CN116920816A - 1-hexene self-disproportionation catalyst and preparation method and application thereof - Google Patents
1-hexene self-disproportionation catalyst and preparation method and application thereof Download PDFInfo
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000004966 Carbon aerogel Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002131 composite material Substances 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 239000004480 active ingredient Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
Abstract
The invention provides a 1-hexene self-disproportionation catalyst, a preparation method and application thereof, wherein the 1-hexene self-disproportionation catalyst comprises a carrier and an active component, the active component is loaded on the carrier, the carrier comprises a metal oxide and a carbon material, and the active component comprises at least one of Mo, W, B, re. According to the invention, the carbon material and the metal oxide particles are mixed, and the composite carrier is obtained through extrusion molding, and the obtained composite carrier has a high specific surface area. The active component is loaded on a composite carrier, active functional groups on the surface of a highly dispersed carbon material in the composite carrier can be combined with the active metal component, so that the active metal has high dispersity and is combined with the carrier more firmly.
Description
Technical Field
The invention relates to the field of olefin disproportionation, in particular to a 1-hexene self-disproportionation catalyst and a preparation method and application thereof.
Background
Decene is an important alpha-olefin, and is mainly used as a synthetic high-grade poly alpha-olefin synthetic oil base oil (PAO) and can be used for producing fine chemical intermediates such as detergents, plasticizers and the like.
Patent CN106927988A describes a preparation method of decene, wherein raw materials are ethylene and alpha-olefin, an organic solvent and a chromium catalyst are added, oligomerization reaction is carried out in a high-pressure reactor, the reaction pressure is 1.0-5 MPa, the reaction temperature is 60-160 ℃, and the reaction time is 0.1-3 hours, so that a decene product is obtained; however, the catalyst in this method is a liquid phase catalyst, and the operation is complicated and the separation is difficult.
Patent US3676523 discloses that the SHOP process comprises three steps of ethylene oligomerization, isomerization and disproportionation: 1, 4-butanediol is taken as solvent, niCl 2 /(C 6 H 5 ) 2 P(CH 2 ) 2 COOH/NaBH 4 /Ph 3 P is a catalyst, oligomerization is carried out in a series autoclave reactor at 80-120 ℃ and 6.8-13.6 MPa, and a heterogeneous catalyst MgO/Al is adopted 2 O 3 Under the existence of liquid phase condition of 80-140 deg.C and 0.35-1.7 MPa making isomerization reaction, the disproportionation reaction is implemented by using Re 2 O 7 /Al 2 O 3 Redistributing the carbon number of one high-carbon olefin and one low-carbon olefin of the isomerised product to generate two medium-carbon olefins as a catalyst so as to increase the yield of the required olefin; in the method, the selectivity of decene is lower, C 10 The selectivity was only 11%.
Patent CN108059580B describes a catalyst for preparing hexene/ethylene by self-disproportionation of 1-butene and a preparation method thereof, wherein the catalyst consists of an active metal component and a composite carrier, and double bond isomerization and other disproportionation side reactions can be effectively inhibited by alkali metal modification of the composite carrier, so that the hexene/ethylene is prepared by self-disproportionation of 1-butene.
Patent CN102040454A discloses a method for preparing hexene by disproportionating butene, which comprises adopting butene as raw material, and adopting a fixed bed reactor, wherein the reaction temperature is 360-450 ℃, the reaction pressure is 0.1-1 MPa, and the weight airspeed is 6-20 h -1 Under the condition that the raw materials and the catalyst are contacted and reacted to generate effluent containing hexene, wherein the catalyst contains 1 to 30 parts of tungsten oxide and 70 to 99 parts of SiO by weight 2 A carrier.
The prior art discloses the preparation of hexene from disproportionation using 1-butene as a feedstock. However, the above catalyst is not suitable for the self-disproportionation of 1-hexene to decene because of catalyst activity and catalytic efficiency problems. Thus, there remains a need in the art for further research into decene preparation methods, 1-hexene self-disproportionation catalysts.
Disclosure of Invention
The invention discloses a 1-hexene self-disproportionation catalyst and a preparation method and application thereof, and aims to solve the problems that in the prior art, the preparation method of decene is complex, the yield is low, the dispersion degree of active sites of the catalyst for preparing decene by self-disproportionation of 1-hexene is low, the catalytic efficiency is limited, and the decene yield in reaction products is low.
In order to achieve the above object, the present invention provides a 1-hexene self-disproportionation catalyst comprising a carrier and an active component, the active component being supported on the carrier, the carrier comprising a metal oxide and a carbon material, the active component comprising at least one of Mo, W, B, re;
wherein the specific surface area of the carbon material is 700-900 m 2 And/g, wherein the pore size distribution is 10-50 nm, and the pore volume is 1.25-2.2 ml/g.
The 1-hexene self-disproportionation catalyst of the present invention, wherein the metal oxide is selected from the group consisting of Al 2 O 3 、TiO 2 、ZnO、MgO、ZrO 2 At least one of them.
The 1-hexene self-disproportionation catalyst provided by the invention is characterized in that the carbon material is at least one selected from activated carbon, carbon aerogel, carbon nanotube and graphene.
The 1-hexene self-disproportionation catalyst of the present invention, wherein the mass ratio of the carbon material to the metal oxide is 1 to 10:1.
the 1-hexene self-disproportionation catalyst of the invention, wherein the mass ratio of the active component to the metal oxide is 0.5% -30% in terms of oxide.
In order to achieve the above purpose, the invention also provides a preparation method of the 1-hexene self-disproportionation catalyst, which comprises the following steps:
step 1, mixing metal oxide with a carbon material, extruding strips and forming to obtain a catalyst carrier;
step 2, loading a precursor of an active component on the catalyst carrier, and roasting to obtain a 1-hexene self-disproportionation catalyst;
wherein the active component comprises at least one of Mo, W, B, re, and the specific surface area of the carbon material is 700-900 m 2 And/g, wherein the pore size distribution is 10-50 nm, and the pore volume is 1.25-2.2 ml/g.
The invention relates to a preparation method of a 1-hexene self-disproportionation catalyst, wherein the carbon material is at least one selected from activated carbon, carbon aerogel, carbon nano tube and graphene; the precursor of the active component is soluble salt of the active component; the roasting temperature is 300-800 ℃.
In order to achieve the above purpose, the present invention further provides a method for preparing decene, wherein the self-disproportionation reaction is performed by using the 1-hexene self-disproportionation catalyst as a catalyst and using 1-hexene as a raw material, so as to obtain decene.
The decene preparation method provided by the invention is characterized in that the self-disproportionation reaction temperature is 40-200 ℃, and the reaction pressure is 0.3-5 Mpa.
The invention has the beneficial effects that:
according to the invention, the carbon material and the metal oxide particles are mixed, and the composite carrier is obtained through extrusion molding, and the obtained composite carrier has a high specific surface area.
The active component is loaded on a composite carrier, active functional groups on the surface of a highly dispersed carbon material in the composite carrier can be combined with the active metal component, so that the active metal has high dispersity and is combined with the carrier more firmly.
Detailed Description
The following embodiments are provided by carrying out the embodiments of the present invention on the premise of the embodiments of the present invention, and the detailed implementation process is given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not specify specific conditions, structures or experimental methods, and generally follow conventional conditions.
The invention provides a 1-hexene self-disproportionation catalyst, which comprises a carrier and an active component, wherein the active component is loaded on the carrier, the carrier comprises a metal oxide and a carbon material, and the active component comprises at least one of Mo, W, B, re;
wherein the specific surface area of the carbon material is 700-900 m 2 And/g, wherein the pore size distribution is 10-50 nm, and the pore volume is 1.25-2.2 ml/g.
In the present invention, the carbon material means a carbon material having a carbon element as a sole constituent element, and has various properties. In one embodiment, the carbon material of the present invention is at least one of activated carbon, carbon aerogel, carbon nanotubes, and graphene.
According to the invention, the carbon material and the metal oxide are mixed to be used as the composite carrier, and the obtained composite carrier has a relatively high specific surface area. Further, after the active component is loaded on the carrier, the active functional groups on the surface of the highly dispersed carbon material in the composite carrier can be combined with the active component, so that the active component has high dispersity and is combined with the carrier more firmly.
In one embodiment, the metal oxide in the support of the present invention is in the form of particles, e.g., 20-100 mesh, selected from the group consisting of Al 2 O 3 、TiO 2 、ZnO、MgO、ZrO 2 At least one of them. In yet another embodiment, the mass ratio of carbon material to metal oxide in the support is from 1 to 10:1, preferably 1 to 5:1.
the active component of the invention is at least one of Mo, W, B, re. In one embodiment, the active ingredient of the present invention is supported on the carrier in the form of an oxide, and the present invention is not particularly limited to the form of the oxide of the active ingredient supported on the carrier, and is generally in the form of an oxide which is easily formed upon calcination of the active ingredient, such as Mo 2 O 3 Etc.
In one embodiment, the mass ratio of active component to metal oxide in the support is 0.5% to 30%, preferably 1% to 20%, more preferably 2% to 10% on oxide basis. The oxide referred to herein is generally an oxide that readily forms upon calcination of the active ingredient.
In one embodiment, the invention also provides a preparation method of the self-disproportionation catalyst of 1-hexene, which comprises the following steps:
step 1, mixing metal oxide with a carbon material, extruding strips and forming to obtain a catalyst carrier;
and 2, loading the precursor of the active component on the catalyst carrier, and roasting to obtain the 1-hexene self-disproportionation catalyst.
The types of metal oxide and carbon materials are described in detail above and will not be described in detail herein. In one embodiment, the mass ratio of carbon material to metal oxide in the support is 1 to 10:1, preferably 1 to 5:1. the method for extruding and molding the strip in the step 1 is not particularly limited, and the method can be used in the conventional way in the field. In another embodiment, the metal oxide is mixed with the carbon material, extruded, and then dried and calcined to obtain the support.
In the present invention, the precursor of the active ingredient is a compound containing the active ingredient, for example, a soluble salt of the active ingredient, and the active ingredient may be present in an anion or cation of the active ingredient precursor, for example, a nitrate of the active ingredient, or the like.
The method of supporting the active component precursor on the carrier is not particularly limited, and may be, for example, impregnation, isovolumetric impregnation, saturation impregnation, multiple impregnation, or the like. Specifically, for example, the active ingredient precursor is dissolved in a solvent and then impregnated into the support, and the present invention is not particularly limited as long as the amount of the active ingredient precursor solution and the like required for the present invention can be satisfied.
In one embodiment, the support loaded with the active component precursor is subjected to drying and calcination at a temperature of 300 to 800 ℃, preferably 300 to 500 ℃.
The catalyst prepared by the method has higher specific surface area, catalyzes 1-hexene to perform self-disproportionation reaction, and has higher 1-hexene conversion rate and high decene selectivity. In one embodiment, the self-disproportionation of 1-hexene adopts a batch or continuous type reaction mode, and the reactor adopts a stirred tank, a fixed bed or a fluidized bed; the self-disproportionation reaction temperature of 1-hexene is 40-200 ℃, and the reaction pressure is 0.3-5 MPa.
The method of the invention carries out the self-disproportionation reaction of 1-hexene, the 1-hexene conversion rate reaches more than 70 percent, and the decene selectivity reaches more than 81 percent.
The technical scheme of the invention will be further described in detail through specific examples. The following reagents are commercially available unless otherwise specified.
Example 1
1) Catalyst preparation
10g of gamma-Al 2 O 3 And 40g of active carbon are uniformly mixed, extruded and molded, and then are baked in an oven at 120 ℃ for 12 hours, and then the sample is put into a muffle furnace for baking at 450 ℃ for 4 hours, so as to obtain the composite carrier. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
1g of the prepared catalyst is weighed and added into a high-pressure reaction kettle, and then 45g of 1-hexene is injected into the high-pressure reaction kettle; introducing nitrogen with partial pressure of 0.5MPa, heating the materials in the reaction kettle to 150 ℃ for reaction for 20 hours, cooling the system to below 20 ℃ after the reaction is finished, and collecting 10g of a product for gas chromatography analysis. The calculated 1-hexene conversion was 71.6% and decene selectivity was 82.7%.
Example 2
1) Catalyst preparation
10g of gamma-Al 2 O 3 And 40g of carbon nano tube are uniformly mixed, extruded and formed, and then baked in an oven at 120 ℃ for 12 hours, and then the sample is put into a muffle furnace for baking at 450 ℃ for 4 hours, so as to obtain the composite carrier. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 71.8% and decene selectivity was 82.6%.
Example 3
1) Catalyst preparation
10g of gamma-Al 2 O 3 And uniformly mixing 40g of graphene, extruding, molding, drying in a baking oven at 120 ℃ for 12 hours, and then placing a sample into a muffle furnace for roasting at 450 ℃ for 4 hours to obtain the composite carrier. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 72.3% and decene selectivity was 82.5%.
Example 4
1) Catalyst preparation
10g of gamma-Al 2 O 3 And 40g of carbon aerogel are uniformly mixed, extruded and molded, and then are baked in an oven at 120 ℃ for 12 hours, and then the sample is put into a muffle furnace for baking at 450 ℃ for 4 hours, so that the composite carrier is obtained. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 73.6% and decene selectivity was 82.8%.
Example 5
1) Catalyst preparation
10g of gamma-Al 2 O 3 And uniformly mixing 30g of carbon nano tubes, extruding, molding, baking in a baking oven at 120 ℃ for 12 hours, and then placing a sample into a muffle furnace for baking at 450 ℃ for 4 hours to obtain the composite carrier. 10g of the carrier obtained above was placed in a crucible,2g of ammonium molybdate is taken and dissolved in 3ml of distilled water, the dissolved ammonium molybdate solution is added into a crucible for 2 hours of dipping, then the catalyst is prepared after drying for 12 hours at 120 ℃ and roasting for 4 hours at 500 ℃ by introducing air.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 76.3% and decene selectivity was 84.6%.
Example 6
1) Catalyst preparation
10g of gamma-Al 2 O 3 And uniformly mixing 30g of carbon nano tubes, extruding, molding, baking in a baking oven at 120 ℃ for 12 hours, and then placing a sample into a muffle furnace for baking at 450 ℃ for 4 hours to obtain the composite carrier. Putting 10g of the obtained carrier into a crucible, dissolving 2g of ammonium metatungstate in 3ml of distilled water, adding the dissolved ammonium metatungstate solution into the crucible, soaking for 2 hours, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours by introducing air to obtain the catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 78.3% and decene selectivity was 85.6%.
Example 7
1) Catalyst preparation
10g of TiO 2 And uniformly mixing 50g of graphene, extruding, molding, drying in a baking oven at 120 ℃ for 12 hours, and then placing a sample into a muffle furnace for roasting at 450 ℃ for 4 hours to obtain the composite carrier. Putting 10g of the obtained carrier into a crucible, dissolving 2g of ammonium molybdate in 3ml of distilled water, adding the dissolved ammonium molybdate solution into the crucible, immersing for 2 hours, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours by introducing air to obtain the catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 77.3% and decene selectivity was 84.5%.
Example 8
1) Catalyst preparation
10g of ZrO 2 And 50g of carbon aerogel are uniformly mixed, extruded and formed, and then dried in an oven at 120 ℃ for 12 hours, and then a sample is put into a muffle furnace and baked at 450 ℃ for 4 hours to obtain the composite carrier. Putting 10g of the obtained carrier into a crucible, dissolving 2g of ammonium metatungstate in 3ml of distilled water, adding the dissolved ammonium metatungstate solution into the crucible, soaking for 2 hours, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours by introducing air to obtain the catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 77.5% and decene selectivity was 85.2%.
Comparative example 1
1) Catalyst preparation
50g of gamma-Al 2 O 3 Extruding and molding, baking for 12 hours in a baking oven at 120 ℃, then placing the sample in a muffle furnace, and baking for 4 hours at 450 ℃ to obtain the carrier. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 58.3% and decene selectivity was 65.6%.
Comparative example 2
1) Catalyst preparation
50g of ZrO 2 Extruding and molding, baking for 12 hours in a baking oven at 120 ℃, then placing the sample in a muffle furnace, and baking for 4 hours at 450 ℃ to obtain the carrier. 10g of the carrier obtained above was placed in a crucible, 1.11g of ammonium perrhenate was dissolved in 2ml of distilled water, the dissolved ammonium perrhenate solution was added to the crucible, immersed for 2 hours, then dried at 120℃for 12 hours, and calcined at 500℃for 4 hours with air to obtain a catalyst.
2) Catalyst evaluation
The catalyst evaluation method was the same as in example 1. 10g of the product was collected for gas chromatography. The calculated 1-hexene conversion was 62.5% and decene selectivity was 72.5%.
TABLE 1 test data for examples 1-8 and comparative examples 1-2
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A 1-hexene self-disproportionation catalyst, characterized by comprising a carrier and an active component, the active component being supported on the carrier, the carrier comprising a metal oxide and a carbon material, the active component comprising at least one of Mo, W, B, re;
wherein the specific surface area of the carbon material is 700-900 m 2 And/g, wherein the pore size distribution is 10-50 nm, and the pore volume is 1.25-2.2 ml/g.
2. The self-disproportionation catalyst of 1-hexene according to claim 1, wherein the metal oxide is selected from the group consisting of Al 2 O 3 、TiO 2 、ZnO、MgO、ZrO 2 At least one of them.
3. The 1-hexene self-disproportionation catalyst according to claim 1, wherein said carbon material is at least one selected from the group consisting of activated carbon, carbon aerogel, carbon nanotubes, graphene.
4. The 1-hexene self-disproportionation catalyst according to claim 1, characterized in that the mass ratio of the carbon material to the metal oxide is 1 to 10:1.
5. the 1-hexene self-disproportionation catalyst according to claim 1, characterized in that the mass ratio of the active component to the metal oxide is 0.5% to 30% in terms of oxide.
6. The 1-hexene self-disproportionation catalyst according to claim 1, characterized in that the mass ratio of the active component to the metal oxide is 2% to 10% in terms of oxide.
7. The preparation method of the 1-hexene self-disproportionation catalyst is characterized by comprising the following steps:
step 1, mixing metal oxide with a carbon material, extruding strips and forming to obtain a catalyst carrier;
step 2, loading a precursor of an active component on the catalyst carrier, and roasting to obtain a 1-hexene self-disproportionation catalyst;
wherein the active component comprises at least one of Mo, W, B, re, and the specific surface area of the carbon material is 700-900 m 2 And/g, wherein the pore size distribution is 10-50 nm, and the pore volume is 1.25-2.2 ml/g.
8. The method for preparing a 1-hexene self-disproportionation catalyst according to claim 7, wherein the carbon material is at least one selected from the group consisting of activated carbon, carbon aerogel, carbon nanotube, and graphene; the precursor of the active component is soluble salt of the active component; the roasting temperature is 300-800 ℃.
9. A process for preparing decene, which comprises the step of carrying out self-disproportionation reaction of 1-hexene with the 1-hexene as a raw material by using the 1-hexene self-disproportionation catalyst as set forth in any one of claims 1 to 6.
10. The method for producing decene according to claim 9, wherein the self-disproportionation reaction temperature is 40 to 200 ℃ and the reaction pressure is 0.3 to 5Mpa.
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