CN115193463B - Method for synthesizing 4-methyl-1-pentene by propylene dimerization - Google Patents

Method for synthesizing 4-methyl-1-pentene by propylene dimerization Download PDF

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CN115193463B
CN115193463B CN202111677275.5A CN202111677275A CN115193463B CN 115193463 B CN115193463 B CN 115193463B CN 202111677275 A CN202111677275 A CN 202111677275A CN 115193463 B CN115193463 B CN 115193463B
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crown
ether
carrier
propylene
catalyst
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CN115193463A (en
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王亚丽
蒋岩
朱丽娜
徐显明
霍宏亮
牟玉强
黄付玲
马鸿钰
王力搏
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 Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a method for synthesizing 4-methyl-1-pentene by propylene dimerization. The propylene dimerization adopts a fixed bed gas phase reaction, and comprises the following steps: filling the catalyst into a constant temperature zone of a fixed bed reactor under the protection of nitrogen; raw material propylene enters a fixed bed reactor through a vaporizer to react, and a reaction product enters a gas-liquid separator after passing through a pressure reducer to obtain a liquid phase containing the 4-methyl-1-pentene; 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 catalyst adopted in the method improves the surface microenvironment of the carrier, so that the carrier surface forms a special vacancy structure and is uniformly dispersed, the uniform dispersion of active metals is facilitated, and the prepared catalyst has good performance, high propylene conversion rate and high selectivity of 4MP 1.

Description

Method for synthesizing 4-methyl-1-pentene by propylene dimerization
Technical Field
The invention relates to the field of propylene dimerization catalysts, in particular to a method for synthesizing 4-methyl-1-pentene by propylene dimerization.
Background
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 4MP 1is 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 above background, it was an object of the present invention to provide a process for the dimerization of propylene to 4-methyl-1-pentene, which is carried out in the presence of a supported alkali metal catalyst and has a high propylene conversion and a high selectivity to 4MP 1.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for the dimerization of propylene to 4-methyl-1-pentene, said dimerization of propylene employing a fixed bed gas phase reaction comprising the steps of:
Filling the catalyst into a constant temperature zone of a fixed bed reactor under the protection of nitrogen; raw material propylene enters a fixed bed reactor through a vaporizer to react, and a reaction product enters a gas-liquid separator after passing through a pressure reducer to obtain a liquid phase containing the 4-methyl-1-pentene;
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.
In the method for synthesizing 4-methyl-1-pentene by propylene dimerization, the carrier of the catalyst is obtained by adding a modifier solution into alkali metal salt, and 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. Further, the firing includes aerobic firing and anaerobic firing.
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.
According to the method of the present invention, preferably, the temperature of the reaction is 0 to 250 ℃; the pressure of the reaction is 0.1-20 MPa; the liquid hourly space velocity is 0.1-10 h -1.
According to the process of the present invention, preferably the temperature of the reaction is 100-170 ℃, more preferably 130-170 ℃, and the pressure of the reaction is 7MPa-13MPa.
According to the method of the invention, preferably, the carrier has a particle size of the most probable primary particles < 1 μm; the pore size distribution is 80nm-12000nm, and the total pore volume is not less than 0.2mL/g.
According to the method of the present invention, preferably, the mass of the sodium and/or potassium is 0.5% -20% of the carrier; more preferably 1% -15%; further preferably 2% -10%.
According to the method 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 method 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 1.50% 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.
According to the method of the present invention, preferably, the carrier has a particle size of 5 to 100 mesh; more preferably 10-80 mesh; further preferably 20 to 60 mesh.
According to the method of the present invention, preferably, the alkali metal salt is selected from at least one of alkali metal carbonate and alkali metal bicarbonate.
More preferably, the alkali metal carbonate comprises potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
Preferably, the crown ether is selected from the group consisting of 18-crown-6, dibenzo-18-crown-6 ether, 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' -acetophenone-18-crown-6-ether, 4' -acetophenone-15-crown-5-ether, 4' -aminobenzo-18-crown-6-ether, N-benzazepine-5-ether, 4' -carboxybenzo-15-crown-5-ether, 2- (hydroxymethyl) -12-crown-4-ether, N-crown-5-ether, N-benzazepine-10-30-ether, N ' -dibenzyl-4, 13-diaza-18-crown-6-ether, 4' -methoxycarbonylbenzo-15-crown-5-ether, 4' -Nitropheno-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, 1, 3-diisopropyloxycycloarene crown-6, 2-aminomethyl-18-crown-6, 4-tert-butylbenzene-15-crown-5, 4-vinylbenzyl-18-crown-6, 2-aminomethyl-15-crown-5, cyclohexane-18-crown-6, 4-tert-butylcyclohexane-15-crown-5, at least one of 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.
According to the 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 method of the present invention, preferably, the temperature of the mixing is from room temperature to 200 ℃ for a period of 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 method of the invention, preferably, the mixing is achieved by stirring, rotation or vibration.
According to the 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. More preferably, 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 invention, preferably, the roasting further comprises the step of sieving under the condition of water and oxygen isolation.
Specifically, the preparation of the catalyst comprises the following steps:
Mixing alkali metal salt with a modifier solution, and roasting to obtain the carrier; and carrying out melt loading on metal sodium and/or potassium and the carrier to obtain the propylene dimerization catalyst.
Preferably, the melt loading is performed in a protective gas atmosphere. The shielding gas is selected from nitrogen, helium, argon and the like. Preferably, the temperature of the melt load is 10-240 ℃ above the melting point of the metallic sodium and/or potassium; more preferably 20-200 c above the melting point of the metallic sodium and/or potassium.
The preferred version of the melting load comprises: 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 process of the 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 metals is facilitated, and the prepared catalyst has good performance, high propylene conversion rate and high selectivity of 4MP 1.
The method for synthesizing 4-methyl-1-pentene by propylene dimerization adopts a special catalyst, so that the propylene conversion rate and the selectivity of 4MP1 are improved. In the preparation process, crown ether with a hole structure is added into alkali metal salt, then complexation is carried out, and then a carrier with a special hole structure and uniform dispersion is formed in a pretreatment mode such as drying and roasting, then alkali metal loading is carried out, the alkali metal and crystal lattice defects on the surface of the carrier are fully combined to reach the equilibrium size, uniform dispersion is realized, and the prepared 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 7.
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.
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 graphite-treated potassium carbonate carrier alone are shown in fig. 2a and 2 b.
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 method for dimerization of propylene into 4-methyl-1-pentene in the examples and comparative examples of the present invention includes:
Method 1: 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.
Method 2: fixed bed gas phase reaction:
Under the protection of nitrogen, a certain amount of catalyst is filled into a constant temperature area of the fixed bed reactor, and the upper end and the lower end of the constant temperature area are filled with glass beads. Pumping polymerization grade propylene into a reaction device through a advection pump, entering a reactor through a vaporizer, heating the vaporizer and the reactor to 0-250 ℃, controlling the pressure to 0.1-20 MPa, and controlling the liquid hourly space velocity to 0.1-10 h -1. The reaction product enters a gas-liquid separator through a pressure reducer, wherein the reaction mixture passes through a six-way valve before entering the gas-liquid separator, and the reaction result is analyzed by online chromatography. 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
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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 ℃,30 g 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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
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%.
3) Method 2 for synthesizing 4-methyl-1-pentene by propylene dimerization
45ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene into a reactor by a constant flow pump through a vaporizer, controlling the temperature of the vaporizer to 145 ℃, the temperature of the reactor to 150 ℃, controlling the pressure to 9.8MPa, adjusting the airspeed to 1.3h -1, and continuously reacting. 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 continued for 48 hours, the propylene conversion was 37.1%, and the 4MP1 selectivity was 89.2%.
Example 2
This example provides a process for the dimerization of propylene to 4-methyl-1-pentene comprising the steps of:
30mL of the catalyst prepared in example 1 was charged into a fixed bed reactor. And pumping propylene into a reactor by a constant flow pump through a vaporizer, controlling the temperature of the vaporizer to 130 ℃, the temperature of the reactor to 130 ℃, controlling the pressure to 5.2MPa, adjusting the airspeed to 0.2h -1, and continuously reacting. When the reaction was carried out for 20 hours, the propylene conversion was 27.2%, and the selectivity to 4MP1 was 86.8%.
The other conditions are unchanged, the airspeed is continuously adjusted for 0.5h -1, when the reaction is continuously carried out for 48h, the propylene conversion rate is 33.1%, and the 4MP1 selectivity is 86.5%.
Continuously adjusting the temperature of the vaporizer to 140 ℃, controlling the temperature of the reactor to 140 ℃, controlling the pressure to 9.0MPa, controlling the space velocity to 1.0h -1, and continuously reacting for 60h, wherein the propylene conversion rate is 36.2%, and the selectivity of 4MP1 is 87.3%.
Example 3
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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 absolute 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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 42g of liquid phase was collected and analyzed by gas chromatography. The propylene conversion was calculated to be 45% and the 4MP1 selectivity was 85.7%.
3) Method 2 for synthesizing 4-methyl-1-pentene by propylene dimerization
30ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene through a vaporizer by adopting a constant flow pump, wherein the temperature of the vaporizer is 160 ℃, the temperature of a reactor is 160 ℃, the pressure is controlled to be 13MPa, the airspeed is adjusted to be 5.0h -1, and the continuous reaction is carried out. When the reaction was carried out for 20 hours, the propylene conversion was 22.5%, and the selectivity to 4MP1 was 86.0%.
The vaporizer temperature was adjusted to 170 ℃, the reactor temperature was 180 ℃, the pressure was controlled to 16MPa, the space velocity was adjusted to 9.0h -1, and when the reaction was continued for 45h, the propylene conversion was 15.1%, and the 4MP1 selectivity was 83.2%.
Example 4
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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 400c for 3 hours and then calcined in a slight nitrogen stream for a further 2 hours.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
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 5
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
1) Catalyst preparation
Preparing a carrier: placing 80g of anhydrous potassium carbonate into a flask, dissolving 1.0g of 15-crown 5-ether into 1.0g of acetone, adding into the anhydrous potassium carbonate in the flask, stirring at a low speed for 2.0h, and adding 0.8g of graphite into the flask; placing the materials in a crucible, roasting for 3 hours at 280 ℃ in a muffle furnace, and then introducing micro nitrogen flow to continue roasting for 1 hour; and after cooling, screening 45g of 20-40 mesh carrier under the condition of water and oxygen isolation, and sealing for loading.
Load metal: weighing the carrier into 200mL pressure bomb in an anhydrous and anaerobic box, weighing 2.5g of potassium into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous reactor, heated to 120 ℃, rotated for 8 hours, and the prepared catalyst is silver gray, the outer surface is slightly blue, and the catalyst is sealed and preserved for standby.
2) Dimerization of propylene to 4-methyl-1-pentene
30ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene through a vaporizer by adopting a constant flow pump, wherein the temperature of the vaporizer is 60 ℃, the temperature of the reactor is 60 ℃, the pressure is controlled to be 2MPa, the airspeed is adjusted to be 1.5h -1, and the continuous reaction is carried out. When the reaction was carried out for 20 hours, the conversion of propylene was 6.5%, and the selectivity of 4MP1 was 85.0%.
The vaporizer temperature is regulated to 100 ℃, the reactor temperature is regulated to 100 ℃, the control pressure is 6.0MPa, the space velocity is 3.0h -1, when the reaction is continued for 45h, the propylene conversion rate is 15.3%, and the 4MP1 selectivity is 86.9%.
Continuously adjusting the temperature of the vaporizer to 150 ℃, controlling the temperature of the reactor to 150 ℃, controlling the pressure to 10.0MPa, controlling the space velocity to 1.0h -1, and continuously reacting for 60h, wherein the propylene conversion rate is 41.5%, and the selectivity of 4MP1 is 86.3%.
Continuously adjusting the temperature of the vaporizer to 200 ℃, controlling the temperature of the reactor to 210 ℃, controlling the pressure to 20.0MPa, controlling the space velocity to 2.0h -1, and continuously reacting for 84h, wherein the propylene conversion rate is 5.6%, and the selectivity of 4MP1 is 34.3%.
Example 6
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
1) Catalyst preparation
Preparing a carrier: adding 50g of anhydrous potassium carbonate into a triangular flask, dissolving 3g of aza-18-crown ether into 2.6g of diethyl ether, adding into the triangular flask, adding 0.7g of graphite into the triangular flask, heating the triangular flask to 120 ℃ in a vibrating box, vibrating at a low speed for 1.0h, placing into a crucible, roasting in a muffle furnace at 300 ℃ for 3h, and continuously roasting under a micro nitrogen flow for 1h; after cooling, 30g of the carrier with 20-60 meshes is screened and sealed for loading in a water-proof and oxygen-proof environment.
Load metal: weighing the carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 2.0g of potassium and 0.5g of sodium into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous phase reactor, heated to 100 ℃, and rotated for 5 hours, so that the prepared catalyst has silvery metallic luster and has a small amount of blue on the surface.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
The same as in 2) of 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%.
2) Method 2 for synthesizing 4-methyl-1-pentene by propylene dimerization
20ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene through a vaporizer by adopting a constant flow pump, wherein the temperature of the vaporizer is 145 ℃, the temperature of the reactor is 150 ℃, the pressure is 9.8MPa, the airspeed is adjusted to 1.3h -1, and the continuous reaction is carried out. 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%.
Example 7
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
1) Catalyst preparation
Preparing a carrier: adding 50g of anhydrous potassium carbonate into a triangular flask, dissolving 2g of 18-crown ether-6 into 1.9g of diethyl ether, adding the solution into the triangular flask, adding 0.5g of graphite into the triangular flask, vibrating the triangular flask at a low speed for 1.0h at normal temperature in a vibrating box, placing the triangular flask into a crucible, roasting the crucible in a muffle furnace at 450 ℃ for 2h, and continuously roasting the crucible in a micro nitrogen flow for 1.5h; after cooling, 30g of the carrier with 20-60 meshes 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. 1b. 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.
Load metal: weighing the carrier into 100mL pressure bomb in an anhydrous and anaerobic box, weighing 1.5g of potassium into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor and heated to 170 ℃ and rotated for 2.5 hours, whereby the catalyst produced had a silvery metallic luster with a few blue colors on the surface.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 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%.
3) Method 2 for synthesizing 4-methyl-1-pentene by propylene dimerization
30ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene through a vaporizer by adopting a constant flow pump, wherein the temperature of the vaporizer is 145 ℃, the temperature of the reactor is 150 ℃, the pressure is 5MPa, and the space velocity is 1.5h -1, so as to continuously react. At 20h, the conversion of propylene was 28.1% and the selectivity of 4MP1 was 88.3%. The space velocity was adjusted to 0.8h -1, and when the reaction proceeded to 48h, the propylene conversion was 42.3%, and the 4MP1 selectivity was 86.4%.
Example 8
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 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 9
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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 in a muffle furnace at 250 ℃ for 5 hours, and continuously roasting in a 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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
The same as in 2) of 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 10
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
The same as in 2) of 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 11
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
The catalyst evaluation method was the same as in 2) 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 12
This example prepared the following catalyst and used the catalyst to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 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%.
Comparative example 1
The following catalysts were prepared and used to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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 3 hours in a muffle furnace at 300 ℃, and then micro nitrogen flow is introduced for continuous roasting for 3 hours; and (3) after the temperature is reduced to below 50 ℃,30 g 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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
Weighing 10g of the prepared catalyst, adding the catalyst into a high-pressure reaction kettle, and 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 gas phase, sampling for gas chromatography analysis, collecting 32g of liquid phase and performing gas chromatography analysis. 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 used to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 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 used to dimerize propylene to 4-methyl-1-pentene, comprising the following steps:
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) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 6g of a 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%.
3) Method 2 for synthesizing 4-methyl-1-pentene by propylene dimerization
30ML of the catalyst prepared above was weighed and charged into a fixed bed reactor. And pumping propylene into a reactor by a constant flow pump through a vaporizer, controlling the temperature of the vaporizer to 160 ℃, controlling the pressure to 13MPa, adjusting the space velocity to 5.0h -1, and continuously reacting. When the reaction was carried out for 20 hours, the conversion of propylene was 6.2%, and the selectivity of 4MP1 was 81.0%.
The vaporizer temperature was adjusted to 170 ℃, the reactor temperature was 180 ℃, the pressure was controlled to 16MPa, the space velocity was adjusted to 9.0h -1, and when the reaction was continued for 45h, the propylene conversion was 7.5%, and the 4MP1 selectivity was 63.9%.
Comparison of experimental data for examples and comparative examples shows that: 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.
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 (13)

1. A method for dimerization of propylene to 4-methyl-1-pentene, characterized in that the propylene dimerization employs a fixed bed gas phase reaction, comprising the following processes:
Filling the catalyst into a constant temperature zone of a fixed bed reactor under the protection of nitrogen; raw material propylene enters a fixed bed reactor through a vaporizer to react, and a reaction product enters a gas-liquid separator after passing through a pressure reducer to obtain a liquid phase containing the 4-methyl-1-pentene;
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 crown ether or a combination of crown ether and graphite;
the addition amount of crown ether in the modifier solution is 0.01-20% of the mass of the alkali metal salt;
The alkali metal salt is selected from at least one of alkali metal carbonate and alkali metal bicarbonate.
2. The method according to claim 1, wherein the temperature of the reaction is 0-250 ℃; the pressure of the reaction is 0.1-20 MPa; the liquid hourly space velocity is 0.1-10 h -1.
3. The method according to claim 1, wherein the temperature of the reaction is 130-170 ℃ and the pressure of the reaction is 7MPa-13MPa.
4. The method 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.
5. The method according to claim 1, wherein the mass of sodium and/or potassium is 0.5% -20% of the carrier.
6. The method according to claim 1, wherein when the modifier is a combination of crown ether and graphite, the amount of graphite added to the modifier solution is 0.2% to 1.50% by mass of the alkali metal salt.
7. The method of claim 1, wherein the carrier has a particle size of 5-100 mesh.
8. The method of claim 1, wherein the alkali metal carbonate comprises potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
9. The process 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-aminodibenzo-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-ether, dibenzo-15-crown-5-ether, N-benzazepine-5-ether, 4 '-carboxybenzo-15-crown-5-ether, 24-crown-8-ether, 4' -acetylbenzo-18-crown-6-ether, 4 '-nitrobenzoic-5-crown-ether, 4-5-methoxyl-18-crown-6-ether, N-5-methoxyl-5-ether, 4' -carboxy-18-crown-6-ether, 4-crown-5-c-5-ether, and the process of claim 1-dibenzo-18-crown-4-crown-4 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.
10. The method of claim 9, 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.
11. The method of claim 1, wherein the solvent of the modifier solution is selected from at least one of alcohols, ketones, ethers, esters, amines, aromatic hydrocarbons, and chlorinated alkanes.
12. The method of claim 11, wherein the solvent is selected from at least one of ethanol, isopropanol, acetone, diethyl ether.
13. The method of claim 1, wherein the firing comprises: roasting 1 h-6 h in an air atmosphere at 200-600 ℃, and then roasting 1 h-4 h in a protective gas atmosphere.
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