CN115193462B - Supported alkali metal catalyst and preparation method thereof - Google Patents

Supported alkali metal catalyst and preparation method thereof Download PDF

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Publication number
CN115193462B
CN115193462B CN202111673208.6A CN202111673208A CN115193462B CN 115193462 B CN115193462 B CN 115193462B CN 202111673208 A CN202111673208 A CN 202111673208A CN 115193462 B CN115193462 B CN 115193462B
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crown
ether
alkali metal
carrier
catalyst
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CN115193462A (en
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王亚丽
王斯晗
徐显明
蒋岩
牟玉强
马立莉
于部伟
黄付玲
马鸿钰
王秀绘
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Petrochina Co Ltd
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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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/24—Catalytic processes with metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a supported alkali metal catalyst and a preparation method thereof. The catalyst comprises: a carrier and sodium and/or potassium supported thereon; the carrier is obtained by mixing alkali metal salt with a modifier solution and then roasting; the modifier comprises a crown ether, or a combination of crown ether and graphite. The carrier is prepared by adding modifier solution into alkali metal salt, wherein the modifier solution is mainly crown ether solution, and graphite can be further added. The invention improves the surface micro-environment of the carrier, forms a special vacancy structure on the surface of the carrier and is uniformly dispersed, which is beneficial to the uniform dispersion of active metal, and the prepared catalyst has good performance, high propylene conversion rate and high selectivity of 4MP 1.

Description

Supported alkali metal catalyst and preparation method thereof
Technical Field
The invention relates to the field of propylene dimerization catalysts, in particular to a supported alkali metal catalyst and a preparation method thereof.
Background
The supported alkali metal is a very important catalyst, has a specific catalytic function in the reactions such as olefin double bond isomerization, mahalanobis addition, aromatic hydrocarbon side chain alkylation, heterocyclic carbon chain substitution and the like, and can obtain a product which is difficult to generate under acid catalysis with high selectivity. If the target product 4-methyl-1-pentene (4 MP1 for short) which is unstable in thermodynamics is obtained by catalyzing propylene dimerization reaction, if an acid catalyst is adopted, 4MP1 is basically obtained. In addition, the solid base catalyst is not deactivated by rapid coking like an acid catalyst, and is replaced by the base catalyst in the environment requiring high temperature and pressure for the acid catalyst, so that the severity of process conditions can be greatly reduced, and the research of the solid base catalyst, particularly the solid super-strong base catalyst, has great application prospect.
4-Methyl-1-pentene (4 MP1 for short) is an important chemical raw material and an organic synthesis intermediate, is mainly used as a comonomer of linear low density polyethylene, has similar effect to 1-hexene, improves the toughness, the optical property and the mechanical property of resin, and is used as a high-grade film and an injection molding material. In addition, the poly 4-methyl-1-pentene (PMP) prepared by homopolymerization of 4MP1 is a novel special thermoplastic material, has the characteristics of general polyolefin materials, and also has high transparency, high softening point, good dielectric property, drug resistance and the like, so that the poly 4-methyl-1-pentene has wide and special application, can be used for manufacturing high-added-value products such as release paper, medical equipment, food packaging materials, electronic and electric parts and the like, and can be particularly used in the fields of the currently emerging 5G industry, high-end medical treatment (artificial lung) and the like.
The production method of 4MP1 is mainly propylene selective dimerization. The catalyst with high 4MP1 selectivity is prepared by mainly taking alkali metal as a main body and dispersing the alkali metal on alkali metal carbonate and/or bicarbonate. The alkali metal salts such as potassium carbonate and the like are used as excellent carriers of the current catalyst for propylene dimerization to 4MP1, and have lower isomerization activity and higher 4MP1 selectivity due to lower specific surface and simple pore structure, but have the problem of low propylene conversion rate caused by low activity. In order to solve the contradiction between the improvement of activity and the assurance of selectivity, the catalyst is generally modified. The modification of the catalyst is mainly developed from the aspects of modification of a carrier, addition of an auxiliary agent and the like, and research is carried out on improving the pore channel structure of the carrier, improving the pore size distribution and the like, or alkaline earth metal oxides such as metallic copper, cobalt, stainless steel powder, mgO and the like are added in the preparation process of the catalyst so as to improve the conversion efficiency.
Patent application US4595787A of Phillips corporation describes the addition of inorganic substances as templating agents, such as graphite, carbon black, coke, etc., to a support, which can be used as a granulating mold lubricant, and also can improve the pore size distribution of potassium carbonate to increase the activity of dimerization catalysts, and promoters such as stainless steel, metallic cobalt, metallic copper, etc. are added to maintain the catalyst activity when the metallic potassium is melt-supported. The company then successively discloses a plurality of carrier improvement methods for improving the propylene conversion rate: US4876410a describes adding water and alcohol to alkali metal carbonate to form a thick paste, extruding the paste, and drying the paste to form a particulate carrier; US5057639a describes a method in which potassium carbonate, sodium carbonate and at least one alumina-containing compound such as aluminium hydroxide, α -Al 2O3 or γ -Al 2O3 are mixed with water to give a paste, which is then dried and calcined to give a carrier; in US5112791a it is described that the catalyst support is prepared from an alkali metal carbonate, at least one low surface area silica-alumina and a liquid. In addition, the potassium carbonate carrier described in CN1405128a should have the following physical parameters: the particle diameter of the most probable primary particles is 0.5-1.5 mu m, the particle diameter of the most probable secondary particles is 100-700 mu m, the total pore volume is more than or equal to 0.08mL/g, and the most probable pore diameter isThe catalyst has high activity, good selectivity and good controllability; CN108554430a discloses a preparation method of catalyst in which talcum powder additive is added into alkali metal salt carrier to make drying treatment and then to make melt load of alkali metal, so that the load state of active intermediate on carrier can be improved, and the catalytic performance of reaction can be raised.
The catalyst is the core of the technology for preparing 4MP1 by propylene dimerization, so that the development of the catalyst with high propylene conversion rate and high selectivity is particularly important.
Disclosure of Invention
Based on the background art, the invention aims to provide a supported alkali metal catalyst and a preparation method thereof. The catalyst is used for preparing 4MP1 by propylene dimerization, and has high propylene conversion rate and high 4MP1 selectivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a supported alkali metal catalyst comprising: a carrier and sodium and/or potassium supported thereon; the carrier is obtained by mixing alkali metal salt with a modifier solution and then roasting; the modifier comprises a crown ether, or a combination of crown ether and graphite.
The carrier is obtained by adding modifier solution into alkali metal salt for treatment, wherein the modifier solution is mainly crown ether solution, and graphite can be further added. Specifically, the processing procedure comprises: mixing alkali metal salt with modifier solution, and roasting to obtain the carrier.
According to the research of the microstructure of the active site and the catalytic mechanism of the catalyst, the catalytic activity of the solid base is related to the number and strength of the surface base, and in addition, the microenvironment of the surface base of the solid base, including the specific surface area, the pore structure, the size, the affinity of the surface to the substrate and the like, are influenced. The dispersion state of alkali metal sodium and/or potassium on the carrier surface is considered by the mainstream theory to be mainly dispersed at unsaturated coordination centers and lattice defects on the carrier surface, and not only the uniform dispersion of a close-packed monolayer on the carrier surface is carried out. Thus, the formation of a specific vacancy structure of the base sites on the support surface and the uniform dispersion are advantageous conditions for the formation of uniformly distributed catalytically active centers.
The invention adds proper guest into alkali metal salt, then forms the needed carrier with special vacancy structure and evenly dispersed through pretreatment modes such as drying and roasting, then carries out the loading of alkali metal, fully combines the lattice defect on the surface of the carrier with the alkali metal to reach the equilibrium size, and realizes even dispersion, thus obtaining the propylene dimerization catalyst with high propylene conversion rate and high selectivity. Through a great deal of intensive research, the invention discovers that after alkali metal salt and crown ether with a hole structure are uniformly mixed, the carrier obtained by drying and roasting treatment is provided with lattice defects on the surface, and the prepared catalyst has high propylene conversion rate and 4MP1 selectivity.
Crown ethers are macrocyclic compounds whose hole structure has a selective action on ions, capable of complexing metal ions, in particular alkali metal ions, while releasing anions outside the hole. Uniformly mixing alkali metal salt and crown ether solution to make crown ether complex ions on the surface of alkali metal salt; and then roasting to remove the organic compound to obtain the alkali metal salt carrier with gray or black surface. The carrier baked after crown ether treatment can not damage the aggregation state of crystal particles, and can not generate a molten gel state, so that the original three-dimensional particle state is maintained. In the scanning electron microscope of the alkali metal salt carrier obtained by the above method, it was found that the carrier was in the form of spherical particle aggregates, the most probable primary particle size of which was < 1. Mu.m ("the most probable primary particle" statement originated from patent application CN 1405128A). The mercury porosimetry characterization result is that the pore size distribution range is 80 nm-12000 nm, the total pore volume is not less than 0.2mL/g, and preferably not less than 0.25mL/g.
The supported alkali metal catalyst according to the present invention, preferably, the mass of the sodium and/or potassium is 0.5% to 20% of the support; more preferably 1% -15%; further preferably 2% -10%.
According to the supported alkali metal catalyst of the present invention, preferably, the crown ether is added to the modifier solution in an amount of 0.01% to 20% by mass of the alkali metal salt; more preferably 0.1% -15%; further preferably 0.2% -10%.
According to the supported alkali metal catalyst of the present invention, preferably, when the modifier is a combination of crown ether and graphite, the amount of graphite added in the modifier solution is 0.2% to 1.5% by mass of the alkali metal salt. The addition amount of the crown ether is still 0.01% -20% of the mass of the alkali metal salt; more preferably 0.1% -15%; further preferably 0.2% -10%.
The addition of graphite can further increase the activity or propylene conversion of the finally obtained propylene dimerization catalyst.
The supported alkali metal catalyst according to the present invention, preferably, the carrier has a particle diameter of 5 to 100 mesh; more preferably 10-80 mesh; further preferably 20 to 60 mesh.
The supported alkali metal catalyst according to the present invention is preferably at least one selected from the group consisting of alkali metal carbonates and alkali metal hydrogencarbonates.
The supported alkali metal catalyst according to the present invention, preferably, the alkali metal carbonate includes potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
The supported alkali metal catalyst according to the present invention is preferably used, preferably, the crown ether is selected from 18-crown-6, dibenzo-18-crown-6, aza-18-crown-6, benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6-ether, 4-hydroaminodibenzo-18-crown (ether) -6, 12-crown-4-ether, 15-crown-5, crown-8-ene, 4 '-nitrobenzo-15-crown-5-ether, 4' -aminobenzo-15-crown-5-ether, N-benzazepine-15-crown-5-ether, 4 '-carboxybenzo-15-crown-5-ether, 2- (hydroxymethyl) -12-crown-4-ether, 24-crown-8-ether, 15-crown-4 [4- (2, 4-dinitrophenylazo) phenol ], 4' -acetylbenzo-18-crown-6-ether, 4 '-acetylbenzo-15-crown-5-ether, 4' -formylbenzo-18-6-crown-ether, 1 '-aza-8-crown-ether, 4' -benzazepine-6-ether, N-crown-10-crown-5-ether, N-benzazepine-6-ether, N-5-crown-ether, N-naphthyridine-18-crown-6-ether, N-dibenzpine-10-5-ether, 4 '-methoxycarbonylbenzo-15-crown 5-ether, 4' -nitrobenzo-18-crown 6-ether, dicyclohexyl-18-crown 6-ether, 2- (allyloxymethyl) -18-crown 6-ether, 4 '-bromobenzo-15-crown 5-ether, 2- (hydroxymethyl) -18-crown 6-ether, 4' -formylbenzo-15-crown 5-ether, 1-aza-15-crown 5-ether, 18-crown 5[4- (2, 4-dinitrophenylazo) phenol ], dibenzo-15-crown 5-ether, dibenzo-21-crown 7-ether, bis (1, 4-phenylene) -34-crown 10-ether, 4, 13-diaza-18-crown 6-ether, dibenzo-24-crown 8-ether, 2- (hydroxymethyl) -15-crown 5-ether, 4-bromobenzo-18-crown 6-ether, 4, 10-diaza-12-crown 4-ether, 3-diisopropylenyl-5-ether, 4-crown 6-methyl-5-amino-4-crown 6-ether, 4-carbamic acid, 4-methyl-5-crown 6-ether, 4-carbamic acid, 4-methyl-5-methyl-crown 6-ether, at least one of cyclohexane-18-crown-6, 4-tert-butylcyclohexane-15-crown-5, poly (dibenzo-18-crown-6), 2, 3-naphtho-15-crown-5, dicyclohexyl-24-crown-8, 4' -amino-5 ' -nitrobenzo-15-crown-5 and 4',4 "(5") -di-tert-butyldicyclohexyl-18-crown-6.
More preferably, the crown ether is selected from at least one of 18-crown ether-6, 15-crown ether-5, benzo-18-crown-6-ether, aza-18-crown ether-6, 4-tert-butylcyclohexane-15-crown-5, dibenzo-24-crown-8-ether.
The second aspect of the present invention provides a method for producing the above supported alkali metal catalyst, comprising the steps of:
Mixing alkali metal salt with a modifier solution, and roasting to obtain the carrier;
And carrying out loading on the metal sodium and/or potassium and the carrier to obtain the supported alkali metal catalyst.
According to the preparation method of the present invention, preferably, the mass of crown ether in the modifier solution is 0.01 to 20wt.% of the mass of the alkali metal salt; more preferably 0.1% -15%; further preferably 0.2% -10%.
According to the preparation method of the present invention, preferably, when the modifier is a combination of crown ether and graphite, the mass of the graphite is 0.2% to 1.0% of the alkali metal salt. The mass of the crown ether is still 0.01-20wt.% of the mass of the alkali metal salt; more preferably 0.1% -15%; further preferably 0.2% -10%.
According to the production method of the present invention, preferably, the solvent of the modifier solution is selected from at least one of alcohols, ketones, ethers, esters, amines, aromatic hydrocarbons, and chlorinated alkanes; more preferably, the solvent is at least one selected from ethanol, isopropanol, acetone, diethyl ether.
According to the preparation method of the present invention, preferably, the temperature of the mixing is 0 to 200 ℃. More preferably, the temperature of the mixing is 60-150 ℃.
According to the preparation method of the present invention, preferably, the temperature of the mixing is from room temperature to 200 ℃ for 0.1h to 3h. More preferably, the temperature of the mixing is 80-150 ℃ and the time is 0.5-2 h.
According to the preparation method of the present invention, preferably, the baking temperature is 200 to 600 ℃.
According to the production method of the present invention, preferably, the calcination time is 1h to 6h.
Roasting is carried out in an air atmosphere, and then inert gas can be introduced to continue roasting or inert gas can be introduced in the slow cooling process. Roasting to remove organic compounds, and obtaining the alkali metal carbonate carrier with gray or black surface.
According to the production method of the present invention, preferably, the firing includes: roasting for 1-6 h in air atmosphere at 200-600 ℃, and then introducing protective gas.
According to the production method of the present invention, preferably, the firing includes: roasting for 1-6 h in an air atmosphere at 200-600 ℃, and then roasting for 1-4 h in a protective gas atmosphere. The firing includes: roasting for 2-4 h in air atmosphere at 250-500 ℃, and roasting for 1-3 h in protective gas atmosphere.
Roasting at high temperature in the presence of oxygen and then in an inert environment to remove organic compounds, so as to obtain the alkali metal salt carrier with grey or black surface.
According to the preparation method of the present invention, preferably, the mixing is achieved by stirring, rotation or vibration.
According to the preparation method of the invention, preferably, the roasting further comprises the step of sieving under the condition of water and oxygen isolation.
According to the production method of the present invention, preferably, the carrier has a particle diameter of 5 to 100 mesh; more preferably 10-80 mesh; further preferably 20 to 60 mesh.
According to the preparation method of the present invention, preferably, the mass of the metallic sodium and/or potassium is 0.5% to 20% of the mass of the carrier; more preferably 1% -15%; further preferably 2% -10%.
Because of the active chemical nature of alkali metals, conventional impregnation, sol-gel and precipitation methods are not applicable, and common loading methods include alkali metal melting loading, alkali metal decomposition loading of azide, impregnation of liquid ammonia solution containing alkali metal, and the like. The loading of the invention can adopt a metal sodium and/or potassium and carrier melting loading mode; alternatively, the catalyst may be obtained by dissolving metallic sodium and/or potassium in liquid ammonia, completely impregnating the support, and then evaporating the ammonia from the solution-impregnated support.
According to the preparation method of the invention, preferably, the loading is carried out by adopting a mode of carrying out molten loading of metallic sodium and/or potassium and a carrier.
According to the production method of the present invention, preferably, the melt-supporting is performed in a protective gas atmosphere.
According to the production method of the present invention, preferably, the shielding gas is selected from nitrogen, helium, argon, and the like.
According to the production method of the present invention, preferably, the temperature of the melt load is 10 to 240 ℃ higher than the melting point of metallic sodium and/or potassium; more preferably 20-200 ℃ above the melting point of metallic sodium and/or potassium; further preferably 30-100 ℃ above the melting point of metallic sodium and/or potassium.
According to the preparation method of the invention, the preferable scheme of the melting load comprises the following steps: the weighed carrier and alkali metal are placed in a pressure bomb in an anhydrous and anaerobic tank, and then the pressure bomb is placed in a homogeneous reactor for heating and rotation.
The preparation method of the supported alkali metal catalyst improves the micro-environment of the surface of the carrier, so that the surface of the carrier forms a special vacancy structure and is uniformly dispersed, the uniform dispersion of active metal is facilitated, and the prepared catalyst has good performance, high propylene conversion rate and high selectivity of 4MP 1.
In a third aspect, the present invention provides the use of the above supported alkali metal catalyst in the dimerization of propylene to 4-methyl-1-pentene.
The invention adds crown ether with hole structure into alkali metal salt, then forms carrier with special hole structure and evenly disperse through pretreatment modes such as drying and roasting, then carries on alkali metal loading, the alkali metal and the crystal lattice defect on the carrier surface are fully combined to reach equilibrium size, and the even disperse is realized, the propylene dimerization catalyst has high propylene conversion rate and high selectivity.
Drawings
FIG. 1a is a scanning electron microscope image of a calcined potassium carbonate support treated with a crown ether solution in example 1.
FIG. 1b is a scanning electron microscope image of a calcined potassium carbonate support treated with a crown ether solution in example 10.
FIG. 2a is a scanning electron microscope image of the calcined potassium carbonate carrier treated with graphite alone in comparative example 1.
FIG. 2b is a scanning electron microscope image of the calcined potassium carbonate carrier treated with graphite alone in comparative example 3.
FIG. 2c is a scanning electron microscope image of the calcined potassium carbonate support without crown ether and graphite treatment of comparative example 4.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about".
In the following examples and comparative examples, "low-speed stirring" means stirring at a rotational speed of 40 to 50 r/min; the speed of the low-speed oscillation is also 40-50r/min.
In the present invention, the primary particle size and aggregation morphology were measured using a scanning electron microscope, and in the preferred embodiment of the present invention, the scanning electron microscope pictures of the potassium carbonate carrier after solution treatment and calcination using crown ether are shown in fig. 1a and 1 b. Scanning electron microscope pictures of the potassium carbonate carrier treated by only the graphite are shown in fig. 2a and 2b, and scanning electron microscope pictures of the potassium carbonate carrier not treated by the graphite and crown ether are shown in fig. 2 c.
The pore size distribution, pore volume, specific surface area and porosity were measured by mercury intrusion, and the carrier particle size was measured by sieving.
The catalyst evaluation process in the implementation of the invention comprises the following steps:
Batch kettle reaction:
The catalyst was prepared in an amount of 250mL autoclave under nitrogen atmosphere. The mass of the kettle body is m 1. Then, propylene was injected into the autoclave, and the autoclave body weight m 2 was measured, and the propylene addition amount was calculated to be m Polypropylene (C) . Subsequently, the reaction vessel was heated to the reaction temperature and reacted for a certain period of time. And cooling the reaction system to below 20 ℃, sampling and then emptying residual gas phase components in the kettle, weighing the mass of the kettle body after emptying to be m 3, and calculating the liquid recovery mass m Liquid and its preparation method . And taking gas and liquid for analysis of the content of the product components. Propylene conversion, 4MP1 selectivity was calculated.
(1) Propylene conversion C:
(2) 4MP1 Selectivity S
Wherein:
m Polypropylene (C) -mass of propylene added before reaction;
m Liquid and its preparation method -the liquid recovery after reaction;
X Liquid C -percentage of propylene in gas chromatography of liquid;
x Air conditioner —percentage of propylene in gas chromatography;
X 4MP1 -4 MP1 percent in liquid gas chromatography.
Fixed bed gas phase reaction:
about 50mL of the catalyst was packed into the fixed bed reactor at the constant temperature zone under nitrogen protection, with the upper and lower ends being supported with glass beads. The polymerization grade propylene is pumped into a reaction device through a advection pump and enters a reactor through a vaporizer, the reaction temperature in the vaporizer and the reactor is 140-160 ℃, the pressure is controlled to be about 10MPa, and a certain airspeed is controlled. The reaction product was analyzed by on-line chromatography via a six-way valve, a pressure reducer. Propylene conversion, 4MP1 selectivity was calculated.
The reaction results were analyzed by on-line chromatography. Propylene conversion, 4MP1 selectivity was calculated.
(1) Propylene conversion C:
C＝(1-X Polypropylene (C) )×100％
(2) 4MP1 Selectivity S
Wherein:
X Polypropylene (C) —percentage of propylene in gas chromatography of the product;
X 4MP1 -4 MP1 percent in gas chromatography of the product.
Example 1
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Preparation of the catalyst
Preparing a carrier: 50g of anhydrous potassium carbonate is put into a flask, then 2.5g of 18-crown ether-6 is dissolved in 2.0g of ethanol and added into the anhydrous potassium carbonate in a sesame seed cake, and the materials are mixed and heated to 80 ℃ and stirred for 1h at a low speed; placing the materials in a crucible, roasting for 2 hours at 450 ℃ in a muffle furnace, and then introducing micro nitrogen flow to continue roasting for 2 hours; and (3) after the temperature is reduced to below 50 ℃, 30g of the 20-60 mesh carrier is screened and sealed under the condition of water and oxygen isolation and is used for loading.
The resulting carrier was subjected to scanning electron microscopy analysis as shown in FIG. 1 a. As can be seen from fig. 1 a: the potassium carbonate carrier is granular, the particles are clustered, and the particle size of the most primary particles is less than 1 mu m; meanwhile, the total pore volume is 0.2630mL/g measured by mercury intrusion method, and the distribution range of the most probable pore diameter is 100-12000 nm.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.5g sodium, adding into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous reactor, heated to 150 ℃, rotated for 5 hours, and the prepared catalyst is silver gray and is sealed and preserved for standby.
2) Catalyst evaluation
Weighing 10g of the prepared catalyst, adding the catalyst into a high-pressure reaction kettle, and then injecting 95g of propylene into the high-pressure kettle; heating the materials in the reaction kettle to 140-155 ℃ for reaction for 20 hours, cooling the system to below 20 ℃ after the reaction is finished, discharging air phase, sampling for gas chromatography analysis, collecting liquid phase 47g, and performing gas chromatography analysis. The propylene conversion was calculated to be 50.5% and the 4MP1 selectivity was 86.9%.
Example 2
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 1, except that in the preparation of the support:
crown ether 1.0g 15-crown 5 ether and solvent 1.5g acetone;
after the materials are mixed, the materials are not heated to 80 ℃ but stirred for 3 hours at a low speed at normal temperature;
The material was calcined in a muffle furnace at 400 c for 3 hours and then calcined in a slight nitrogen stream for a further 2 hours.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 28g of liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 30.1% and the 4MP1 selectivity was 93.1%.
Example 3
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was essentially the same as in example 1, except that:
During the preparation of the carrier:
Crown ether 7.0g benzo-18-crown-6-ether and solvent 5.5g ethanol;
after mixing, the materials were not heated to 80 ℃, but stirred at low speed for 1.5h at 100 ℃;
Roasting the material in a muffle furnace at 550 ℃ for 1.5 hours, and then continuously roasting the material in a micro nitrogen flow for 1.5 hours;
screening is to screen 30g of 5-40 mesh vector;
3.0g of potassium is adopted to replace sodium in the metal loading process; the pressure solvent bomb is heated to 120 ℃ in a homogeneous reactor and rotated for 8 hours, and the surface of the prepared catalyst is light blue, and the inside of the catalyst is dark silver.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 42g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 45% and the 4MP1 selectivity was 85.7%.
Example 4
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
Preparing a carrier: adding 30g of anhydrous potassium carbonate and 20g of anhydrous sodium carbonate into a triangular flask, adding 0.5g of 4-tert-butylcyclohexane-15-crown-5 into the triangular flask after dissolving in 1.0g of ethanol, adding 0.3g of graphite into the triangular flask, heating the triangular flask to 150 ℃ in a vibrating box, vibrating at a low speed for 0.5h, placing the triangular flask into a crucible, roasting in a muffle furnace for 4h at 300 ℃, and continuously roasting in a micro nitrogen flow for 2h; and (3) after the temperature is reduced to below 50 ℃, 30g of the 20-80 mesh carrier is screened and sealed for loading in a water and oxygen isolation environment.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.0g potassium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 120 ℃ and rotated for 8 hours, whereby the catalyst produced had a silver metallic luster.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 38g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 40.7% and the 4MP1 selectivity was 87.3%.
Example 5
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 4, except that:
50g of anhydrous sodium bicarbonate is taken to replace anhydrous potassium carbonate and anhydrous sodium carbonate, 1.5g of 4-tert-butylcyclohexane-15-crown-5 is taken to be dissolved in 2.0g of isopropanol, and the amount of graphite is 0.5g; heating to 200 ℃ in a vibration box, and vibrating at a low speed for 0.2h. Roasting for 5 hours at 250 ℃ in a muffle furnace, and beginning to cool and introduce micro nitrogen flow for 2 hours. 30g of a 40-80 mesh carrier is screened, 1.5g of sodium is added, and the mixture is heated to 200 ℃ in a pressure bomb and rotated for 5 hours. The catalyst prepared was black gray.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 41g of liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 43.2% and the 4MP1 selectivity was 83.6%.
Example 6
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 4, except that:
50g of anhydrous potassium carbonate is taken to replace the anhydrous potassium carbonate and the anhydrous sodium carbonate, 0.3g of 18-crown ether-6 and 0.1g of dibenzo-24-crown 8-ether are taken to be dissolved in 0.5g of ethanol, and the amount of graphite is 0.1g; heating to 120 ℃ in a vibrating box, and vibrating at a low speed for 1h. Roasting for 3 hours at 480 ℃ in a muffle furnace, introducing micro nitrogen flow, and continuously roasting for 3 hours. 30g of a carrier with 20-100 meshes is screened, 2.0g of potassium is added, and the mixture is heated to 150 ℃ in a pressure bomb and rotated for 5 hours. The catalyst obtained had metallic luster.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 69g of liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 73% and the 4MP1 selectivity was 69.7%.
Example 7
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 6, except that:
3g of aza-18-crown ether was dissolved in 2.6g of diethyl ether, and the amount of graphite was 0.7g. Roasting for 3 hours at 300 ℃ in a muffle furnace, introducing micro nitrogen flow, continuously roasting for 1 hour, starting cooling, and continuously introducing nitrogen flow for 2 hours. 30g of a 20-60 mesh carrier is screened, 2.0g of potassium and 0.5g of sodium are added, and the mixture is heated to 100 ℃ in a pressure bomb and rotated for 5 hours. The catalyst obtained had metallic luster.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. The liquid phase was collected at 53g and analyzed by gas chromatography. The propylene conversion was calculated to be 56.1% and the 4MP1 selectivity was 86.4%.
Example 8
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 7, except that:
5.0g of aza-18-crown ether was dissolved in 3.5g of diethyl ether, and the amount of graphite was 0.3g. 30g of a 20-60-mesh carrier is screened, 5.5g of potassium is added, and the mixture is heated to 100 ℃ in a pressure bomb and rotated for 8 hours. The catalyst solid produced was blocked blue and had a silver gray interior.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 54g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 57.0% and the 4-MP-1 selectivity was calculated to be 63.2%.
Example 9
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 7, except that:
0.1g of 18-crown ether-6 is dissolved in 0.5g of ethanol, the amount of graphite is 0.3g, and the materials are mixed at normal temperature and vibrated for 1h at a low speed. 30g of a 20-60-mesh carrier is screened, 0.3g of potassium is added, and the mixture is heated to 100 ℃ in a pressure bomb and rotated for 4 hours. The catalyst produced was slightly silvery.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 15g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 16.5% and the 4MP1 selectivity was 96.1%.
Example 10
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
The catalyst preparation was the same as in example 9, except that:
2.0g of 18-crown ether-6 is dissolved in 1.9g of ethanol, the amount of graphite is 0.5g, 30g of 20-60 mesh carrier is selected, 1.5g of potassium is added, and the mixture is heated to 170 ℃ in a pressure bomb and rotated for 2.5h. The catalyst produced was blue and silver.
The resulting carrier was subjected to scanning electron microscopy analysis as shown in FIG. 1 b. As can be seen from fig. 1 b: the potassium carbonate carrier is granular, the particles are clustered, and the particle size of most primary particles is less than 1 mu m. The total pore volume 0.3085mL/g is measured by mercury intrusion method, and the distribution range of the most probable pore diameter is 80-10000 nm.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 63g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 65.3% and the 4MP1 selectivity was 86.5%.
Comparative example 1
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
Preparing a carrier: 50g of anhydrous potassium carbonate is taken and placed in a crucible, 0.5g of graphite is added, roasting is carried out for 3 hours at 300 ℃ in a muffle furnace, then micro nitrogen flow is introduced for continuous roasting for 1 hour, cooling is started, and nitrogen flow is introduced for 2 hours; and (3) after the temperature is reduced to below 50 ℃, 30g of the 20-60 mesh carrier is screened and sealed for loading in a water and oxygen isolation environment.
The resulting carrier was subjected to scanning electron microscopy analysis as shown in fig. 2 a. As can be seen from fig. 2 a: the potassium carbonate carrier which is not treated by crown ether is lamellar and aggregated in a cross-linked state, the most probable primary particle size is more than 1 mu m total pore volume 0.1254mL/g, and the most probable pore diameter is in multi-stage irregular distribution of mesopores and macropores.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.5g potassium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 170 ℃ and rotated for 2.5h, whereby the catalyst was prepared to have metallic luster.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 32g of the liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 35.0% and the 4MP1 selectivity was 84.3%.
Comparative example 2
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
Preparing a carrier: taking 50g of sodium bicarbonate in a crucible, adding 0.5g of graphite, roasting in a muffle furnace at 250 ℃ for 5 hours, and then introducing micro nitrogen flow to continue roasting for 2 hours; after the temperature is reduced to below 50 ℃, 30g of 40-80 carriers are screened and sealed for loading in a water-proof and oxygen-proof environment.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.5g sodium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 200 ℃, and rotated for 5 hours, whereby the prepared catalyst was silver gray.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 22g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 24.0% and the 4MP1 selectivity was 82.8%.
Comparative example 3
The following catalysts were prepared and evaluated using batch-kettle reactions:
1) Catalyst preparation
Preparing a carrier: 50g of anhydrous potassium carbonate is taken and placed in a crucible, 0.5g of graphite is added, the mixture is roasted for 1.5 hours in a muffle furnace at 550 ℃, and then micro nitrogen flow is introduced to continue roasting for 1.5 hours; after the temperature is reduced to below 50 ℃,30 g of 5-40 mesh carrier is screened and sealed for loading in a water-proof and oxygen-proof environment.
The resulting carrier was subjected to scanning electron microscopy analysis as shown in FIG. 2 b. As can be seen from fig. 2 b: the potassium carbonate carrier which is not treated by crown ether is aggregated in a cross-linked state, the particle size of the most probable primary particles is more than 1 mu m, the total pore volume is 0.0913mL/g, and the most probable pore diameter is in multi-stage irregular distribution of mesopores and macropores.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 3.0g potassium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 150 ℃, rotated for 8 hours, and the catalyst thus prepared was blue-gray and agglomerated.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 6g of the liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 7.3% and the 4MP1 selectivity was 84.2%.
Comparative example 4
The following catalysts were prepared and evaluated using batch-kettle reactions:
Preparing a carrier: 50g of anhydrous potassium carbonate is taken and put in a crucible, roasting is carried out for 2 hours at 450 ℃ in a muffle furnace, and then micro nitrogen flow is introduced for continuous roasting for 2 hours; and (3) after the temperature is reduced to below 50 ℃, 30g of the 20-60 mesh carrier is screened and sealed for loading in a water and oxygen isolation environment.
The resulting carrier was subjected to scanning electron microscopy analysis as shown in FIG. 2 c. As can be seen from fig. 2 c: the potassium carbonate carrier which is not treated by crown ether is aggregated in a cross-linked state, the particle size of the most probable primary particles is more than 1 mu m, the total pore volume is 0.0745mL/g, and the most probable pore diameter is in multi-stage irregular distribution of mesopores and macropores.
Load metal: adding the 30g carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.5g sodium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 150 ℃ and rotated for 5 hours, whereby the catalyst prepared was grey.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1, and 11g of a liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 11.4% and the 4MP1 selectivity was 84.5%.
Table 1 is the test data of examples 1 to 10 and comparative examples 1 to 4, and it can be seen from the comparison of the data in the table: the crown ether is added during the carrier treatment, and compared with the catalyst prepared by the carrier without the crown ether treatment, the propylene conversion rate and the selectivity of 4MP1 are improved.
Table 1 experimental data for example 1-example 10 and comparative examples 1-4
Example 11
This example uses a fixed bed continuous reaction to evaluate the catalyst prepared in example 1:
45mL of the catalyst of example 1 was weighed and charged into a fixed bed reactor. Propylene is pumped by a advection pump, the temperature of the reactor is raised to 150 ℃, the pressure is 9.8MPa, the airspeed is adjusted to 1.3h -1, and the reaction is continuously carried out. When the reaction was carried out for 20 hours, the propylene conversion was 30.5%, and the selectivity for 4MP1 was 87.0%. When the reaction was carried out for 48 hours, the propylene conversion was 37.1%, and the 4MP1 selectivity was 89.2%.
Example 12
This example uses a fixed bed continuous reaction to evaluate the catalyst prepared in example 7:
The catalyst evaluation method was the same as in example 11. The difference is that: 20mL of the catalyst in example 7 was measured. When the reaction was carried out for 20 hours, the propylene conversion was 27.1%, and the selectivity to 4MP1 was 90.2%. When the reaction proceeded to 48h, the propylene conversion was 38.3% and the 4MP1 selectivity was 89.5%.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (21)

1. A supported alkali metal catalyst, characterized in that the catalyst comprises: a carrier and sodium and/or potassium supported thereon;
The carrier is obtained by mixing alkali metal salt with a modifier solution and then roasting;
the modifier is crown ether or the combination of crown ether and graphite;
When the modifier is crown ether, the addition amount of crown ether in the modifier solution is 0.01-20% of the mass of the alkali metal salt;
When the modifier is a combination of crown ether and graphite, the addition amount of the graphite in the modifier solution is 0.2-1.50% of the mass of the alkali metal salt, and the addition amount of the crown ether in the modifier solution is 0.01-20% of the mass of the alkali metal salt.
2. The supported alkali metal catalyst according to claim 1, wherein the carrier has a primary particle size of < 1 μm; the pore size distribution is 80 nm-12000 nm, and the total pore volume is not less than 0.2 mL/g.
3. The supported alkali metal catalyst according to claim 1, wherein the mass of sodium and/or potassium is 0.5% -20% of the carrier.
4. The supported alkali metal catalyst according to claim 1, wherein the particle size of the support is 5-100 mesh.
5. The supported alkali metal catalyst according to claim 1, wherein the alkali metal salt is selected from at least one of an alkali metal carbonate and an alkali metal bicarbonate.
6. The supported alkali metal catalyst of claim 5, wherein the alkali metal carbonate comprises potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
7. The supported alkali metal catalyst according to claim 1, wherein the crown ether is selected from the group consisting of 18-crown-6, dibenzo-18-crown-6, aza-18-crown-6, benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6, 4-hydroaminodibenzo-18-crown (ether) -6, 12-crown-4-ether, 15-crown-5, 4' -nitrobenzo-15-crown-5-ether, 4' -aminobenzo-15-crown-5-ether, N-benzazepine-15-crown-5-ether, 4' -carboxybenzo-15-crown-5-ether, 2- (hydroxymethyl) -12-crown-4-ether, 24-crown-8-ether, 4' -acetylbenzo-18-crown-6-ether, 4' -acetylbenzo-15-crown-5-ether, 4' -formylbenzo-18-crown-6-ether, 1-aza-12-crown-5-ether, N-benzazepine-15-crown-5-ether, 4' -carboxybenzo-5-ether, 2- (hydroxymethyl) -12-crown-4-crown-ether, 24-crown-8-ether, 4' -acetylbenzo-6-crown-ether, 4' -nitrobenzo-6-crown-5-ether, N-nitro-5-c-5-ether, N-benzazepine-5-ether, N-18-crown-5-ether, 5-methoxyl-5-yl-benzoyl-crown-6-5-ether, N-benzo-crown-6-5-nitro-naphtyl ether Dicyclohexyl-18-crown-6 ether, 2- (allyloxymethyl) -18-crown-6-ether, 4 '-bromobenzo-15-crown-5-ether, 2- (hydroxymethyl) -18-crown-6-ether, 4' -formylbenzo-15-crown-5-ether, 1-aza-15-crown-5-ether, dibenzo-21-crown-7-ether, bis (1, 4-phenylene) -34-crown-10-ether, 4, 13-diaza-18-crown-6-ether, dibenzo-24-crown-8-ether, 2- (hydroxymethyl) -15-crown-5-ether, 4-bromobenzo-18-crown-6-ether, 4, 10-diaza-12-crown-4-ether, 1, 3-diisopropyloxycycloarene crown-6, 2-aminomethyl-18-crown-6, 4-tert-butylbenzo-15-crown-5-ether, 4-vinylbenzyl-18-crown-6, 2-benzyl-6-n-5-ether, 3-bromobenzo-18-crown-6-ether, 4-naphtyl-crown-5-ether, 4-bromo-18-crown-6-ether, 4, 5-naphtalene-5-crown-5-ether, at least one of dicyclohexyl-24-crown-8, 4' -amino-5 ' -nitrobenzo-15-crown-5 and 4',4' ' (5 ' ') -di-tert-butyldicyclohexyl-18-crown-6.
8. The supported alkali metal catalyst according to claim 7, wherein the crown ether is selected from at least one of 18-crown ether-6, 15-crown ether-5, benzo-18-crown-6-ether, aza-18-crown ether-6, 4-t-butylcyclohexane-15-crown-5, dibenzo-24-crown-8-ether.
9. A process for the preparation of a supported alkali metal catalyst as claimed in any one of claims 1 to 8, characterized in that the process comprises the steps of:
Mixing alkali metal salt with a modifier solution, and roasting to obtain the carrier;
carrying out loading on metal sodium and/or potassium and the carrier to obtain the loaded alkali metal catalyst;
Wherein the mass of crown ether in the modifier solution is 0.01-20% of the mass of alkali metal salt, and when the modifier is the combination of crown ether and graphite, the mass of graphite in the modifier solution is 0.2-1.50% of the mass of alkali metal salt.
10. The method according to claim 9, wherein the solvent of the modifier solution is at least one selected from the group consisting of alcohols, ketones, ethers, esters, amines, aromatic hydrocarbons and chlorinated alkanes.
11. The method according to claim 10, wherein the solvent is at least one selected from ethanol, isopropanol, acetone, and diethyl ether.
12. The method of claim 9, wherein the temperature of the mixing is 0-200 ℃.
13. The method of claim 9, wherein the firing temperature is 200-600 ℃.
14. The method of claim 13, wherein the firing time is 1h to 6 h.
15. The method of preparing according to claim 9, wherein the firing comprises: roasting 1 h-6 h in an air atmosphere at 200-600 ℃, and then introducing protective gas.
16. The method of claim 9, wherein the roasting further comprises a step of sieving under a water-proof and oxygen-proof condition.
17. The method of claim 16, wherein the carrier has a particle size of 5-100 mesh.
18. The preparation method according to claim 9, wherein the mass of the metallic sodium and/or potassium is 0.5% -20% of the mass of the carrier.
19. The method according to claim 9, wherein the supported alkali metal catalyst is obtained by melt-supporting the metal sodium and/or potassium with the carrier.
20. The method of claim 19, wherein the melt loading is performed in a protective gas atmosphere.
21. The method of claim 19, wherein the temperature of the melt load is 10-240 ℃ above the melting point of the metallic sodium and/or potassium.
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