时间可为0.5-50小时，优选为1-20小时，更优选为2-10小时。
实现本发明目的的技术方案可以概括如下：
1.一种催化剂，其包括包含负载在载体材料上的金属的第一催化剂层以及包含H型分子筛的第二催化剂层，其中第一催化剂层和第二催化剂层在空间上隔离。
2.如实施方案1所述的催化剂，其中第一催化剂层中的金属为Ca、Ag、Ce、Pt、Pd、Ga、Zn、Mg、Au、Co、Fe、Zr、Ni或Cu中的一种或多种，优选为Cu、Pd、Ag、Ce、Co、Ga、Zr、Zn或Fe中的一种或多种，最优选为Cu或Pd中的一种或多种。
3.如实施方案1或2所述的催化剂，其中第一催化剂层中的载体材料为二氧化硅、氧化锆、二氧化钛、二氧化铈、活性炭、石墨烯、碳纳米管或其组合，优选为二氧化硅、活性炭、石墨烯、碳纳米管或其组合。
4.如实施方案1-3中任一项所述的催化剂，其中H型分子筛为H型ZSM-34、ZSM-35、MOR、CHA、OFF、EU-12、Al-RUB-41或HSUZ-4，优选为H型OFF、EU-12、Al-RUB-41、ZSM-34或MOR，更优选为H-MOR。
5.如实施方案1-4中任一项所述的催化剂，其中第一催化剂层中的载体材料的金属负载量为0.001-30重量％，优选为0.01-25重量％，更优选为0.1-20重量％，最优选为0.5-15重量％，在每种情况下基于金属和载体材料的总重量。
6.如实施方案1-5中任一项所述的催化剂，其中第一催化剂层和第二催化剂在空间上相距达0.5-100cm，优选1-100cm，更优选1-50cm，更优选1-20cm，最优选1-10cm的距离。
7.一种由二甲醚和/或甲醇羰基化制备乙酸甲酯的方法，其中使用如实施方案1-6中任一项所述的催化剂。
具体实施方式
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
实施例1
Cu/SiO2的制备
Cu/SiO2通过初湿含浸法制备。以获自日本Fujisilysia公司的SiO2(CARiACT Q系列，Q3，粒径75-150μm，孔体积0.30mL/g，比表面积550m3/g)为载体，Cu源为Cu(NO3)2·3H2O。将5g SiO2在120℃下真空脱气处理6小时，然后置于玻璃烧杯中，将含有2.27g Cu(NO3)2·3H2O的10mL水溶液在超声辅助下缓慢浸渍到SiO2中30分钟。在浸渍过程中，加入2g水，以确保铜前驱体溶液在SiO2中的均匀分散。将得到的潮湿固体在120℃下真空脱气48小时，在120℃下干燥12小时，然后在500℃下煅烧3小时。Cu负载量为12wt％。
将0.5g Cu/SiO2(第一催化剂层)和0.5g获自日本TOSOH公司的H-MOR(第二催化剂层)置于内径为9.5mm的不锈钢反应器中，Cu/SiO2催化剂层与H-MOR之间的距离为1cm，使用石英棉隔离。
催化剂活性测试
在暴露于反应物之前，将催化剂在流动的20mL/分钟高纯度H2中在400℃下预处理3小时。反应在2.0MPa、220℃恒温下进行，反应气体Ar/DME/CO(3.1mol％Ar，5.2mol％DME，余量为CO，获自Sumitomo Chemical)以20mL/分钟的流速流过催化剂层。
实施例2
重复实施例1的程序，不同的是Cu(NO3)2·3H2O水溶液的铜含量为1.14g Cu(NO3)2·3H2O，从而制备Cu负载量为6wt％的Cu/SiO2。
实施例3
重复实施例1的程序，不同的是Cu(NO3)2·3H2O水溶液的铜含量为0.57g Cu(NO3)2·3H2O，从而制备Cu负载量为3wt％的Cu/SiO2。
实施例4
重复实施例1的程序，不同的是Cu(NO3)2·3H2O水溶液的铜含量为0.29g Cu(NO3)2·3H2O，从而制备Cu负载量为1.5wt％的Cu/SiO2。
实施例5
重复实施例1的程序，不同的是Cu(NO3)2·3H2O水溶液的铜含量为0.15g Cu(NO3)2·3H2O，从而制备Cu负载量为0.75wt％的Cu/SiO2。
实施例6
重复实施例1的程序，不同的是Cu(NO3)2·3H2O水溶液的铜含量为0.11g Cu(NO3)2·3H2O，从而制备Cu负载量为0.6wt％的Cu/SiO2。
实施例7
重复实施例1的程序，不同的是使用含有1.48g Pd(NO3)2的10mL水溶液，从而制备Pd负载量为12wt％的Pd/SiO2。
实施例8
重复实施例1的程序，不同的是使用0.5g通过DOI https://doi.org/10.1039/C2JM31479G文献方法合成的H型ZSM-34(第二催化剂层)代替H-MOR。
实施例9
重复实施例1的程序，不同的是使用0.5g获自Clariant公司的H-CHA(第二催化剂层)代替H-MOR。
对比例1
仅使用H-MOR作为催化剂。
对比例2
与实施例1相同，不同的是使用H-MOR作为第一催化剂层，使用实施例1制备的Cu/SiO2作为第二催化剂层。
对比例3
与实施例1相同，不同的是仅使用Cu-MOR作为催化剂。Cu-MOR的制备与实施例1相同，不同的是用H-MOR代替其中所用的SiO2。
对比例4
与实施例1相同，不同的是将Cu/SiO2和H-MOR物理混合，然后用作催化剂。
测定各催化剂的乙酸甲酯的时空产率和选择性。结果汇总在表1中。
表1
从表1可见，本发明的催化剂具有显著提高的乙酸甲酯的时空产率且具有相当的选择性。与使用纯H-MOR的对比例1相比，本发明催化剂的乙酸甲酯时空产率最高提高了170％。

Claims (7)

  1. 一种催化剂，其包括包含负载在载体材料上的金属的第一催化剂层以及包含H型分子筛的第二催化剂层，其中第一催化剂层和第二催化剂层在空间上隔离。
  2. 如权利要求1所述的催化剂，其中第一催化剂层中的金属为Ca、Ag、Ce、Pt、Pd、Ga、Zn、Mg、Au、Co、Fe、Zr、Ni或Cu中的一种或多种，优选为Cu、Pd、Ag、Ce、Co、Ga、Zr、Zn或Fe中的一种或多种，最优选为Cu或Pd中的一种或两种。
  3. 如权利要求1或2所述的催化剂，其中第一催化剂层中的载体材料为二氧化硅、氧化锆、二氧化钛、二氧化铈、活性炭、石墨烯、碳纳米管或其组合，优选为二氧化硅、活性炭、石墨烯、碳纳米管或其组合。
  4. 如权利要求1-3中任一项所述的催化剂，其中H型分子筛为H型ZSM-34、ZSM-35、MOR、CHA、OFF、EU-12、Al-RUB-41或HSUZ-4，优选为H型OFF、EU-12、Al-RUB-41、ZSM-34或MOR，更优选为H-MOR。
  5. 如权利要求1-4中任一项所述的催化剂，其中第一催化剂层中的载体材料的金属负载量为0.001-30重量％，优选为0.01-25重量％，更优选为0.1-20重量％，最优选为0.5-15重量％，在每种情况下基于金属和载体材料的总重量。
  6. 如权利要求1-5中任一项所述的催化剂，其中第一催化剂层和第二催化剂在空间上相距达0.5-100cm，优选1-100cm，更优选1-50cm，更优选1-20cm，最优选1-10cm的距离。
  7. 一种由二甲醚和/或甲醇羰基化制备乙酸甲酯的方法，其中使用如权利要求1-6中任一项所述的催化剂。
PCT/CN2023/124541 2022-10-17 2023-10-13 用于由二甲醚和/或甲醇羰基化制备乙酸甲酯的催化剂及其用途 WO2024083048A1 (zh)

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