CN106824257B - Molecular sieve catalyst, and preparation method and application thereof - Google Patents

Molecular sieve catalyst, and preparation method and application thereof Download PDF

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CN106824257B
CN106824257B CN201710065638.7A CN201710065638A CN106824257B CN 106824257 B CN106824257 B CN 106824257B CN 201710065638 A CN201710065638 A CN 201710065638A CN 106824257 B CN106824257 B CN 106824257B
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CN106824257A (en
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陈志伟
吴全贵
周红军
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Beijing Zhongshida New Energy Research Institute Co ltd
China University of Petroleum Beijing
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China University of Petroleum Beijing
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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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J35/615—
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38

Abstract

The invention relates to a molecular sieve catalyst, a preparation method and application thereof. The preparation method of the molecular sieve catalyst comprises the following steps: sequentially adding an alkali source, an aluminum source, a silicon source and a template agent into deionized water, and stirring to form a uniform solution; slowly adding C1-C4 alcohol, and continuously stirring to form a sol solution; crystallizing the sol solution under a hydrothermal condition, filtering, drying and roasting to obtain sodium type molecular sieve raw powder; performing ion exchange on the sodium type molecular sieve raw powder and an ammonium salt solution or dilute hydrochloric acid, and filtering and drying to obtain hydrogen type molecular sieve raw powder; and mixing the hydrogen type molecular sieve raw powder, a binder and a proper amount of water, then carrying out extrusion forming, drying and roasting to obtain the molecular sieve catalyst. The molecular sieve catalyst prepared by the preparation method can solve the problems of quick carbon deposit inactivation, short service life, serious side reaction in the process of preparing isobutene by n-butene skeletal isomerization and the like of the catalyst.

Description

Molecular sieve catalyst, and preparation method and application thereof
Technical Field
The invention relates to a molecular sieve catalyst for preparing isobutene by skeletal isomerization of n-butene, belonging to the technical field of molecular sieve catalysts.
Background
In the petroleum refining and petrochemical production process, a large amount of carbon-tetrad hydrocarbons can be produced as byproducts. At present, the comprehensive utilization rate of the carbon four resources in countries and regions such as the United states, Japan, Western Europe and the like exceeds 60 percent, the carbon four utilization rate in China is lower than 40 percent, and the rest is used as civil fuel, thereby causing resource waste to a certain extent. Isobutene is an important way for comprehensive utilization of carbon-four hydrocarbons, and isobutene products are mainly used for producing methyl tert-butyl ether, tert-butyl alcohol, methyl methacrylate, polybutene, p-tert-octylphenol and isoprene. With the increasing demand of downstream products in recent years, the market demand of isobutene is gradually increased, so that n-butene skeletal isomerization technology is actively developed at home and abroad. The catalyst for preparing isobutene by n-butene skeletal isomerization at present stage is mainly a molecular sieve catalyst with a ferrierite topological structure.
For the molecular sieve catalyst for preparing isobutene by skeletal isomerization of n-butene, the synthesis condition of the molecular sieve and the preparation process of the catalyst have decisive influence on the catalytic performance of the molecular sieve catalyst. CN105709841A discloses a preparation method of an N-butene skeletal isomerization catalyst, wherein a cerium-zirconium-aluminum composite oxidant composite material is placed in a reaction kettle, N-propylpyridine tosylate and tetrafluoroboric acid (1-methyl-3-octyl imidazolium) are added and then react to obtain the isomerization catalyst, the longest one-way reaction life of the catalyst reaches 43 days after cerium-zirconium is doped, organic matter auxiliaries used in the method are expensive, and the production cost of the catalyst is increased to a certain extent. CN105413739A discloses a method for preparing a high-activity n-butene skeletal isomerization catalyst by secondary crystallization, which comprises the steps of firstly mixing ferrierite micron mother crystal plate-shaped crystal grains with silica-alumina sol by using a binder, extruding the mixture into strips, and then carrying out secondary crystallization on the strips to finally obtain a combined crystal ferrierite molecular sieve catalyst. The method can improve the integral crystallinity of the molecular sieve catalyst, but the secondary crystallization operation process is more complicated, and the strength of the formed catalyst can be reduced after hydrothermal reaction.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a molecular sieve catalyst and a preparation method thereof, the molecular sieve catalyst prepared by the preparation method has high specific surface area, high activity and high selectivity, and can be used as a catalyst for preparing isobutene by n-butene skeletal isomerization, so that the problems of fast carbon deposit inactivation, short service life, serious side reaction in the process of preparing isobutene by n-butene skeletal isomerization and the like of the catalyst can be solved.
In order to achieve the above object, the present invention provides a method for preparing a molecular sieve catalyst, comprising the steps of:
sequentially adding an alkali source, an aluminum source, a silicon source and a template agent into deionized water, and stirring to form a uniform solution;
slowly adding C1-C4 alcohol, and continuously stirring to form a sol solution;
crystallizing the sol solution under a hydrothermal condition, filtering, drying and roasting to obtain sodium type molecular sieve raw powder;
performing ion exchange on sodium type molecular sieve raw powder and an ammonium salt solution or dilute hydrochloric acid, and filtering and drying to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder, a binder and a proper amount of water, then carrying out extrusion forming, drying and roasting to obtain the molecular sieve catalyst.
In the above preparation method, preferably, the sodium type molecular sieve raw powder includes, but is not limited to, ferrierite ZSM-35.
In the above preparation method, preferably, the binder may be selected from binders conventional in the art, more preferably, including but not limited to one or both of an aluminum source and a silicon source, preferably the silicon source or the aluminum source used in the preparation method;
the alkali source includes but is not limited to one or both of sodium hydroxide and potassium hydroxide;
the aluminum source comprises but is not limited to one or a combination of more of pseudo-boehmite, aluminum hydroxide and aluminum sol;
the silicon source comprises but is not limited to one or a combination of several of water glass, acidic silica sol, neutral silica sol and alkaline silica sol;
the template agent comprises but is not limited to one or a combination of several of ethylenediamine, n-butylamine, pyrrolidone, tetrahydrofuran and pyridine;
the C1-C4 alcohol includes but is not limited to one or the combination of several of methanol, ethanol, propanol and butanol;
the ammonium salt includes but is not limited to one or a combination of ammonium chloride, ammonium nitrate and ammonium sulfate.
In the above production method, preferably, the concentration of the ammonium salt solution is 0.5 to 2.0mol/L, and the concentration of the dilute hydrochloric acid is 0.5 to 2.0 mol/L.
In the above preparation method, preferably, the silicon source and the aluminum source have a silicon-aluminum molar ratio of 20 to 70: 1, the mass ratio of the alkali source, the aluminum source, the silicon source, the template agent, the C1-C4 alcohol and the deionized water is (0.074-0.081): (0.009-0.071):1, (0.087-0.142): 0.46-0.97): 2.302-2.908).
In the preparation method, preferably, the mass ratio of the sodium type molecular sieve raw powder to the ammonium salt solution is 1.0 (10-50), and the mass ratio of the sodium type molecular sieve raw powder to the dilute hydrochloric acid is 1.0 (10-50).
In the above preparation method, preferably, the mass ratio of the hydrogen type molecular sieve raw powder, the binder and the water is 10 (2-3.5) to (2-4).
In the above preparation method, preferably, the temperature of the hydrothermal condition is 180-; the temperature of the ion exchange is 60-90 ℃, and the time is 2-6 hours; the drying temperature is 80-120 ℃, and the drying time is 8-24 hours; the roasting temperature is 500-650 ℃, and the roasting time is 4-10 hours.
In the molecular sieve catalyst prepared by the preparation method, the hydrogen type molecular sieve raw powder accounts for 80-95% of the mass of the molecular sieve catalyst.
The molecular sieve catalyst prepared by the preparation method can be used as a catalyst in the process of preparing isobutene by skeletal isomerization of n-butene.
The preparation method of the molecular sieve catalyst has less side reaction, the molecular sieve raw powder with high specific surface area is prepared by changing the surface tension of a synthesis system by adding a proper amount of C1-C4 alcohol in the synthesis process, and the molecular sieve catalyst with high activity, long one-way service life, strong carbon deposition resistance and low liquid phase yield is prepared by using a silicon source or an aluminum source selected in the synthesis as a binder for extrusion molding.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a molecular sieve catalyst prepared by the following steps:
3.06g of sodium hydroxide, 1.08g of aluminum hydroxide, 4.41g of ethylenediamine and 41.27g of acidic silica sol (25% by weight of SiO)2Content) were added to 95g of deionized water in succession,stirring at normal temperature to form a uniform solution;
slowly adding 35g of methanol into the solution under stirring until the solution is formed uniformly, and continuously stirring for 2 hours at normal temperature to ensure that the solution does not splash, and finally forming a white uniform sol solution;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 180 ℃ for 72 hours, filtering, washing, drying at 80 ℃ for 12 hours, heating to 550 ℃ at a heating rate of 2 ℃/min, roasting for 4 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 25;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium chloride solution, performing ion exchange in a water bath at 80 ℃ for 6 hours, filtering, washing, and drying at 100 ℃ for 8 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of silica sol and 3g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 550 ℃ at a heating rate of 2 ℃/min for roasting, and roasting for 4 hours to obtain the molecular sieve catalyst A1.
Example 2
This example provides a molecular sieve catalyst prepared by the following steps:
3.06g of sodium hydroxide, 5.33g of n-butylamine, 41.27g of neutral silica sol (25% by weight of SiO)2Content) and 2.93g of alumina sol (30 wt.% Al)2O3Content) was added to 95g of deionized water in sequence, and stirred at normal temperature until a homogeneous solution was formed;
adding 28g of ethanol into the solution slowly under stirring, and continuously stirring for 2 hours at normal temperature to ensure that the solution does not splash, and finally forming a white uniform sol solution;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 50 hours at 190 ℃, filtering, washing, drying for 20 hours at 80 ℃, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 8 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 40;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium nitrate solution, carrying out ion exchange in a water bath at 90 ℃ for 4 hours, filtering, washing, and drying at 120 ℃ for 12 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.0g of aluminum sol and 2.0g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 120 ℃ for 10 hours after molding, heating to 500 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst A2 after roasting for 6 hours.
Example 3
This example provides a molecular sieve catalyst prepared by the following steps:
3.15g of sodium hydroxide, 0.47g of aluminum hydroxide, 4.77g of pyrrolidone and 41.27g of basic silica sol (25% by weight of SiO)2Content) was added to 120g of deionized water in sequence, and stirred at normal temperature until a homogeneous solution was formed;
adding 19g of propanol into the solution slowly under stirring, and continuously stirring for 6 hours at normal temperature to ensure that the solution does not splash, and finally forming a white uniform sol solution;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 200 ℃ for 68 hours, filtering, washing, drying at 120 ℃ for 10 hours, heating to 600 ℃ at a heating rate of 2 ℃/min, roasting for 8 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide of 70;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium sulfate solution, performing ion exchange in a water bath at 90 ℃ for 4 hours, filtering, washing, and drying at 120 ℃ for 10 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of aluminum hydroxide and 2.5g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 120 ℃ for 12 hours after molding, heating to 600 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst A3 after roasting for 8 hours.
Example 4
This example provides a molecular sieve catalyst prepared by the following steps:
3.21g of sodium hydroxide, 0.43g of pseudoboehmite, 5.86g of tetrahydrofuran and 41.27g of basic silica sol (25% by weight of SiO)2Content) was added to 115g of deionized water in sequence, and stirred at normal temperature until a uniform transparent solution was formed;
adding 18g of methanol and 15g of ethanol into the solution slowly under stirring, and continuously stirring for 2 hours at normal temperature to ensure that the solution does not splash, and finally forming a white uniform sol solution;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 96 hours at 220 ℃, filtering, washing, drying for 20 hours at 100 ℃, heating to 650 ℃ at the heating rate of 2 ℃/min, roasting for 10 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 80;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium chloride solution, carrying out ion exchange in a water bath at 80 ℃ for 2 hours, filtering, washing, and drying at 100 ℃ for 8 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of pseudo-boehmite and 4.0g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 550 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst A4 after roasting for 6 hours.
Example 5
This example provides a molecular sieve catalyst prepared by the following steps:
3.35g of sodium hydroxide, 0.38g of aluminum hydroxide, 3.58g of pyridine and 41.27g of silica sol (25% by weight of SiO)2Content) was added to 100g of deionized water in sequence and stirred at normal temperature until a uniform transparent solution was formed;
slowly adding 40g of methanol into the solution under stirring, and continuously stirring for 2 hours at normal temperature to ensure that the solution does not splash and finally form a white uniform sol solution;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 240 ℃ for 48 hours, filtering, washing, drying at 100 ℃ for 8 hours, heating to 550 ℃ at a heating rate of 2 ℃/min, roasting, and roasting for 10 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide of 70;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium nitrate solution, carrying out ion exchange in a water bath at 80 ℃ for 6 hours, filtering, washing, and drying at 120 ℃ for 6 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of silica sol and 3.5g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 500 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst A5 after roasting for 8 hours.
Molecular sieve catalysts were also prepared in comparative examples 1-5, however, the molecular sieve raw powder was prepared without adding C1-C4 alcohols, and the other steps were the same as those for the molecular sieve catalysts prepared in examples 1-5, respectively.
Comparative example 1
This comparative example provides a molecular sieve catalyst prepared by the steps of:
sequentially adding 3.06g of sodium hydroxide, 1.08g of aluminum hydroxide and 4.41g of ethylenediamine into 95g of deionized water, and stirring at normal temperature until a uniform and transparent solution is formed;
41.27g of silica sol (25% by weight of SiO)2Content) is added into the solution in turn under stirring, and the solution is continuously stirred for 2 hours at normal temperature, so that the solution is ensured not to splash, and finally white uniform sol solution is formed;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 180 ℃ for 72 hours, filtering, washing, drying at 100 ℃ for 8 hours, heating to 550 ℃ at a heating rate of 2 ℃/min, roasting for 4 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 25;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium nitrate solution, carrying out ion exchange in a water bath at 80 ℃ for 2 hours, filtering, washing, and drying at 100 ℃ for 12 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of silica sol and 3.0g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 550 ℃ at the heating rate of 2 ℃/min for roasting, and roasting for 4 hours to obtain the molecular sieve catalyst D1.
Comparative example 2
This comparative example provides a molecular sieve catalyst prepared by the steps of:
sequentially adding 3.06g of sodium hydroxide and 5.33g of n-butylamine into 95g of deionized water, and stirring at normal temperature until a uniform and transparent solution is formed;
41.27g of silica sol (25% by weight of SiO)2Content) and 2.93g of alumina sol (30 wt.% Al)2O3Content) is added into the solution in turn under stirring, and the solution is continuously stirred for 2 hours at normal temperature, so that the solution is ensured not to splash, and finally white uniform sol solution is formed;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 50 hours at 190 ℃, filtering, washing, drying for 20 hours at 80 ℃, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 8 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 40;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium nitrate solution, carrying out ion exchange in a water bath at 90 ℃ for 4 hours, filtering, washing, and drying at 120 ℃ for 12 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.0g of aluminum sol and 2.0g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 120 ℃ for 10 hours after molding, heating to 500 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst D2 after roasting for 6 hours.
Comparative example 3
This comparative example provides a molecular sieve catalyst prepared by the steps of:
sequentially adding 3.15g of sodium hydroxide, 0.47g of aluminum hydroxide and 4.77g of pyrrolidone into 120g of deionized water, and stirring at normal temperature until a uniform and transparent solution is formed;
41.27g of silica sol (25% by weight of SiO)2Content) is added into the solution in turn under stirring, and the solution is continuously stirred for 6 hours at normal temperature, so that the solution is ensured not to splash, and finally white uniform sol solution is formed;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 200 ℃ for 68 hours, filtering, washing, drying at 120 ℃ for 10 hours, heating to 600 ℃ at a heating rate of 2 ℃/min, roasting for 8 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 60;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium sulfate solution, performing ion exchange for 4 hours in a water bath at 95 ℃, filtering, washing, and drying for 10 hours at 120 ℃ to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of aluminum hydroxide and 2.5g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 120 ℃ for 12 hours after molding, heating to 600 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst D3 after roasting for 8 hours.
Comparative example 4
This comparative example provides a molecular sieve catalyst prepared by the steps of:
sequentially adding 3.21g of sodium hydroxide, 0.43g of pseudo-boehmite and 5.86g of tetrahydrofuran into 115g of deionized water, and stirring at normal temperature until a uniform and transparent solution is formed;
41.27g of basic silica sol (25% by weight of SiO)2Content), 18g of methanol and 15g of ethanol are sequentially added into the solution under stirring, and the solution is continuously stirred for 2 hours at normal temperature, so that the solution is prevented from splashing, and finally a white uniform sol solution is formed;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing for 96 hours at 220 ℃, filtering, washing, drying for 20 hours at 100 ℃, heating to 650 ℃ at the heating rate of 2 ℃/min, roasting for 10 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide being 80;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium chloride solution, carrying out ion exchange in a water bath at 80 ℃ for 2 hours, filtering, washing, and drying at 100 ℃ for 8 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of pseudo-boehmite and 4.0g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 550 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst D4 after roasting for 6 hours.
Comparative example 5
This comparative example provides a molecular sieve catalyst prepared by the steps of:
sequentially adding 3.35g of sodium hydroxide, 0.38g of aluminum hydroxide and 3.58g of pyridine into 100g of deionized water, and stirring at normal temperature until a uniform and transparent solution is formed;
41.27g of silica sol (25% by weight of SiO)2Content) and 40g of methanol are added into the solution in turn under stirring, and the solution is continuously stirred for 2 hours at normal temperature, so that the solution is ensured not to splash, and finally a white uniform sol solution is formed;
transferring the sol solution into a hydrothermal crystallization kettle, crystallizing at 240 ℃ for 48 hours, filtering, washing, drying at 100 ℃ for 8 hours, heating to 550 ℃ at a heating rate of 2 ℃/min, roasting, and roasting for 10 hours to obtain sodium type molecular sieve raw powder with the molar ratio of silicon-aluminum oxide of 70;
taking 10g of sodium type molecular sieve raw powder, mixing with 100mL of 1mol/L ammonium nitrate solution, carrying out ion exchange in a water bath at 80 ℃ for 6 hours, filtering, washing, and drying at 120 ℃ for 6 hours to obtain hydrogen type molecular sieve raw powder;
mixing hydrogen type molecular sieve raw powder with 2.5g of silica sol and 3.5g of deionized water, mechanically stirring, putting into a strip extruding machine for extruding strips, drying at 100 ℃ for 8 hours after molding, heating to 500 ℃ at the heating rate of 2 ℃/min for roasting, and obtaining the molecular sieve catalyst D5 after roasting for 8 hours.
The results of the performance measurement of the molecular sieve catalysts in the examples and comparative examples are shown in table 1. The reaction evaluation conditions were: at normal pressure and 380 ℃, the total weight WHSV is 6h-1The loading amount of the molecular sieve catalyst is 5 g; the raw material is C4 after etherification, which contains 45% of n-butene, 25% of butylene, 19% of maleic anhydride, 6% of n-butane and 5% of isobutane.
TABLE 1 Performance of molecular sieve catalysts in the examples and comparative examples
Figure GDA0001241832060000081
Figure GDA0001241832060000091
As can be seen from Table 1, when a proper amount of C1-C4 alcohol is added during synthesis, the specific surface area of the synthesized molecular sieve raw powder can be effectively increased, and the conversion rate of n-butene and the selectivity of isobutene in the isomerization reaction process are increased; meanwhile, the molecular sieve prepared by adding a proper amount of C1-C4 alcohol during synthesis can effectively inhibit side reactions such as olefin dimerization and the like in the reaction process, so that the total liquid-phase yield of the reaction is greatly reduced, the carbon deposition stability of the molecular sieve is also obviously improved, the longest reaction day of the molecular sieve with the conversion rate of more than 30 percent can reach 71 days under the condition of high weight hourly space velocity, and the reaction performance of the molecular sieve is obviously superior to that of the comparative molecular sieve.

Claims (11)

1. A preparation method of a molecular sieve catalyst for preparing isobutene by skeletal isomerization of n-butene comprises the following steps:
sequentially adding an alkali source, an aluminum source, a silicon source and a template agent into deionized water, and stirring to form a uniform solution;
slowly adding C1-C4 alcohol, and continuously stirring to form a sol solution;
crystallizing the sol solution under a hydrothermal condition, filtering, drying and roasting to obtain sodium type molecular sieve raw powder;
performing ion exchange on the sodium type molecular sieve raw powder and an ammonium salt solution or dilute hydrochloric acid, and filtering and drying to obtain hydrogen type molecular sieve raw powder;
mixing the hydrogen type molecular sieve raw powder, a binder and a proper amount of water, then carrying out extrusion forming, drying and roasting to obtain a molecular sieve catalyst;
the aluminum source comprises one or a combination of more of pseudo-boehmite, aluminum hydroxide and aluminum sol;
the silicon source comprises one or a combination of more of water glass, acidic silica sol, neutral silica sol and alkaline silica sol;
the template agent comprises one or a combination of more of ethylenediamine, n-butylamine, pyrrolidone, tetrahydrofuran and pyridine;
the C1-C4 alcohol comprises one or more of methanol, ethanol, propanol and butanol;
wherein the mass ratio of the alkali source, the aluminum source, the silicon source, the template agent, the C1-C4 alcohol and the deionized water is (0.074-0.081): (0.009-0.071):1: (0.087-0.142): 0.46-0.97): 2.302-2.908);
the temperature of the hydrothermal condition is 180-240 ℃, and the time is 48-96 hours;
the roasting temperature is 500-650 ℃, and the roasting time is 4-10 hours.
2. The method of claim 1, wherein the sodium molecular sieve raw powder comprises ferrierite molecular sieve.
3. The method of claim 2, wherein the sodium molecular sieve raw powder is ZSM-35.
4. The production method according to claim 1 or 2, wherein the binder comprises one or both of an aluminum source and a silicon source.
5. The production method according to claim 4, wherein the alkali source comprises one or both of sodium hydroxide and potassium hydroxide;
the ammonium salt comprises one or more of ammonium chloride, ammonium nitrate and ammonium sulfate.
6. The production method according to any one of claims 1 to 3 and 5, wherein the concentration of the ammonium salt solution is 0.5 to 2.0mol/L, and the concentration of the dilute hydrochloric acid is 0.5 to 2.0 mol/L.
7. The method of claim 6, wherein the silicon source and the aluminum source have a molar ratio of silicon to aluminum of 20 to 70: 1;
the mass ratio of the sodium type molecular sieve raw powder to the ammonium salt solution is 1.0 (10-50), and the mass ratio of the sodium type molecular sieve raw powder to the dilute hydrochloric acid is 1.0 (10-50);
the mass ratio of the hydrogen type molecular sieve raw powder to the binder to the water is 10 (2-3.5) to (2-4).
8. The method of claim 1, wherein the temperature of the ion exchange is 60 to 90 ℃ and the time is 2 to 6 hours;
the drying temperature is 80-120 ℃ and the drying time is 8-24 hours.
9. A molecular sieve catalyst prepared by the method of any one of claims 1 to 8.
10. The molecular sieve catalyst of claim 9, wherein the hydrogen form of the molecular sieve raw powder is 80-95% by mass of the molecular sieve catalyst.
11. Use of the molecular sieve catalyst of claim 9 or 10 as a catalyst in the skeletal isomerization of n-butenes to isobutene.
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