CN115193463A - Method for synthesizing 4-methyl-1-pentene by propylene dimerization - Google Patents
Method for synthesizing 4-methyl-1-pentene by propylene dimerization Download PDFInfo
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- CN115193463A CN115193463A CN202111677275.5A CN202111677275A CN115193463A CN 115193463 A CN115193463 A CN 115193463A CN 202111677275 A CN202111677275 A CN 202111677275A CN 115193463 A CN115193463 A CN 115193463A
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- Prior art keywords
- crown
- ether
- propylene
- catalyst
- carrier
- Prior art date
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 122
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 91
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 45
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 31
- -1 alkali metal salt Chemical class 0.000 claims abstract description 30
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 25
- 239000011591 potassium Substances 0.000 claims abstract description 25
- 239000006200 vaporizer Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
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- 230000008569 process Effects 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
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- SQAYGJNMLDVSHZ-UHFFFAOYSA-N 4-[(2,4-dinitrophenyl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O SQAYGJNMLDVSHZ-UHFFFAOYSA-N 0.000 claims description 3
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- HFRGASADQCZXHH-UHFFFAOYSA-N 1,4,7,10,13,16-hexaoxacyclooctadec-2-ylmethanol Chemical compound OCC1COCCOCCOCCOCCOCCO1 HFRGASADQCZXHH-UHFFFAOYSA-N 0.000 claims description 2
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- AGNCFNQAIMILOU-UHFFFAOYSA-N 1,4,7,10,13-pentaoxacyclopentadec-2-ylmethanamine Chemical compound NCC1COCCOCCOCCOCCO1 AGNCFNQAIMILOU-UHFFFAOYSA-N 0.000 claims description 2
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- REKDBTBSNFSNGP-UHFFFAOYSA-N bis(1,4-phenylene)-34-crown 10-ether Chemical compound O1CCOCCOCCOCCOC(C=C2)=CC=C2OCCOCCOCCOCCOC2=CC=C1C=C2 REKDBTBSNFSNGP-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
-
- 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)
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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
- 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
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- B01J35/399—
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- B01J35/60—
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- 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
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- 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
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 processes: under the protection of nitrogen, filling a catalyst into a constant temperature area of a fixed bed reactor; feeding raw material propylene into a fixed bed reactor through a vaporizer for reaction, feeding reaction products into a gas-liquid separator through a pressure reducer, and obtaining a liquid phase containing the 4-methyl-1-pentene; the catalyst comprises a carrier and sodium and/or potassium loaded 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 a crown ether and graphite. The catalyst adopted in the method improves the surface microcosmic environment of the carrier, so that a special vacancy structure is formed on the surface of the carrier and is uniformly dispersed, the uniform dispersion of active metal is facilitated, and the prepared catalyst has good performance, and has high propylene conversion rate and high 4MP1 selectivity.
Description
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 action with 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 for short) polymerized by 4MP1 is a novel special thermoplastic material, has the characteristics of a general polyolefin material, high transparency, high softening point, good dielectric property, drug resistance and the like, has wide and special application, can be used for manufacturing high-value-added products such as release paper, medical instruments, food packaging materials, electronic and electrical components and the like, and can be particularly used in the fields of the emerging 5G industry, high-end medical treatment (artificial lung) and the like.
The production process of 4MP1 is mainly propylene selective dimerization process. The catalyst for high 4MP1 selectivity is prepared by mainly using alkali metal and dispersing the alkali metal on alkali metal carbonate and/or bicarbonate. Alkali metal salts such as potassium carbonate and the like are used as excellent carriers of the existing propylene dimerization to synthesize 4MP1 catalyst, and have lower isomerization activity and higher 4MP1 selectivity due to lower specific surface and simple pore structure, but also have the problem of low conversion rate of propylene caused by low activity. In order to solve the contradiction between the improvement of the activity and the assurance of the selectivity, the catalyst is generally modified. The modification of the catalyst is mainly developed from the aspects of modification of the carrier, addition of an auxiliary agent and the like, the research on the improvement of the pore structure of the carrier, the improvement of the pore size distribution and the like is carried out, or alkaline earth metal oxides such as copper, cobalt, stainless steel powder, mgO and the like are added in the preparation process of the catalyst, so that the conversion efficiency is improved.
Phillips U.S. Pat. No. 3,8978,8978,8978 discloses that inorganic substances such as graphite, carbon black, coke, etc. can be added to a carrier as a template agent, and can be used as a die lubricant for granulation, and can improve the pore size distribution of potassium carbonate to improve the activity of a dimerization catalyst, and promoters such as stainless steel, metallic cobalt, metallic copper, etc. are added when metal potassium is molten and supported, so that the activity of the catalyst is maintained. The company then successively disclosed several vector improvement methods to increase propylene conversion: in US4876410AThe method comprises adding water and alcohol into alkali carbonate to obtain thick paste, extruding, and drying to obtain granular carrier; the use of potassium carbonate, sodium carbonate and at least one alumina-containing compound, such as aluminium hydroxide, alpha-Al, is described in US5057639A 2 O 3 Or gamma-Al 2 O 3 Mixing the mixture with water to obtain paste, drying and calcining to obtain a carrier; US5112791a describes a catalyst support prepared from an alkali metal carbonate, at least one low surface area silica-alumina and a liquid. In addition, the potassium carbonate carrier introduced in CN1405128a should have the following physical parameters: the particle diameter of the most probable primary particles is 0.5-1.5 μm, the particle diameter of the most probable secondary particles is 100-700 μm, the total pore diameter is Rong 0.08.08 mL/g, and the most probable pore diameter is
The catalyst has high activity, good selectivity and good controllability; CN108554430A discloses a method for preparing a catalyst by adding a talcum powder auxiliary agent into an alkali metal salt carrier for drying treatment and then melting and loading alkali metal, which improves the loading state of an active intermediate on the carrier and improves the catalytic performance of the reaction.
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, the present invention aims to provide a method for dimerization of propylene into 4-methyl-1-pentene, which is carried out in the presence of a supported alkali metal catalyst and has high propylene conversion rate and high 4MP1 selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing 4-methyl-1-pentene by propylene dimerization, wherein the propylene dimerization adopts a fixed bed gas phase reaction, and the method comprises the following steps:
under the protection of nitrogen, filling a catalyst into a constant temperature area of a fixed bed reactor; feeding raw material propylene into a fixed bed reactor through a vaporizer for reaction, feeding reaction products into a gas-liquid separator through a pressure reducer, and obtaining a liquid phase containing the 4-methyl-1-pentene;
the catalyst comprises a carrier and sodium and/or potassium loaded 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 a crown ether and graphite.
In the method for synthesizing 4-methyl-1-pentene by propylene dimerization, the carrier of the adopted catalyst is obtained by adding a modifier solution into an alkali metal salt for treatment, wherein the modifier solution is mainly a crown ether solution, and in addition, graphite can be further added. Specifically, the processing procedure includes: and mixing alkali metal salt with the modifier solution, and roasting to obtain the carrier. Further, the roasting includes aerobic roasting and anaerobic roasting.
According to the active site microstructure and catalytic mechanism research of the catalyst, the catalytic activity of the solid base is related to the number and strength of surface base sites, and in addition, the micro environment of the surface base sites of the solid base, including specific surface area, pore structure, size, surface affinity to the substrate and the like, has influence. The main theory of the dispersion state of alkali metal sodium and/or potassium on the surface of the carrier is that the alkali metal sodium and/or potassium is mainly dispersed in unsaturated coordination centers and lattice defects on the surface of the carrier, and not only is the alkali metal sodium and/or potassium uniformly dispersed in a close monolayer on the surface of the carrier. Therefore, it is an advantage to form a specific vacancy structure of the base sites on the surface of the carrier and to uniformly disperse the vacancy structure to form a uniformly distributed catalytic active center.
In the invention, a proper object is added into alkali metal salt, complexing is carried out, and then a required carrier with a special vacancy structure and uniform dispersion is formed by a pretreatment mode such as drying roasting, and the like, then loading of alkali metal is carried out, the alkali metal is fully combined with lattice defects on the surface of the carrier, so that the balanced size is achieved, uniform dispersion is realized, and the propylene dimerization catalyst with high propylene conversion rate and high selectivity is prepared. Through a great deal of intensive research, the invention discovers that the surface of the carrier obtained by uniformly mixing the alkali metal salt and the crown ether with the cavity structure and then drying and roasting the mixture has lattice defects, and the prepared catalyst has high propylene conversion rate and 4MP1 selectivity.
Crown ethers are macrocyclic compounds whose cavity structure has a selective effect on ions, and are capable of complexing metal ions, especially alkali metal ions, while freeing negative ions outside the cavity. Uniformly mixing alkali metal salt and crown ether solution to complex ions on the surface of the alkali metal salt by the crown ether; then roasting to remove the organic compound, and obtaining the alkali metal salt carrier with gray or black surface. The carrier roasted after the crown ether treatment does not destroy the aggregation state of crystal particles, does not generate a melt crosslinking state, and keeps the original three-dimensional particle state. The scanning electron microscope of the alkali metal salt support prepared by the process described above found that the support was aggregated in the form of spherical particles having a particle size of < 1 μm for the first time (the term "first time particles" is derived from patent application CN1405128 a). The characterization result of the mercury intrusion method is that the pore size distribution range is 80nm-12000nm, the total pore volume is not less than 0.2mL/g, and the preferred total pore volume is 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 reaction pressure is 0.1-20 MPa; the liquid hourly space velocity is 0.1 to 10h -1 。
According to the process of the present invention, preferably, the temperature of the reaction is from 100 to 170 ℃, more preferably from 130 to 170 ℃, and the pressure of the reaction is from 7MPa to 13MPa.
According to the process of the present invention, preferably, the support has a particle size of the most probable primary particle of < 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 invention, preferably, the mass of the sodium and/or potassium is 0.5% -20% of the carrier; more preferably 1% -15%; further preferably 2% to 10%.
According to the method of the invention, preferably, the crown ether is added into the modifier solution in an amount of 0.01-20% of the mass of the alkali metal salt; more preferably 0.1% to 15%; further preferably 0.2% to 10%.
According to the method of the invention, preferably, when the modifier is the combination of crown ether and graphite, the adding amount of the graphite in the modifier solution is 0.2-1.50% of the 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% to 15%; further preferably 0.2% to 10%.
The addition of graphite may further increase the activity or propylene conversion of the finally obtained propylene dimerization catalyst.
According to the method of the present invention, preferably, the particle size of the carrier is 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 an alkali metal carbonate and an alkali metal bicarbonate.
More preferably, the alkali metal carbonates include potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
According to the process of the invention, 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-aminodibenzo-18-crown (ether) -6 hydrochloride, 12-crown-4-ether, 15-crown-5, crown-8-ene, 4 '-nitrobenz-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-18-6-ether, 4 '-acetylbenzo-15-5-ether, 4' -dibenzo-1-crown-6-ether, N-crown-10-crown-6-ether, N '-dibenzyl-4,13-diaza-18-crown-6-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, and mixtures thereof 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-diisopropoxycaprolarene 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, dibenzo-24-crown-8-ether, dibenzo-15-crown-5, dibenzo-ol, and dibenzo-15-crown-5-methyl-6-methyl-isopropyl-6, 4-tert-butylcyclohexane-15-crown-5, and mixtures thereof, 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-6, 15-crown-5, benzo-18-crown-6-ether, aza-18-crown-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 selected from at least one of ethanol, isopropanol, acetone, and diethyl ether.
According to the method of the present invention, preferably, the temperature of the mixing is between room temperature and 200 ℃ and the time is between 0.1h and 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 present invention, preferably, the mixing is achieved by stirring, rotation or vibration.
According to the method of the present invention, preferably, the firing comprises: roasting for 1h-6h at the temperature of 200-600 ℃ in the air atmosphere, and then roasting for 1h-4h in the protective gas atmosphere. More preferably, the firing comprises: roasting for 2-4 h in air atmosphere at 250-500 ℃, and then roasting for 1-3 h in protective gas atmosphere.
Roasting at high temperature in an oxygen-first inert environment to remove organic compounds and obtain the alkali metal salt carrier with gray or black surface.
According to the preparation method of the invention, preferably, the roasting further comprises a step of sieving under water-proof and oxygen-proof conditions.
Specifically, the preparation of the catalyst comprises the following steps:
mixing alkali metal salt with a modifier solution, and then 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 melting load is carried out in a protective gas atmosphere. The protective gas is selected from nitrogen, helium, argon and the like. Preferably, the temperature of the melting load is 10-240 ℃ higher than 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 embodiment of the melt load includes: the weighed carrier and alkali metal are put into a pressure bomb in an anhydrous oxygen-free box, and then the pressure bomb is put into a homogeneous reactor to be heated and rotated.
The preparation process of the catalyst improves the microscopic environment of the surface of the carrier, so that a special vacancy structure is formed on the surface of the carrier and is uniformly dispersed, the uniform dispersion of active metal is facilitated, and the prepared catalyst has good performance, and has high propylene conversion rate and high 4MP1 selectivity.
The method for synthesizing 4-methyl-1-pentene by propylene dimerization provided by the invention adopts a special catalyst, and improves the conversion rate of propylene and the selectivity of 4MP 1. In the preparation process of the catalyst, crown ether with a cavity structure is added into alkali metal salt, then complexation is carried out, then a carrier with a special vacancy structure and uniform dispersion is formed through pretreatment modes such as drying roasting and the like, then loading of alkali metal is carried out, the alkali metal is fully combined with lattice defects on the surface of the carrier, the balance size is achieved, 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 micrograph of the calcined potassium carbonate support treated with the crown ether solution of example 1.
FIG. 1b is a scanning electron micrograph of the calcined potassium carbonate support treated with the crown ether solution of example 7.
FIG. 2a is a scanning electron micrograph of the calcined potassium carbonate support treated with graphite alone in comparative example 1.
FIG. 2b is a scanning electron micrograph of the calcined potassium carbonate support treated with graphite alone in comparative example 3.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) in increments of 0.1 or 1.0 as appropriate. All numerical designations should 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 size of the primary particle diameter and the aggregation morphology are measured by scanning electron microscopy, and in a preferred embodiment of the present invention, the scanning electron microscopy images of the potassium carbonate carrier after the solution treatment and calcination by the crown ether are shown in fig. 1a and fig. 1 b. Scanning electron micrographs of graphite-only treated potassium carbonate support are shown in figures 2a and 2 b.
The pore size distribution, pore volume, specific surface area and porosity are measured by mercury intrusion method, and the particle size of the carrier is measured by screening method.
The method for synthesizing 4-methyl-1-pentene by propylene dimerization in the embodiment of the invention and the comparative example comprises the following steps:
the method comprises the following steps: batch kettle type reaction:
a predetermined amount of the obtained catalyst was taken out under a nitrogen atmosphere and charged into a 250mL autoclave. The mass of the kettle body is called as m 1 . Then propylene is injected into the autoclave and the mass m of the autoclave body is weighed 2 Calculating the propylene addition as m C3 . Then, the reaction kettle is heated to the reaction temperature and reacted for a certain time. Cooling the reaction system to below 20 ℃, sampling the residual gas phase components in the kettle, emptying, and weighing the obtained kettle body with mass m 3 Calculating the liquid receiving mass m Liquid for medical purpose . And (4) taking gas and liquid to analyze the component content of the product. The propylene conversion and 4MP1 selectivity were calculated.
(1) Propylene conversion rate C:
(2) 4MP1 Selective S
Wherein:
m c3 -the mass of propylene added before the reaction;
m liquid for treating urinary tract infection The mass of the reacted solution is collected;
X liquid C -percentage propylene in gas chromatography of the liquid;
X qi C -percentage propylene in gas chromatography of the gas;
X 4MP1 -4 MP1 percentage in gas chromatography of the liquid.
The method 2 comprises the following steps: 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 polymer-grade propylene into a reaction device through an advection pump, feeding the polymer-grade propylene into a reactor through a vaporizer, raising the temperature in 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, and the reaction result of the reaction mixture is analyzed by on-line chromatography through a six-way valve before entering the gas-liquid separator. The propylene conversion and 4MP1 selectivity were calculated.
The reaction results were analyzed by on-line chromatography. The propylene conversion and 4MP1 selectivity were calculated.
(1) Propylene conversion C:
C＝(1-X c3 )×100％
(2) 4MP1 Selective S
Wherein:
X c3 -percentage propylene in gas chromatography of the product;
X 4MP1 -4 MP1 percentage in gas chromatography of the product.
Example 1
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Preparation of the catalyst
Preparing a carrier: putting 50g of anhydrous potassium carbonate into a flask, dissolving 2.5g of 18-crown ether-6 in 2.0g of ethanol, adding into the anhydrous potassium carbonate in the sesame seed cake, mixing and heating the materials to 80 ℃, and stirring at a low speed for 1h; placing the material in a crucible, roasting for 2 hours in a muffle furnace at 450 ℃, and then introducing micro nitrogen flow to continue roasting for 2 hours; after the temperature is reduced to below 50 ℃, 30g of 20-60-mesh carriers are screened and sealed for loading under the condition of water and oxygen isolation.
The resulting support was analyzed by scanning electron microscopy 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 probable primary particle is less than 1 mu m; meanwhile, the total pore volume is 0.2630mL/g measured by mercury intrusion method, and the most probable pore size distribution range is 100-12000 nm.
Loading metal: in an anhydrous oxygen-free box, adding 30g of the carrier into 100mL of pressure bomb, weighing 1.5g of 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 stored for later use.
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 reaction kettle; and (3) 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, emptying the gas phase, sampling for gas chromatographic analysis, collecting 47g of liquid phase and carrying out gas chromatographic analysis. Calculated propylene conversion was 50.5% and 4MP1 selectivity was 86.9%.
3) Method for synthesizing 4-methyl-1-pentene by propylene dimerization 2
45mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene into a reactor by a constant flow pump through a vaporizer, wherein the temperature of the vaporizer is 145 ℃, the temperature of the reactor is 150 ℃, the control pressure is 9.8MPa, and the adjusted airspeed is 1.3h -1 And (4) continuously reacting. When the reaction is carried out for 20 hours, the conversion rate of the propylene is 30.5 percent, and the selectivity of the 4MP1 is 87.0 percent. When the reaction was continued for 48h, the propylene conversion was 37.1% and the 4MP1 selectivity was 89.2%.
Example 2
This example provides a method for dimerization of propylene into 4-methyl-1-pentene, comprising the following steps:
30mL of the catalyst prepared in example 1 was charged into a fixed-bed reactor. Pumping propylene into a reactor by a constant flow pump through a vaporizer, wherein the vaporizer temperature is 130 ℃, the reactor temperature is 130 ℃, the control pressure is 5.2MPa, and the space velocity is adjusted to be 0.2h -1 And (4) continuously reacting. When the reaction time is 20 hours, the conversion rate of the propylene is 27.2 percent, and the selectivity of the 4MP1 is 86.8 percent.
Other conditions are not changed, and the airspeed is continuously adjusted for 0.5h -1 When the reaction was continued for 48 hours, the propylene conversion was 33.1% and the 4MP1 selectivity was 86.5%.
Continuously adjusting the temperature of the vaporizer to 140 ℃, the temperature of the reactor to 140 ℃, the control pressure to 9.0MPa and the space velocity to 1.0h -1 When the reaction was continued for 60 hours, the propylene conversion was 36.2% and the 4MP1 selectivity was 87.3%.
Example 3
This example prepared the following catalyst and used it to dimerize propylene to 4-methyl-1-pentene, comprising the following process:
1) Catalyst preparation
The catalyst preparation method was substantially the same as in example 1, except that:
in the process of preparing the carrier:
7.0g of benzo-18-crown-6-ether is adopted as the crown ether, and 5.5g of absolute ethyl alcohol is adopted as the solvent;
after the materials are mixed, the materials are not heated to 80 ℃ but stirred at a low speed for 1.5h at 100 ℃;
roasting the material in a muffle furnace for 1.5h at 550 ℃, and then continuously roasting for 1.5h in micro-nitrogen flow;
screening is to screen 30g of 5-40 mesh vectors;
3.0g of potassium is adopted to replace sodium in the process of loading metal; the pressure bomb is heated to 120 ℃ in the homogeneous reactor and rotated for 8h, and the surface of the prepared catalyst is light blue, and the interior of the catalyst is dark silver.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
In the same manner as in 2) in example 1, 42g of the liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 45% and 4MP1 selectivity was 85.7%.
3) Method for synthesizing 4-methyl-1-pentene by propylene dimerization 2
30mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene by a constant flow pump through a vaporizer, wherein the temperature of the vaporizer is 160 ℃, the temperature of the reactor is 160 ℃, the control pressure is 13MPa, and the airspeed is adjusted to be 5.0h -1 And (4) continuously reacting. When the reaction time reaches 20h, the conversion rate of propylene is 22.5 percent, and the selectivity of 4MP1 is 86.0 percent.
The temperature of the vaporizer is adjusted to 170 ℃, the temperature of the reactor is adjusted to 180 ℃, the control pressure is 16MPa, and the airspeed is adjusted to 9.0h -1 When the reaction was continued for 45 hours, the propylene conversion was 15.1% and the 4MP1 selectivity was 83.2%.
Example 4
This example prepared the following catalyst and used it to dimerize propylene to 4-methyl-1-pentene, comprising the following process:
1) Catalyst preparation
The catalyst preparation method was the same as in example 1, except that in the preparation of the support:
1.0g of 15-crown 5-ether is adopted as the crown ether, and 1.5g of acetone is adopted as the solvent;
after the materials are mixed, the mixture is not heated to 80 ℃ but stirred at low speed for 3 hours at normal temperature;
the material was calcined in a muffle furnace at 400 ℃ for 3h and then further calcined in a stream of micro-nitrogen for 2h.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
Same as in example 1. 28g of liquid phase were collected and analyzed by gas chromatography. Calculated propylene conversion was 30.1% with 4MP1 selectivity 93.1%.
Example 5
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: placing 80g of anhydrous potassium carbonate into a flask, then 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 then adding 0.8g of graphite into the flask; placing the material in a crucible, roasting for 3 hours in a muffle furnace at 280 ℃, and then introducing micro nitrogen flow to continue roasting for 1 hour; after cooling, under the condition of water and oxygen isolation, 45g of 20-40 meshes of carriers are screened and sealed for loading.
Loading metal: in an anhydrous oxygen-free box, weighing the carrier, adding the carrier into 200mL of pressure bomb, weighing 2.5g of potassium, adding the potassium into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous reactor, heated to 120 ℃, rotated for 8 hours, the prepared catalyst is silver gray, the outer surface is slightly blue, and the catalyst is sealed and stored for later use.
2) Dimerization of propylene into 4-methyl-1-pentene
30mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene by a constant flow pump through a vaporizer, wherein the temperature of the vaporizer is 60 ℃, the temperature of the reactor is 60 ℃, the control pressure is 2MPa, and the airspeed is adjusted for 1.5h -1 And (4) continuously reacting. When the reaction is carried out for 20 hours, the conversion rate of the propylene is 6.5 percent, and the selectivity of the 4MP1 is 85.0 percent.
The temperature of the vaporizer is adjusted to 100 ℃, the temperature of the reactor is adjusted to 100 ℃, the control pressure is 6.0MPa, and the space velocity is 3.0h -1 When the reaction was continued for 45 hours, the propylene conversion was 15.3% and the 4MP1 selectivity was 86.9%.
Continuously adjusting the temperature of the vaporizer to 150 ℃, the temperature of the reactor to 150 ℃, the control pressure to 10.0MPa and the airspeed to 1.0h -1 When the reaction is continued for 60 hours, the conversion rate of propylene is41.5 percent and the selectivity of 4MP1 is 86.3 percent.
Continuously adjusting the temperature of the vaporizer to 200 ℃, the temperature of the reactor to 210 ℃, the control pressure to 20.0MPa and the airspeed to 2.0h -1 When the reaction was continued for 84 hours, the propylene conversion was 5.6% and the 4MP1 selectivity was 34.3%.
Example 6
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: adding 50g of anhydrous potassium carbonate into a triangular flask, dissolving 3g of aza-18-crown ether in 2.6g of diethyl ether, then adding into the triangular flask, then adding 0.7g of graphite into the triangular flask, then heating the triangular flask in a vibration box to 120 ℃, vibrating at a low speed for 1.0h, then placing into a crucible, then roasting in a muffle furnace at 300 ℃ for 3h, and continuing to roast for 1h under a micro nitrogen flow; after cooling, screening 30g of 20-60 meshes of carriers and sealing the carriers for loading in a water-proof and oxygen-proof environment.
Loading metal: in an anhydrous oxygen-free box, weighing the carrier, adding the carrier into 100mL of pressure bomb, weighing 2.0g of potassium and 0.5g of sodium, adding the potassium and the sodium into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 100 ℃ and rotated for 5 hours, and the catalyst thus obtained had a silver metallic luster and a little blue color on the surface.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
Same as 2) in example 1. The liquid phase 53g was collected and analyzed by gas chromatography. Calculated propylene conversion was 56.1% and 4MP1 selectivity was 86.4%.
2) Method for synthesizing 4-methyl-1-pentene by propylene dimerization 2
20mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene by a constant flow pump through a vaporizer, wherein the temperature of the vaporizer is 145 ℃, the temperature of the reactor is 150 ℃, the pressure is 9.8MPa, and the space velocity is adjusted to be 1.3h -1 And (4) continuously reacting. When the reaction is carried out for 20 hours, the conversion rate of the propylene is 27.1 percent, and the selectivity of the 4MP1 is 90.2 percent. When the reaction is carried out for 48 hours, the conversion rate of the propylene is 38.3 percent, and the selectivity of the 4MP1 is 89.5％。
Example 7
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
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, then adding into the triangular flask, then adding 0.5g of graphite into the triangular flask, then vibrating the triangular flask in a vibrating box at a low speed for 1.0h at normal temperature, then placing into a crucible, then roasting in a muffle furnace at 450 ℃ for 2h, and continuing to roast in a micro nitrogen flow for 1.5h; after cooling, screening 30g of 20-60 meshes of carriers and sealing the carriers for loading in a water-proof and oxygen-proof environment.
The resulting support was analyzed by scanning electron microscopy 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 the most probable primary particle is less than 1 mu m. The total pore volume is 0.3085mL/g measured by mercury intrusion method, and the most probable pore size distribution range is 80-10000 nm.
Loading metal: in an anhydrous oxygen-free box, weighing the carrier, adding the carrier into 100mL of pressure bomb, weighing 1.5g of potassium, adding the potassium into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 170 ℃ and rotated for 2.5 hours, and the catalyst thus obtained had a silvery metallic luster and a little blue color on the surface.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
In the same manner as in 2) in example 1, 63g of the liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 65.3% and 4MP1 selectivity was 86.5%.
3) Method for synthesizing 4-methyl-1-pentene by propylene dimerization 2
30mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene by a constant flow pump through a vaporizer, 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 And (4) continuously reacting. When the reaction is carried out for 20 hours, the conversion rate of the propylene is 28.1 percent, and the selectivity of the 4MP1 is 88.3 percent. Adjusting airspeed for 0.8h -1 The reaction proceeds toAt 48h, the propylene conversion was 42.3% and the 4MP1 selectivity was 86.4%.
Example 8
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: adding 30g of anhydrous potassium carbonate and 20g of anhydrous sodium carbonate into a triangular flask, dissolving 0.5g of 4-tert-butylcyclohexane-15-crown-5 in 1.0g of ethanol, adding into the triangular flask, adding 0.3g of graphite into the triangular flask, heating the triangular flask in a vibration box to 150 ℃, vibrating at a low speed for 0.5h, placing in a crucible, roasting in a muffle furnace at 300 ℃ for 4h, and continuously roasting in a micro nitrogen flow for 2h; after the temperature is reduced to below 50 ℃, 30g of 20-80 mesh carriers are screened and sealed for loading in a water-proof and oxygen-proof environment.
Loading metal: in an anhydrous oxygen-free box, adding 30g of the carrier into 100mL of pressure bomb, weighing 1.0g of potassium, adding into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous reactor, heated to 120 ℃ and rotated for 8 hours, and the prepared catalyst has silver metallic luster.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
In the same manner as in 2) in example 1, 38g of a liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 40.7% and 4MP1 selectivity was 87.3%.
Example 9
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
The catalyst preparation method was the same as 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 dissolved in 2.0g of isopropanol, and the amount of graphite is 0.5g; heating to 200 deg.C in a vibration box, and vibrating at low speed for 0.2h. Roasting for 5 hours in a muffle furnace at 250 ℃, and continuing roasting for 2 hours in a micro nitrogen flow. Screening 30g of 40-80 mesh carrier, adding 1.5g of sodium, heating to 200 ℃ in a pressure bomb, and rotating for 5h. The catalyst obtained is dark grey.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
Same as 2) in example 1. The liquid phase 41g was collected and analyzed by gas chromatography. Calculated propylene conversion was 43.2% and 4MP1 selectivity was 83.6%.
Example 10
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
The catalyst preparation method was the same as 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-6 and 0.1g of dibenzo-24-crown-8-ether are dissolved in 0.5g of ethanol, and the amount of graphite is 0.1g; heating to 120 deg.C in a vibration box, and vibrating at low speed for 1h. Roasting for 3 hours at 480 ℃ in a muffle furnace, introducing micro nitrogen flow, and continuing roasting for 3 hours. Screening 30g of 20-100 mesh carrier, adding 2.0g of potassium, heating to 150 ℃ in a pressure bomb, and rotating for 5h. The prepared catalyst has metallic luster.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
Same as 2) in example 1. 69g of liquid phase were collected and analyzed by gas chromatography. Calculated propylene conversion was 73% and 4MP1 selectivity was 69.7%.
Example 11
This example prepared the following catalyst and used it to dimerize propylene to 4-methyl-1-pentene, comprising the following process:
1) Catalyst preparation
The catalyst preparation method was the same as example 7, except that:
5.0g of aza-18-crown ether was dissolved in 3.5g of diethyl ether, the amount of graphite being 0.3g. Screening 30g of 20-60 mesh carrier, adding 5.5g of potassium, heating to 100 ℃ in a pressure bomb, and rotating for 8h. The obtained catalyst solid had a blue-colored agglomerate and a silver gray color inside.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
The same method as in example 1 was used for evaluating the catalyst 2) in example 1, and 54g of a liquid phase was collected and analyzed by gas chromatography. Calculated propylene conversion was 57.0% with 4-MP-1 selectivity 63.2%.
Example 12
This example prepares the following catalyst and uses it to dimerize propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
The catalyst preparation method was the same as example 7, except that:
0.1g of 18-crown-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 at low speed for 1 hour. Screening 30g of 20-60 mesh carrier, adding 0.3g of potassium, heating to 100 ℃ in a pressure bomb, and rotating for 4h. The catalyst obtained was slightly silvery.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 15g of the liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 16.5% and 4MP1 selectivity was 96.1%.
Comparative example 1
This comparative example prepared the following catalyst and used the catalyst for the dimerization of propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: taking 50g of anhydrous potassium carbonate into a crucible, adding 0.5g of graphite, roasting for 3 hours in a muffle furnace at 300 ℃, and then introducing micro nitrogen flow to continue roasting for 3 hours; and after the temperature is reduced to below 50 ℃, screening 30g of 20-60-mesh carrier in a water-proof and oxygen-proof environment, and sealing for loading.
The resulting support was analyzed by scanning electron microscopy as shown in FIG. 2 a. As can be seen from fig. 2 a: the potassium carbonate carrier which is not added with the crown ether is in a lamellar shape and aggregated in a cross-linking state, the most probable primary particle diameter is larger than 1 mu m, the total pore volume is 0.1254mL/g, and the most probable pore diameter is in multi-stage irregular distribution of mesopores and macropores.
Loading metal: in an anhydrous oxygen-free box, adding 30g of the carrier into 100mL of pressure bomb, weighing 1.5g of potassium, adding into the pressure bomb, and sealing; the pressure bomb is placed in a homogeneous reactor, heated to 170 ℃ and rotated for 2.5 hours, and the catalyst prepared by the method has 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 20h, cooling the system to below 20 ℃ after the reaction is finished, discharging the gas phase, sampling for gas chromatographic analysis, collecting 32g of liquid phase and carrying out gas chromatographic analysis. Calculated propylene conversion was 35.0% with 4MP1 selectivity 84.3%.
Comparative example 2
This comparative example prepared the following catalyst and used the catalyst for the dimerization of propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: taking 50g of sodium bicarbonate into a crucible, adding 0.5g of graphite, roasting for 5 hours in a muffle furnace at 250 ℃, and then introducing micro nitrogen flow to continue roasting for 2 hours; and (3) after the temperature is reduced to below 50 ℃, screening 30g of 40-80 carriers in a water-proof and oxygen-proof environment, and sealing for loading.
Loading metal: in an anhydrous oxygen-free box, adding 30g of the carrier into 100mL of pressure bomb, weighing 1.5g of sodium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 200 ℃ and rotated for 5h, whereby the catalyst was silver gray.
2) Method 1 for synthesizing 4-methyl-1-pentene by propylene dimerization
As in 2) in example 1, 22g of the liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 24.0% and 4MP1 selectivity was 82.8%.
Comparative example 3
This comparative example prepared the following catalyst and used the catalyst for the dimerization of propylene to 4-methyl-1-pentene, comprising the following processes:
1) Catalyst preparation
Preparing a carrier: taking 50g of anhydrous potassium carbonate into a crucible, adding 0.5g of graphite, roasting for 1.5h at 550 ℃ in a muffle furnace, and then introducing micro nitrogen flow to continue roasting for 1.5h; and (3) after the temperature is reduced to below 50 ℃, screening 30g of carriers with 5-40 meshes in a water-proof and oxygen-proof environment, and sealing for loading.
The resulting support was analyzed by scanning electron microscopy as shown in FIG. 2 b. As can be seen from fig. 2 b: the potassium carbonate carrier without crown ether treatment is aggregated in a cross-linked state, the most probable primary particle diameter is larger 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.
Loading metal: in an anhydrous oxygen-free box, adding 30g of the carrier into 100mL of pressure bomb, weighing 3.0g of potassium, adding into the pressure bomb, and sealing; the pressure bomb was placed in a homogeneous reactor, heated to 150 ℃ and rotated for 8h, whereby the catalyst 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 the liquid phase was collected and subjected to gas chromatography. Calculated propylene conversion was 7.3% and 4MP1 selectivity was 84.2%.
3) Method for synthesizing 4-methyl-1-pentene by propylene dimerization 2
30mL of the catalyst prepared above was measured and charged into a fixed-bed reactor. Pumping propylene into a reactor by a constant flow pump through a vaporizer, wherein the temperature of the vaporizer is 160 ℃, the temperature of the reactor is 160 ℃, the control pressure is 13MPa, and the space velocity is adjusted to be 5.0h -1 And (4) continuously reacting. When the reaction time reaches 20h, the conversion rate of propylene is 6.2 percent, and the selectivity of 4MP1 is 81.0 percent.
The temperature of the vaporizer is adjusted to 170 ℃, the temperature of the reactor is adjusted to 180 ℃, the control pressure is 16MPa, and the airspeed is adjusted to 9.0h -1 When the reaction was continued for 45 hours, the propylene conversion was 7.5% and the 4MP1 selectivity was 63.9%.
The experimental data of the examples and comparative examples are compared to each other to show that: and crown ether is added during carrier treatment, so that the propylene conversion rate and the selectivity of 4MP1 are improved compared with a catalyst prepared by a carrier without crown ether treatment.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (15)
1. The method for synthesizing 4-methyl-1-pentene by propylene dimerization is characterized in that the propylene dimerization adopts a fixed bed gas phase reaction and comprises the following processes:
under the protection of nitrogen, filling a catalyst into a constant temperature area of a fixed bed reactor; feeding raw material propylene into a fixed bed reactor through a vaporizer for reaction, feeding reaction products into a gas-liquid separator through a pressure reducer, and obtaining a liquid phase containing the 4-methyl-1-pentene;
the catalyst comprises a carrier and sodium and/or potassium loaded 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 a crown ether and graphite.
2. The method of claim 1, wherein the temperature of the reaction is 0 to 250 ℃; the reaction pressure is 0.1-20 MPa; the liquid hourly space velocity is 0.1 to 10h -1 。
3. The method according to claim 1, wherein the reaction temperature is 130-170 ℃ and the reaction pressure is 7-13 MPa.
4. The method according to claim 1, wherein the support has a particle size of < 1 μm in the most probable primary particle size; the pore size distribution is 80nm-12000nm, and the total pore volume is not less than 0.2mL/g.
5. The method of claim 1, wherein the sodium and/or potassium is present in an amount of 0.5% to 20% by weight of the carrier.
6. The method according to claim 1, characterized in that the crown ether is added in the modifier solution in an amount of 0.01-20% by mass of the alkali metal salt.
7. The method according to claim 1, wherein when the modifier is a combination of crown ether and graphite, the graphite is added to the modifier solution in an amount of 0.2 to 1.50% by mass of the alkali metal salt.
8. The method according to claim 1, wherein the particle size of the carrier is 5 to 100 mesh.
9. The method according to claim 1, wherein the alkali metal salt is at least one selected from the group consisting of an alkali metal carbonate and an alkali metal bicarbonate.
10. The method of claim 9, wherein the alkali metal carbonate comprises potassium carbonate and sodium carbonate; the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate.
11. The method of 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-ether, 4-hydrochlorinated aminodibenzo-18-crown (ether) -6, 12-crown 4-ether, 15-crown-5, crown-8-ene, 4 '-nitrobenz-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-3236 zxft (5236- (5262-dinitrophenylazo) phenol), 4' -acetylbenzo-18-6-ether, 4 '-acetylbenzo-15-dibenzo-5-ether, N-dibenzo-18-crown-6-ether, N-benzoyl-1-18-crown-6-ether, N-benzoyl-6-crown-ether, 4' -carboxybenzo-15-crown-5-ether, 2- (hydroxymethyl) -12-crown-5-ether, 24-naphthoyl-5-dibenzo-3263-6-dibenzoyl-ether, N-dibenzoyl-1-6-1-crown-6-ether, N-dibenzoyl-6-ether, N-1-dibenzoyl-6-ether, and N-dibenzoyl-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, and mixtures thereof 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-diisopropoxycaprolarene 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, dibenzo-24-crown-8-ether, dibenzo-15-crown-5, dibenzo-ol, and dibenzo-15-crown-5-methyl-6-methyl-isopropyl-6, 4-tert-butylcyclohexane-15-crown-5, and mixtures thereof, 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.
12. The method of claim 11, wherein the crown ether is selected from at least one of 18-crown-6, 15-crown-5, benzo-18-crown-6-ether, aza-18-crown-6, 4-tert-butylcyclohexane-15-crown-5, dibenzo-24-crown-8-ether.
13. 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.
14. The method according to claim 13, wherein the solvent is selected from at least one of ethanol, isopropanol, acetone, and diethyl ether.
15. The method of claim 1, wherein the firing comprises: roasting for 1-6 h in air atmosphere at the temperature of 200-600 ℃, and then roasting for 1-4 h in protective gas atmosphere.
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