WO2022206673A1 - 低温羰基化分子筛催化剂及其用途 - Google Patents

低温羰基化分子筛催化剂及其用途 Download PDF

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WO2022206673A1
WO2022206673A1 PCT/CN2022/083366 CN2022083366W WO2022206673A1 WO 2022206673 A1 WO2022206673 A1 WO 2022206673A1 CN 2022083366 W CN2022083366 W CN 2022083366W WO 2022206673 A1 WO2022206673 A1 WO 2022206673A1
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catalyst
zsm
molecular sieve
reaction
shaped body
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French (fr)
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高潮
杨国辉
椿范立
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高化学株式会社
高潮
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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
    • B01J29/70—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
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions

Definitions

  • the present invention relates to a catalyst for the carbonylation of dimethyl ether to methyl acetate comprising ZSM-34 molecular sieve as catalytically active material; a shaped body comprising the catalyst and a method for producing the shaped body; and A method for preparing methyl acetate from the carbonylation of dimethyl ether using the catalyst.
  • molecular sieve catalysts have been widely studied and applied as mature porous materials, such as gas adsorption and separation materials, precursors for ion exchange, and shape-selective catalysts for the production of chemicals. Due to the tunable active sites, ordered pore structures, and excellent shape selectivity of molecular sieves, this class of catalysts has greatly influenced the traditional field of heterogeneous catalysis. So far, there are more than 230 molecular sieve catalysts whose topology structures have been determined, but only a very small number of molecular sieves are actually used for catalytic reactions. Because molecular sieve catalysts have great potential in chemical production and application, it is a direction of great research significance and practical application value to discover and design more new molecular sieves for catalytic reactions.
  • Methyl acetate is widely used in fragrances, coatings, adhesives and pharmaceuticals. It is not only a good environmentally friendly solvent, which 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 and vinyl acetate, acetamide, etc. The demand for methyl acetate at home and abroad continues to increase. In recent years, methyl acetate has developed some new applications, such as hydrogenation to synthesize ethanol.
  • methyl acetate is usually prepared from dimethyl ether by carbonylation.
  • the inventor of the present invention has carried out extensive and in-depth research on the molecular sieve catalyst for the production of methyl acetate by carbonylation of dimethyl ether, and found that a main reason for the deactivation of the carbonylation molecular sieve catalyst is that the molecular sieve catalyst is deactivated at high temperature. Internally or surface-generated coke covers acidic active sites. If the reaction temperature of carbonylation can be lowered, the carbon deposition reaction can be greatly suppressed or even eliminated. However, the currently generally accepted carbonylation temperature of dimethyl ether is 220 °C. Once the temperature is lower than this temperature, the existing molecular sieve catalysts all show extremely low catalytic activity.
  • the inventors of the present invention have surprisingly found a catalyst with excellent low-temperature carbonylation activity, which comprises ZSM-34 as the catalytically active material, and can obtain a fairly high conversion of dimethyl ether and nearly 100 dimethyl ether even at low temperature % methyl acetate selectivity and also exhibits excellent stability.
  • the present invention relates to a catalyst for the carbonylation of dimethyl ether to methyl acetate comprising ZSM-34 molecular sieve as catalytically active material.
  • the catalyst comprises ZSM-34 molecular sieve as the only catalytically active material.
  • ZSM-34 molecular sieves are well known in the art and are either commercially available or can be synthesized by hydrothermal methods.
  • hydrothermal synthesis of ZSM-34 molecular sieve may include the following steps:
  • mixture A The aluminum source, alkali source, silicon source, optional template agent and water are uniformly mixed and aged to obtain mixture A;
  • the aluminum source can be selected from one or more of sodium metaaluminate, aluminum nitrate, aluminum isopropoxide, and aluminum chloride; the alkali source can be selected from sodium hydroxide, sodium carbonate, and potassium hydroxide. one or more; the silicon source can be selected from one or more of silicon dioxide, silica sol, water glass, organosilane; when used, the template agent can be selected from choline chloride, four One or more of ethylammonium hydroxide and tetramethylammonium chloride.
  • Hydrothermal crystallization can adopt static or dynamic crystallization, and crystallization can adopt one-stage or two-stage crystallization method.
  • the crystallization temperature can range from 100-200°C, preferably 140°C; the crystallization time can be 1 hour to 10 days, preferably 4 hours to 5 days.
  • the drying conditions in steps b and c may be 80-150° C. for 6-24 hours.
  • the roasting temperature in steps b and c may be 450-600°C, preferably 500-600°C; the roasting time may be 0.5-15 hours, preferably 1-10 hours.
  • the ZSM-34 molecular sieve can obtain extremely high methyl acetate selectivity and yield at low temperature, and also has excellent stability.
  • the ZSM-34 molecular sieve may be in an unmodified form, ie, H-ZSM-34.
  • molecular sieves do not need to support precious metals and are easy to regenerate, which effectively reduces the cost of preparing methyl acetate or acetic acid.
  • the ZSM-34 molecular sieve can also be optionally modified, wherein the modification is selected from one or more of mesopore formation, metal ion exchange or basic organic adsorption, preferably one or two kind.
  • the modification is a mesopore-forming comprising treating the ZSM-34 molecular sieve with a pore-forming agent.
  • the interior of the molecular sieve is usually a microporous structure, specifically, pores smaller than 2 nm. When small molecules react within the pores, there is a problem of mass transfer. Mesopores can build 2-50nm channels or holes inside the molecular sieve, which can speed up the transport of reactants and products on the catalyst and speed up the reaction.
  • Creating mesopores involves treating ZSM-34 molecular sieves with a pore-forming agent.
  • the formation of mesopores includes dispersing ZSM-34 molecular sieves in a solution of a pore-forming agent with a certain concentration, and stirring for a period of time at a set temperature.
  • the obtained product can be filtered, washed to neutrality, and then the obtained filter cake can be dried, and the drying conditions can be, for example, 80-150° C. for 6-24 hours. After drying, the resulting material can be fired.
  • the calcination temperature can be, for example, 450-600°C, preferably 500-600°C; the calcination time can be 0.5-15 hours, preferably 1-10 hours.
  • the obtained molecular sieve can be subjected to ion exchange treatment to obtain the mesopore-modified ZSM-34 molecular sieve in the H form.
  • Suitable pore formers are known to those skilled in the art, such as alkaline substances such as one or more of sodium hydroxide, potassium hydroxide, sodium carbonate.
  • the solid-liquid ratio of the treatment can be 1:5-50.
  • the concentration of the alkaline substance solution may be 0.01-2M, preferably 0.1-1M, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 or 1M.
  • the treatment temperature can be from room temperature to 100°C; the treatment time can be from 10 minutes to 10 hours, preferably 1-8 hours.
  • the modification is metal ion exchange, thereby obtaining a metal-modified ZSM-34 molecular sieve.
  • the metal can be selected from one or more of copper, silver, zinc, iron, gallium, zirconium and cobalt, preferably one or more of copper, silver, zinc, iron, cobalt and gallium, more It is preferably one or more selected from copper, silver, gallium and cobalt, most preferably gallium or copper.
  • the metal ion exchange may include contacting the ZSM-34 molecular sieve with a solution comprising the metal ion, thereby performing ion exchange.
  • the metal precursor for ion exchange can be selected from one or more of nitrates, sulfates, and hydrochlorides of the metals.
  • the solid-liquid ratio of ion exchange can be 1:5-50; the concentration of metal ion solution can be 0.01-5M.
  • the number of ion exchanges may be 1-5 times.
  • the temperature of the ion exchange treatment can be from room temperature to 100°C; the time can be from 10 minutes to 5 hours. After ion exchange, the resulting product can be filtered and washed to neutrality.
  • the resulting filter cake is then dried, and the drying conditions may be, for example, 80-150° C. for 6-24 hours. After drying, the resulting material can be fired.
  • the calcination temperature can be, for example, 450-600°C, preferably 500-600°C; the calcination time can be 0.5-15 hours, preferably 1-10 hours.
  • the modification is basic organic adsorption. After the adsorption of basic organic matter, the deactivation sites in the molecular sieve will be covered by basic substances, and the deactivation of the reaction will be greatly slowed down.
  • the basic organic substance is selected from one or more of pyridine and its derivatives.
  • the pyridine derivative is a compound in which the hydrogen atoms on the pyridine ring are independently substituted by halogen, alkyl, haloalkyl or nitro, preferably by F, Cl, Br, I, CH 3 , CF 3 , CH 3 CH 2 or NO 2 substituted compounds.
  • the pyridine derivative may be selected from C 1 -C 10 alkylpyridines such as 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-methylpyridine Ethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, etc., halogen-substituted pyridines, such as 2-chloropyridine, 3-chloropyridine or 4-chloropyridine, etc.
  • C 1 -C 10 alkylpyridines such as 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-methylpyridine Ethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, etc.
  • halogen-substituted pyridines such as 2-chloropyridine, 3-chloropyridine or 4-chloropyridine, etc.
  • the adsorption method may be gas phase adsorption, which may include passing a carrier gas carrying vapors of pyridine or derivatives thereof through ZSM-34 molecular sieves.
  • gas phase adsorption the original powder or shaped body of ZSM-34 molecular sieve can be placed in a fixed bed or tube furnace, and then heated to the target temperature, so that the carrier gas carrying the vapor of pyridine or its derivatives passes through the ZSM-34 molecular sieve After a period of time, the temperature is lowered to obtain the product.
  • the adsorption temperature can be 200-400°C, and the adsorption pressure can be from normal pressure to 5MPa.
  • the carrier gas can be one or more of inert gases such as nitrogen, helium, and argon, and the flow rate is 1-100 mL/min.
  • the treatment time can be from 10 minutes to 10 hours, such as 1-5 hours.
  • the catalyst can be in the form of raw powder, the particle size of which is, for example, 50 nm to 50 ⁇ m; or can be formed into shaped bodies together with a binder and optionally other auxiliaries. After molding, although the methyl acetate selectivity and STY of the catalyst decreased slightly, its compressive strength increased, making it suitable for industrial applications.
  • the present invention relates to a catalyst shaped body for the carbonylation of dimethyl ether to methyl acetate, wherein the catalyst shaped body comprises ZSM-34 molecular sieve as catalytically active material; preferably Typically, the catalyst shaped body contains ZSM-34 molecular sieve as the sole catalytically active material.
  • the catalyst shaped bodies may be in the form of extrudates.
  • the shaped body can be obtained by mixing the ZSM-34 molecular sieve with a binder and optional other auxiliary agents, followed by shaping, and then calcining the resulting shaped body.
  • the present invention relates to a method for preparing the catalyst shaped body, which comprises mixing the ZSM-34 molecular sieve with a binder and optionally other auxiliary agents, followed by shaping, The resulting shaped body is then fired.
  • the binder may be selected from one or more of phosphoric acid, pseudo-boehmite, hydroxymethyl cellulose, and silica sol.
  • the other auxiliary agents can be selected from one or more of self-extruding agents, peptizers and pore-enlarging agents.
  • the extrusion aid can be selected from one or more of saffron powder, polytetrafluoroethylene and starch.
  • the peptizer can be selected from one or more of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid.
  • the pore-enlarging agent can be selected from one or more of polyethylene glycol, polyether, hexamethylenetetraethylamine, and urea.
  • Shaping can be carried out by various means, such as extrusion, pressing, etc., preferably extrusion.
  • the shaped body can be in various desired shapes, such as spherical, cylindrical, sheet-like, cylindrical, and the like.
  • the shaped body may have a diameter of 30-10 mm and a length of 5-20 mm.
  • the ZSM-34 molecular sieve can be modified, wherein the modification is selected from one or more of mesopore formation, metal ion exchange or basic organic adsorption.
  • the modification is selected from one or more of mesopore formation, metal ion exchange or basic organic adsorption.
  • specific modification methods see the methods described above for catalyst modification.
  • the catalyst or catalyst shaped body of the present invention can be used for the carbonylation of dimethyl ether to produce methyl acetate, and even at low temperature, a relatively high conversion rate of dimethyl ether and a selectivity of nearly 100% of methyl acetate can be obtained, and the performance is also excellent stability.
  • the present invention relates to a process for the preparation of methyl acetate from the carbonylation of dimethyl ether, wherein the catalyst or catalyst shaped bodies of the present invention are used.
  • the method comprises passing a reaction gas comprising carbon monoxide and dimethyl ether through the catalyst or catalyst shaped body.
  • the catalyst or shaped body can be packed in a fixed-bed reactor, and the reaction gas can be introduced to increase the pressure, and the temperature can be raised to the reaction temperature after reaching the target pressure.
  • the catalytic reaction is carried out at a steady flow rate, pressure and temperature, and the products are analyzed online in real time.
  • the catalyst mass can be 0.1-10 g at 10-200 mL/min reaction gas flow rate.
  • the reaction pressure may be 0.1-20 MPa, preferably 1-5 MPa.
  • the reaction temperature may be 80-250°C, preferably 100-220°C, more preferably 150-200°C, eg 180°C.
  • the reaction gas flow rate can be 10-200 mL/min.
  • the composition of the reaction gas is carbon monoxide and dimethyl ether, wherein the content of dimethyl ether is less than or equal to 5 mol%.
  • the catalyst or shaped catalyst bodies may optionally be reduced after the catalyst or shaped catalyst bodies have been placed in the reactor and before the start of the reaction.
  • the reduction is carried out, for example, using hydrogen.
  • the reduction temperature may be 200-600°C, preferably 250-450°C; the reduction time may be 1-20 hours, preferably 5-15 hours.
  • the present invention relates to the use of ZSM-34 molecular sieve as a catalytically active material in the carbonylation of dimethyl ether to methyl acetate; preferably, ZSM-34 molecular sieve is used as the sole catalytically active material used in this reaction.
  • the ZSM-34 molecular sieve is as described above.
  • the ZSM-34 molecular sieve can be in an unmodified form, or in a modified form, wherein the modification is selected from one or more of mesoporous, metal ion exchange or basic organic adsorption, preferably one or more. two kinds.
  • the present invention compares the performance of various molecular sieve catalysts that have been reported and that may have carbonylation activity.
  • the inventors found through reaction evaluation that compared with general molecular sieve catalysts, such as H-MOR, H-ZSM-35, H-SAPO-34, H-SUZ-4, H-EU-12, etc., ZSM-34 molecular sieve showed Superior low temperature activity. Only a reaction temperature of 180 °C is required, and the space-time yield (STY) of methyl acetate can reach about 700 mmol/kg h.
  • STY space-time yield
  • the catalytic stability of molecular sieves modified by adsorption of pyridine and its derivatives has been greatly improved.
  • the formed ZSM-34 molecular sieve product has stronger mechanical strength and acid content.
  • Fig. 1 is the structural representation of the H-ZSM-34 molecular sieve catalyst of the present invention.
  • FIG. 2 is a graph showing the change in the life evaluation results of H-ZSM-34 catalysts treated with basic organic matter adsorption and without any treatment in Example 4.
  • FIG. 2 is a graph showing the change in the life evaluation results of H-ZSM-34 catalysts treated with basic organic matter adsorption and without any treatment in Example 4.
  • the H-ZSM-34 zeolite with Si/Al of 3.6 was prepared using choline chloride (ChCl) as an organic template.
  • the original molar composition of the aluminosilicate gel was 1.3ChCl : 12.7SiO2 : 1.0Al2O3 : 0.76K2O : 2.5Na2O : 216H2O .
  • H-MOR Commercial molecular sieves H-MOR, H-ZSM-35, H-SAPO-34, H-SUZ-4, H-EU-12 purchased from Tosoh Corporation were used as comparative catalysts for the reaction for activity comparison.
  • the molecular sieve catalyst was modified with different concentrations of basic substances to create mesopores.
  • the operation process is as follows:
  • the H-ZSM-34 molecular sieve prepared in Example 1 is used as the precursor.
  • Alkali modification was performed with different concentrations of aqueous NaOH (0.2, 0.4, 0.6, 1.0, 2.0 M).
  • the H-ZSM-34 molecular sieves were treated with NaOH solutions of the above concentrations at 80 °C for 4 hours (solid-liquid ratio 1:10). After filtration, the resulting sample was washed to neutral pH and dried at 100°C for 8 hours.
  • H-ZSM-34 was prepared.
  • the mesoporous modified sample was denoted as H-ZSM-34(X), where X was the concentration of sodium hydroxide.
  • the molecular sieve catalyst was modified by different metal ion exchange.
  • the operation process is as follows:
  • the H-ZSM-34 molecular sieve prepared in Example 1 is used as the precursor.
  • Ion exchange was performed with 1 M aqueous metal nitrates (Ag, Cu, Fe, Co, Zn or Ga).
  • the H-ZSM-34 molecular sieves were treated with 1M solutions of the various metal nitrates mentioned above at 80°C for 4 hours (solid-to-liquid ratio 1:10). After filtration, the resulting sample was washed to neutral pH and dried at 100°C for 8 hours. Then, the catalyst was calcined at 550° C. for 4 hours to prepare a ZSM-34 molecular sieve catalyst modified by metal ion exchange.
  • the sample modified by metal ions is denoted as H-ZSM-34(Y), where Y is the metal used.
  • the adsorption of basic organics on the molecular sieve catalyst improves the stability.
  • the operation procedure was as follows: 0.5 g of the H-ZSM-34 sample prepared in Example 1 was treated with N2 saturated with pyridine at room temperature in a fixed bed reactor. The pyridine saturated vapor carried by pure N 2 was passed into the reaction tube at 300 °C (flow rate 30 mL/min) to process the H-ZSM-34 sample loaded therein. Processing time was 4 hours. The pyridine tube was then removed and the purge continued for 1 hour under nitrogen flow to remove excess physisorbed pyridine. After the above adsorption operation was completed, the carbonylation reaction described in Example 1 was carried out directly.
  • the H-ZSM-34 catalyst without any modification was also evaluated for the catalytic reaction lifetime.
  • the comparison results are shown in Figure 2. It can be seen from Figure 2 that the stability of the molecular sieve catalyst after treatment with pyridine adsorption is higher than that of H-ZSM-34 without any modification, and its dimethyl ether conversion rate remains basically constant even in the reaction time of 500 hours . In contrast, H-ZSM-34 without any modification continued to decrease in the reaction time.
  • the molecular sieve catalyst powder is shaped.
  • the mass ratio of , Z represents the mass ratio of pseudo-boehmite.
  • H-ZSM34 molecular sieve original powder mix with 1g of hydroxymethyl cellulose, 1g, 3g, 5g or 7g of pseudoboehmite, 0.56g of saffron powder, and 2g of polyethylene glycol, mix them evenly for 10min, and then slowly add 2.4g of nitric acid and 14g of water were continuously stirred for 30min to obtain a sticky dough.
  • Example 4 Using the obtained shaped catalyst, the carbonylation reaction described in Example 1 was carried out, and the compressive strength and catalytic activity of the product are shown in Table 4.
  • H-ZSM-34 has excellent low-temperature carbonylation activity, and its activity at a reaction temperature of 180°C is about 7 times that of H-MOR, the best known carbonylation catalyst.
  • the selectivity to the product methyl acetate was 100%.
  • the activity of H-ZSM-34 first increased and then decreased with the increase of sodium hydroxide concentration, and the optimal sodium hydroxide modification concentration was around 0.6M.
  • the addition of different metals has an effect on the catalytic activity of H-ZSM-34 zeolite. In addition to Zn, other metals can effectively improve the catalytic activity.
  • the catalyst modified by Cu has the best activity, and the modified STY can reach 835 (mmol/kg h). After molding, the compressive strength of the catalyst increased with the addition of pseudo-boehmite, but the selectivity and STY of methyl acetate decreased.

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Abstract

本发明涉及一种全新的高效二甲醚低温羰基化制乙酸甲酯用催化剂，其包含ZSM-34作为催化活性材料，并且可对该催化剂进行造介孔、金属离子交换或碱性有机物吸附中的一种或多种改性来提升其催化活性，以及包含所述催化剂的催化剂成型体以及所述催化剂成型体的制备方法。所述催化剂在用于二甲醚羰基化制乙酸甲酯时，可以在低温获得极高的乙酸甲酯选择性和收率，并且还具有极佳的稳定性。

Description

低温羰基化分子筛催化剂及其用途 技术领域
本发明涉及一种用于由二甲醚羰基化制乙酸甲酯的催化剂，其包含ZSM-34分子筛作为催化活性材料；一种包含所述催化剂的成型体和制备所述成型体的方法；以及一种使用所述催化剂由二甲醚羰基化制备乙酸甲酯的方法。
背景技术
在工业领域中，分子筛催化剂已作为成熟的多孔材料被广泛地研究和应用，例如作为气体吸附和分离材料，离子交换的母体和用于生产化学品的择形催化剂。由于分子筛具有可调节的活性位点，有序的孔结构和出色的择形性，这类催化剂对传统的非均相催化领域产生了巨大影响。迄今为止，确定了拓扑结构的分子筛催化剂一共有230多种，但是真正用于催化反应的分子筛只占极少数。由于分子筛催化剂在化工生产应用上具有巨大的潜力，因此发现和设计更多新分子筛用于催化反应是一个极具研究意义和实际应用价值的方向。
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通过羰基化反应制备。
二甲醚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RhW 12PO 4/SiO 2为催化剂进行二甲醚羰基化反应，获得16％的乙酸甲酯收率。Volkova等人(Catalyst Letters 2002，80(3-4)，175-179)应用Rh/CsxH 3-xPW 12O 40研究了二甲醚羰基化反应，获得了比RhW 12P(VSiO 2)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。
然而，目前所采用的丝光沸石和ZSM-35分子筛仍然具有稳定性差，易失活的特点，在二甲醚羰基化过程中仍然需要频繁更换催化剂，不能实现长时间连续制备乙酸甲酯的目的。近年来，伞晓广等人(CN 108047030A)在使用两步法制备醋酐的反应中使用了金属离子交换改性的丝光沸石催化剂(其主要特征是具有八元环和十二元环)，从而增加该催化剂的活性。当中述及，引入的金属离子可与八元环结构中的β酸协同作用提高催化剂的反应活性；但稳定性方面，由于金属离子不能选择性地结合所有十二元环的酸性位，随着反应的进行，催化剂还是存在严重失活的现象。于吉红等人(CN 108586247A)分别使用氢型斜发沸石和氢型丝光沸石催化二甲醚羰化反应，结果表明仅具有八元环的斜发沸石稳定性具有明显优势，但随着反应时间的延长(100小时以上)催化剂开始出现失活。
发明内容
鉴于现有技术的上述状况，本发明的发明人在二甲醚羰基化制乙酸甲酯用分子筛催化剂方面进行了广泛而深入的研究，发现羰基化分子筛催化剂失活的一个主要原因是高温下分子筛内部或者表面生成的焦炭覆盖了酸性的活性位。如果能降低羰基化的反应温度，积碳反应可以被大大抑制甚至消除。然而，目前普遍接受的二甲醚羰基化温度为220℃，一旦低于此温度，现有分子筛催化剂均表现出极低的催化活性，且由于分子筛的拓扑结构和酸性位紧密相关，这基本上不能通过现有的改性手段加以改进。本发明的发明人令人惊讶地发现了一种具有优异低温羰基化活性的催化剂，其包含ZSM-34作为催化活性材料，即使在低温下仍可以获得相当高的二甲醚转化率和近乎100％的乙酸甲酯选择性，并且还表现出极佳的稳定性。
因此，在本发明的第一方面中，本发明涉及一种用于由二甲醚羰基化制乙酸甲酯的催化剂，其包含ZSM-34分子筛作为催化活性材料。优选地，所述催化剂包含ZSM-34分子筛作为唯一的催化活性材料。
ZSM-34分子筛是现有技术公知的，其可以商购获得，或者可通过水热法合成。
例如，ZSM-34分子筛水热合成可包括如下步骤：
a.将铝源、碱源、硅源、任选的模板剂和水均匀混合、陈化得到混合物A；
b.将混合物A充分搅拌后进行水热晶化，然后抽滤、洗涤、干燥、焙烧得到Na-ZSM-34分子筛；
c.将Na-ZSM-34以一定比例加入硝酸铵溶液中进行铵离子交换。交换、过滤、洗涤、干燥、焙烧步骤过程可重复多次，直至得到H-ZSM-34。
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，例如其摩尔比可为n(Al 2O 3):n(Na 2O):n(K 2O):n(SiO 2):n(H 2O):n(SDA)＝1:(2.5-5.1):(0.76-9.13):(10.54-30):(130-216):(0-1.3)。
水热晶化可采取静态或动态晶化，晶化可采取一段或两段晶化法。晶化温度范围可为100-200℃，优选140℃；晶化时间可为1小时至10天，优选4小时至5天。
步骤b和c中的干燥条件可为80-150℃，6-24小时。
步骤b和c中的焙烧温度可为450-600℃，优选500-600℃；焙烧时间可为0.5-15小时，优选1-10小时。
所述ZSM-34分子筛可以在低温下获得极高的乙酸甲酯选择性和收率，并且还具有极佳的稳定性。因此，所述ZSM-34分子筛可呈未改性形式，即H-ZSM-34。在这种情况下，分子筛不需要负载贵金属，易于再生，这有效地降低了制备乙酸甲酯或乙酸的成本。当然，也可任选地对所述ZSM-34分子筛进行改性，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种，优选 一种或两种。
在本发明的一个实施方案中，所述改性为造介孔，其包括用造孔剂处理所述ZSM-34分子筛。分子筛内部通常为微孔结构，具体而言为小于2nm的孔道。当小分子在孔道内发生反应时，存在传质的问题。造介孔可以在分子筛内部构筑2-50nm的通道或空洞，可以加快反应物和产物在催化剂上的传输，加快反应速度。
造介孔包括用造孔剂处理ZSM-34分子筛。具体地，造介孔包括将ZSM-34分子筛分散于一定浓度的造孔剂溶液中，在设定温度下搅拌一段时间。在造介孔后，可将得到的产物过滤，洗涤至中性，然后将得到的滤饼干燥，干燥条件可例如为80-150℃，6-24小时。在干燥后，可将得到的材料焙烧。焙烧温度可例如为450-600℃，优选500-600℃；焙烧时间可为0.5-15小时，优选1-10小时。此外，在造介孔后，可对所得分子筛进行离子交换处理，以得到H形式的造介孔改性的ZSM-34分子筛。
合适的造孔剂是本领域技术人员所已知的，例如碱性物质，例如氢氧化钠、氢氧化钾、碳酸钠中的一种或多种。处理的固液比可为1：5-50。碱性物质溶液的浓度可为0.01-2M，优选为0.1-1M，例如0.2、0.3、0.4、0.5、0.6、0.7、0.8或0.9或1M。处理温度可为室温至100℃；处理时间可为10分钟至10小时，优选为1-8小时。
在本发明的另一个实施方案中，所述改性为金属离子交换，从而得到金属修饰的ZSM-34分子筛。这有助于提高催化剂的羰基化活性。所述金属可选自铜、银、锌、铁、镓、锆和钴中的一种或多种，优选选自铜、银、锌、铁、钴和镓中的一种或多种，更优选选自铜、银、镓和钴中的一种或多种，最优选为镓或铜。
金属离子交换可包括使ZSM-34分子筛与包含所述金属离子的溶液接触，从而进行离子交换。用于离子交换的金属前驱体可选自所述金属的硝酸盐、硫酸盐、盐酸盐中的一种或多种。离子交换的固液比可为1：5-50；金属离子溶液浓度可为0.01-5M。离子交换次数可为1-5次。离子交换处理的温度可为室温至100℃；时间可为10分钟至5小时。在离子交换后，可将得到的产物过滤并洗涤至中性。然后得到的滤饼干燥，干燥条件可例如为80-150℃，6-24小时。在 干燥后，可将得到的材料焙烧。焙烧温度可例如为450-600℃，优选500-600℃；焙烧时间可为0.5-15小时，优选1-10小时。
在本发明的另一个实施方案中，所述改性为碱性有机物吸附。在碱性有机物吸附后，分子筛中的失活位点将被碱性物质覆盖，反应的失活将被大大减缓。所述碱性有机物选自吡啶及其衍生物中的一种或多种。
所述吡啶衍生物是吡啶环上的氢原子独立地被选自卤素、烷基、卤代烷基或硝基取代的化合物，优选被F、Cl、Br、I、CH 3、CF 3、CH 3CH 2或NO 2取代的化合物。例如，吡啶衍生物可选自C 1-C 10烷基吡啶，例如2-甲基吡啶、3-甲基吡啶、4-甲基吡啶，2-乙基吡啶、3-乙基吡啶、4-乙基吡啶，2-丙基吡啶、3-丙基吡啶、4-丙基吡啶等，卤素取代的吡啶，例如2-氯吡啶、3-氯吡啶或4-氯吡啶等。
吸附方法可为气相吸附，其可包括使携带有吡啶或其衍生物的蒸气的载气通过ZSM-34分子筛。在气相吸附中，可将ZSM-34分子筛原粉或成型体置于固定床或管式炉内，然后升温至目标温度，使携带有吡啶或其衍生物的蒸气的载气通过ZSM-34分子筛一段时间，然后降温得到产物。吸附温度可为200-400℃，吸附压力可为常压至5MPa。载气可为氮气、氦气、氩气等惰性气体中的一种或多种，流速为1-100mL/min。处理时间可为10分钟至10小时，例如1-5小时。
所述催化剂可呈原粉形式，其粒径例如为50nm至50μm；或者可与粘结剂和任选的其他助剂一起形成成型体。在成型后，尽管催化剂的乙酸甲酯的选择性和STY会稍有降低，但是其抗压强度会增加，这使得其适于工业应用。
因此，在本发明的另一个方面中，本发明涉及一种用于由二甲醚羰基化制乙酸甲酯的催化剂成型体，其中所述催化剂成型体包含ZSM-34分子筛作为催化活性材料；优选地，所述催化剂成型体包含ZSM-34分子筛作为唯一的催化活性材料。所述催化剂成型体可呈挤出物的形式。
所述成型体可通过将所述ZSM-34分子筛与粘结剂和任选的其他助剂混合，然后进行成型，然后将所得成型体焙烧而获得。
因此，在本发明另一个方面中，本发明涉及一种制备所述催化剂成型体的方法，其包括将所述ZSM-34分子筛与粘结剂和任选的其他助剂混合，然后进行成型，然后将所得成型体焙烧。
所述粘结剂可选自磷酸、拟薄水铝石、羟甲基纤维素、硅溶胶中的一种或多种。所述其他助剂可选自助挤剂、胶溶剂和扩孔剂中的一种或多种。所述助挤剂可选自田菁粉、聚四氟乙烯、淀粉中的一种或多种。所述胶溶剂可选自硝酸、盐酸、硫酸、醋酸中的一种或多种。所述扩孔剂可选自聚乙二醇、聚醚、六次甲基四乙胺、尿素中的一种或多种。
成型可通过各种方式进行，例如挤出、压制等，优选为挤出。成型体可呈各种所需的形状，例如球形、圆柱形、片状、柱状等。例如，成型体的直径可为30-10mm，长度可为5-20mm。
优选地，在混合之前，可对所述ZSM-34分子筛进行改性，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种。具体的改性方法参见上文就催化剂改性所述的方法。
本发明的催化剂或催化剂成型体可用于二甲醚羰基化制乙酸甲酯，即使在低温下，仍可以获得相当高的二甲醚转化率和近乎100％的乙酸甲酯选择性，并且还表现出极佳的稳定性。
因此，在本发明的又一个方面中，本发明涉及一种由二甲醚羰基化制备乙酸甲酯的方法，其中使用本发明的催化剂或催化剂成型体。优选地，所述方法包括使包含一氧化碳和二甲醚的反应气体通过所述催化剂或催化剂成型体。
特别地，可将所述催化剂或成型体填装于固定床反应器，通入反应气体升压，到达目标压力后升温至反应温度。催化反应在平稳流速、压力和温度下进行，产物实时在线分析。催化剂质量可为0.1-10g，在10-200mL/min反应气体流速下。反应压力可为0.1-20Mpa，优选为1-5MPa。反应温度可为80-250℃，优选为100-220℃，更优选为150-200℃，例如180℃。反应气体流速可为10-200mL/min。反应气体的组成为一氧化碳和二甲醚，其中二甲醚含量小于等于5摩尔％。
在本发明的一个实施方案中，在将所述催化剂或催化剂成型体置于反应器之后且在反应开始之前，可任选将所述催化剂或催化剂成型体还原。还原例如使用氢气进行。还原温度可为200-600℃，优选为250-450℃；还原时间可为1-20小时，优选为5-15小时。
在本发明的在一方面中，本发明涉及ZSM-34分子筛在由二甲醚羰基化制乙 酸甲酯的反应中作为催化活性材料的用途；优选地，ZSM-34分子筛作为唯一的催化活性材料用于该反应中。所述ZSM-34分子筛如上文所述。所述ZSM-34分子筛可呈未改性形式，或者呈改性形式，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种，优选一种或两种。
本发明通过广泛而深入的研究，对比了多种已报道和可能具有羰基化活性的分子筛催化剂性能。发明人通过反应评测发现，ZSM-34分子筛相比于一般分子筛催化剂，例如H-MOR，H-ZSM-35，H-SAPO-34，H-SUZ-4，H-EU-12等，表现出优越的低温活性。仅仅需要180℃的反应温度，乙酸甲酯时空收率(STY)即可达到约700mmol/kg h。在对分子筛进行造介孔、金属离子交换改性后，其催化活性又进一步提高。经吡啶及其衍生物吸附改性的分子筛的催化稳定性得到了极大的提升。成型的ZSM-34分子筛产品具有更强的机械强度和酸量。
本发明的这些和其它目的、特征和优点在结合下文考虑本发明后，将易于为普通技术人员所明白。
附图说明
图1是本发明H-ZSM-34分子筛催化剂的结构示意图。
图2是实施例4中用碱性有机物吸附处理和无任何处理的H-ZSM-34催化剂的寿命评价结果变化曲线图。
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
催化剂的制备
使用氯化胆碱(ChCl)作为有机模板制备Si/Al为3.6的H-ZSM-34沸石。硅铝酸盐凝胶的原始摩尔组成为1.3ChCl：12.7SiO 2：1.0Al 2O 3：0.76K 2O：2.5Na 2O：216H 2O。首先将2.36g NaAlO 2(36-38wt％Al 2O 3纯度，日本Wako公司)，1.02g KOH(85wt％纯度，Wako)和0.88g NaOH(97wt％纯度，Wako)与10.0g去离子 水混合形成溶液A；将1.82g ChCl(95wt％纯度，Wako)溶解在11.60g去离子水中，形成溶液B。在剧烈搅拌下混合溶液A和B后，滴加24.0g二氧化硅溶胶(LUDOX-40，Aldrich)，并搅拌60分钟得到凝胶前驱体。在140℃晶化5天后过滤、洗涤固体产物至中性，在120℃下干燥4小时后，在550℃下焙烧5小时获得Na-ZSM-34。随后，通过在1M NH 4NO 3(Wako)溶液中80℃离子交换3次(固液比1:10)，过滤并洗涤至中性，在120℃下干燥4小时后，在550℃下焙烧4小时，得到H-ZSM-34终产物。
将由Tosoh株式会社购买的商业分子筛H-MOR，H-ZSM-35，H-SAPO-34，H-SUZ-4，H-EU-12作为对比催化剂用于反应以进行活性比较。
催化剂的反应
分别称取0.5g上述分子筛催化剂，装入内径8mm的竖立放置的管式固定床反应器中，催化剂床的两端用石英棉填充。从反应管上端通入流速为40mL/min的反应气体，该反应气体中所含各组分的摩尔比是：二甲醚:CO＝1:20。在反应温度180℃和气体总压力2MPa(表压)下开始反应，连续反应，测算反应第6小时的转化率和产物选择性。结果见表1。
实施例2
对分子筛催化剂进行不同浓度的碱性物质造介孔改性。操作过程如下：以实施例1制备的H-ZSM-34分子筛作为母体。用不同浓度的NaOH水溶液(0.2，0.4，0.6，1.0，2.0M)进行碱改性。首先将H-ZSM-34分子筛在80℃下分别用上述浓度的NaOH溶液处理4小时(固液比1:10)。在过滤后，将所得样品洗涤至中性pH，再在100℃下干燥8小时。在80℃下用1M NH 4NO 3溶液对得到的样品进行三次离子交换(固液比1:10)，过滤并洗涤至中性，在120℃下干燥4小时后，在550℃下焙烧4小时，制备得到H-ZSM-34。经造介孔改性的样品记为H-ZSM-34(X)，X为氢氧化钠浓度。
使用所得催化剂，进行实施例1中描述的羰基化反应，结果见表2。
实施例3
对分子筛催化剂进行不同金属离子交换改性。操作过程如下：以实施例1制备的H-ZSM-34分子筛作为母体。用1M的金属硝酸盐水溶液(Ag、Cu、Fe、Co、Zn或Ga)进行离子交换。首先将H-ZSM-34分子筛在80℃下用上述各种金属硝酸盐的1M溶液处理4小时(固液比1:10)。在过滤后，将所得样品洗涤至中性pH，再在100℃下干燥8小时。接着于550℃下焙烧4小时，制备得到金属离子交换改性的ZSM-34分子筛催化剂。经金属离子改性得到的样品记为H-ZSM-34(Y)，Y为所使用的金属。
使用所得催化剂，于400℃下进行氢气还原10小时后，进行实施例1中描述的羰基化反应，结果见表3。
实施例4
对分子筛催化剂进行碱性有机物吸附提升稳定性。操作过程如下：在固定床反应器中用吡啶室温饱和的N 2处理0.5g实施例1制备的H-ZSM-34样品。将纯N 2携带的吡啶饱和蒸气通入300℃的反应管(流速30mL/min)，处理负载其中的H-ZSM-34样品。处理时间为4小时。接着移去吡啶管，在氮气流下继续吹扫1小时以除去多余的物理吸附吡啶。在上述吸附操作完毕后，直接进行实施例1中描述的羰基化反应。
作为对比例，未经任何改性的H-ZSM-34催化剂也进行催化反应寿命评价。对比结果见图2。从图2可以看出，用吡啶吸附处理后分子筛催化剂的稳定性高于未经任何改性的H-ZSM-34，即使在500小时的反应时间内，其二甲醚转化率基本上保持恒定。与此相反，未经任何改性的H-ZSM-34在反应时间内持续降低。
实施例5
对分子筛催化剂粉体进行成型处理。操作过程如下：以H-ZSM-34：羟甲基纤维素：拟薄水铝石：田菁粉：聚乙二醇：硝酸：水＝1:0.05:Z:0.028:0.1:0.12:0.7,的质量比进行成型，Z代表拟薄水铝石的质量比。取20g H-ZSM34分子筛原粉，分别与1g羟甲基纤维素，1g、3g、5g或7g拟薄水铝石，0.56g田菁粉，2g聚 乙二醇混合均匀搅拌10min，再缓慢加入2.4g硝酸和14g水继续搅拌30min得到粘料团。将粘料团置于挤条机的加料槽中，转速50rmp，挤条成型。120℃干燥4小时后于550℃焙烧6小时，得到成型产品。
使用所得成型催化剂，进行实施例1中描述的羰基化反应，产品的抗压强度和催化活性见表4。
表1
Figure PCTCN2022083366-appb-000001
表2
Figure PCTCN2022083366-appb-000002
表3
Figure PCTCN2022083366-appb-000003
表4
Figure PCTCN2022083366-appb-000004
根据表1-4的结果可见，H-ZSM-34具有极佳的低温羰基化活性，在180℃的反应温度下其活性是目前已知最好羰基化催化剂H-MOR的约7倍。产物乙酸甲酯的选择性为100％。经过氢氧化钠改性后，H-ZSM-34的活性随着氢氧化钠浓度的升高而先升高后降低，最佳的氢氧化钠改性浓度在0.6M附近。不同金属的加入对H-ZSM-34分子筛催化活性有影响。除了Zn，其他金属能够有效提升催化活性，Cu改性后的催化剂活性最好，改性后STY能到835(mmol/kg h)。在成型后，催化剂的抗压强度随拟薄水铝石加入量的增加而增加，但乙酸甲酯的选择性和STY降低。

Claims (33)

  1. 一种用于由二甲醚羰基化制乙酸甲酯的催化剂，其包含ZSM-34分子筛作为催化活性材料。
  2. 根据权利要求1所述的催化剂，其包含ZSM-34分子筛作为唯一的催化活性材料。
  3. 根据权利要求1或2所述的催化剂，其中所述ZSM-34分子筛呈未改性形式，或者呈改性形式，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种。
  4. 根据权利要求3所述的催化剂，其中所述造介孔包括用造孔剂处理所述ZSM-34分子筛。
  5. 根据权利要求4所述的催化剂，其中所述造孔剂为碱性物质。
  6. 根据权利要求5所述的催化剂，其中所述造孔剂为氢氧化钠、氢氧化钾、碳酸钠中的一种或多种。
  7. 根据权利要求3-6中任一项所述的催化剂，其中金属离子交换中所用的金属选自铜、银、锌、铁、镓、锆、钴中的一种或多种。
  8. 根据权利要求7所述的催化剂，其中金属离子交换中所用的金属选自铜、银、锌、铁、钴和镓中的一种或多种。
  9. 根据权利要求7所述的催化剂，其中金属离子交换中所用的金属选自铜、银、镓和钴中的一种或多种。
  10. 根据权利要求7所述的催化剂，其中金属离子交换中所用的金属为镓或铜。
  11. 根据权利要求3-10中任一项所述的催化剂，其中所述碱性有机物选自吡啶及其衍生物中的一种或多种。
  12. 一种用于由二甲醚羰基化制乙酸甲酯的催化剂成型体，其中所述催化剂成型体包含ZSM-34分子筛作为催化活性材料。
  13. 根据权利要求12所述的催化剂成型体，其中所述催化剂成型体包含ZSM-34分子筛作为唯一的催化活性材料。
  14. 一种制备根据权利要求12或13所述的催化剂成型体的方法，其包括将 所述ZSM-34分子筛与粘结剂和任选的其他助剂混合，然后进行成型，然后将所得成型体焙烧。
  15. 根据权利要求14所述的方法，其中所述粘结剂选自磷酸、拟薄水铝石、羟甲基纤维素、硅溶胶中的一种或多种；和/或，所述其他助剂选自助挤剂、胶溶剂和扩孔剂中的一种或多种；和/或，所述助挤剂选自田菁粉、聚四氟乙烯、淀粉中的一种或多种；所述胶溶剂选自硝酸、盐酸、硫酸、醋酸中的一种或多种；和/或，所述扩孔剂选自聚乙二醇、聚醚、六次甲基四乙胺、尿素中的一种或多种。
  16. 根据权利要求14或15的方法，其中在混合之前，对所述ZSM-34分子筛进行改性，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种。
  17. 根据权利要求16的方法，其中造介孔包括用造孔剂处理所述ZSM-34分子筛。
  18. 根据权利要求16或17所述的方法，其中所述碱性有机物吸附包括使所述ZSM-34分子筛与包含所述碱性有机物的载气接触。
  19. 一种由二甲醚羰基化制备乙酸甲酯的方法，其中使用根据权利要求1-11中任一项所述的催化剂或根据权利要求12或13所述的催化剂成型体或根据权利要求14-18中任一项的方法获得的催化剂成型体。
  20. 根据权利要求19所述的方法，其包括在将所述催化剂或催化剂成型体置于反应器之后且在反应开始之前，将所述催化剂或催化剂成型体还原。
  21. 根据权利要求19或20所述的方法，其包括使包含一氧化碳和二甲醚的反应气体通过所述催化剂或催化剂成型体。
  22. 根据权利要求19-21中任一项所述的方法，其中反应在80-250℃的温度下进行。
  23. 根据权利要求22所述的方法，其中反应在100-220℃的温度下进行。
  24. 根据权利要求22所述的方法，其中反应在150-200℃的温度下进行。
  25. 根据权利要求22所述的方法，其中反应在180℃的温度下进行。
  26. ZSM-34分子筛在由二甲醚羰基化制乙酸甲酯的反应中作为催化活性材料的用途。
  27. 根据权利要求26所述的用途，其中ZSM-34分子筛作为唯一的催化活性材料用于该反应中。
  28. 根据权利要求26或27所述的用途，其中所述ZSM-34分子筛呈未改性形式，或者呈改性形式，其中所述改性选自造介孔、金属离子交换或碱性有机物吸附中的一种或多种。
  29. 根据权利要求28所述的用途，其中所述造介孔包括用造孔剂处理所述ZSM-34分子筛。
  30. 根据权利要求29所述的用途，其中所述造孔剂为碱性物质。
  31. 根据权利要求30所述的用途，其中所述造孔剂为氢氧化钠、氢氧化钾、碳酸钠中的一种或多种。
  32. 根据权利要求28-31中任一项所述的用途，其中所述金属选自铜、银、锌、铁、镓、锆、钴中的一种或多种。
  33. 根据权利要求28-32中任一项所述的用途，其中所述碱性有机物选自吡啶及其衍生物中的一种或多种。
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