CN112337454B - Olefin skeleton isomerisation oxide catalyst and preparation method thereof - Google Patents
Olefin skeleton isomerisation oxide catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112337454B CN112337454B CN201910738903.2A CN201910738903A CN112337454B CN 112337454 B CN112337454 B CN 112337454B CN 201910738903 A CN201910738903 A CN 201910738903A CN 112337454 B CN112337454 B CN 112337454B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- isomerization
- olefin
- roasting
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 150000001336 alkenes Chemical group 0.000 title claims abstract description 69
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 238000002791 soaking Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 239000012688 phosphorus precursor Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QRDXAXVMXIPGDB-UHFFFAOYSA-N 2-methylpropane;prop-1-ene Chemical group CC=C.CC(C)C QRDXAXVMXIPGDB-UHFFFAOYSA-N 0.000 description 1
- -1 C 6 Hydrocarbon Chemical class 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- B01J21/12—Silica and 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2705—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with metal oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
- C07C5/2716—Acids of phosphorus; Salts thereof; Phosphorus oxides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an olefin skeleton isomerization oxide catalyst, which comprises the following steps: step 1, roasting an alumina-silica composite oxide; step 2, impregnating the composite oxide obtained in the step 1 with impregnating solution to finish modification, and then drying and roasting to obtain an olefin skeleton isomerization oxide catalyst precursor; step 3, soaking and washing the catalyst precursor obtained in the step 2 by deionized water, and then drying and roasting to obtain the olefin skeleton isomerization oxide catalyst; wherein the impregnating solution contains a group IIIA element precursor. The method can obtain the light olefin skeleton isomerization catalyst with high activity, high selectivity and high stability.
Description
Technical Field
The invention relates to a light straight-chain olefin skeleton isomerism oxide catalyst and a preparation method thereof.
Background
Skeletal isomerism olefin is an important chemical product, can be used for etherification to produce tertiary alkyl ether, is used as a high-octane blending component of gasoline, and can also be used for copolymerization and homopolymerization to produce rubber and high polymer plastics. Because the special framework structure of the composite material is also often used for synthesizing various deep processing chemicals, the composite material is an important fine chemical raw material and plays a great role in industries such as pesticides, medicines, spices, foods and the like.
The method for producing the isoolefin is numerous, and the existing industrial production methods of the isoolefin mainly comprise a sulfuric acid extraction method, an adsorption separation method, an iso-butane propylene co-oxidation co-production method, an alcohol dehydration method, an ether cracking method, an normal olefin isomerization method and the like. The process technology for producing the isoolefins by isomerizing normal olefins mainly comprises the following steps: the isomerization component is added into the cracking catalyst to improve 3 methods of the content of the isomerization olefin in the cracking gas, the dehydrogenation of the isoparaffin, the skeletal isomerization of the linear olefin and the like.
The linear olefin skeleton isomerization technology has the advantages of simple operation, reasonable process equipment, low energy consumption, environmental protection and the like, and can also realize the byproduct C of the oil refinery 4 、C 5 、C 6 And the like. The technology starts in the 70 th century of 20, and a successful n-butene skeletal isomerization production process has been developed.
Skeletal isomerization of olefins needs to be carried out under the catalysis of acidic catalysts, and the key of research and development is the development of efficient catalysts. The catalyst for olefin skeleton isomerization reaction includes three kinds of oxide catalyst, halide catalyst and molecular sieve catalyst. Compared with a halide catalyst which is easy to deactivate and endanger the environment, a molecular sieve catalyst which is complex in manufacturing process and high in manufacturing cost, the oxide catalyst has the advantages of wide sources, low price, environmental friendliness and the like. However, research at home and abroad is focused on molecular sieve catalysts, and oxide catalysts for the skeletal isomerization reaction of linear olefins have been rarely studied.
US5817907 provides a process for skeletal isomerisation of olefins using a catalyst which is a pretreated molecular sieve having a pore size of 0.4 to 0.8nm, such as SAPO-11, SAPO-31, EU-1, OMEGA, nu-10, nu-86, nu-87, ferrierite, ZSM-23, ZSM-12, etc. The pretreatment ensures that coke is deposited in the pore channels of the molecular sieve to block micropores, thereby improving the selectivity and experimental stability of the isoolefin.
US5849975 discloses an isomerism C 4 -C 6 The olefin is prepared with SSZ-32 molecular sieve with the ratio of alkali metal to alkali earth metal being 20 to 1-40 to 1.
US5463160 describes a process for the skeletal isomerisation of linear olefins using a zeolite having a pore size of 0.42-0.6nm and having cross-channels of 10-and 8-membered rings, characterised in that n-pentene may be selectively isomerised to 2-methylbutene.
US9414861 discloses a process for the preparation of an isomerisation catalyst which is effective for the skeletal isomerisation of linear olefins to methyl branched isoolefins by modifying a zeolite having a 10 membered ring pore size of 0.42-0.7nm with at least one monobasic and inorganic acid and at least one dibasic acid and using alumina as binder, and mixing granulating and calcining the catalyst to obtain the catalyst.
US9811115 discloses a C 4 -C 15 Is a first step of isomerizing olefins by adding C 4 -C 15 The olefin raw material and aromatic compound are alkylated, then dealkylated, the product contains isoolefin with different skeleton distribution corresponding to the raw material, and the yield of the isoolefin obtained by the method is very low.
CN1827565A and CN101376617a disclose one type of catalyst that can be used for C 6 C (C) 6+ The olefin skeleton isomerization process uses beta zeolite with Si content of 1-20 wt% and Mg content of 0.1-3.5 wt%, and has high multi-branched product yield.
CN1109039a discloses a C 4 -C 20 The preparation process of olefin skeleton isomerization catalyst includes the first soaking and modifying alumina with one or two kinds of organic siloxane, and the subsequent heat treatment to obtain catalyst for n-C in the skeleton isomerization of pentene 5 ＝ About 70% conversion, about 75% isomerism selectivity, i-C 5 ＝ The yield was about 50%.
The olefin skeleton isomerization catalyst in the above publication has the defects of complex preparation method, high cost, low activity and poor stability, and particularly has the conversion rate of linear olefin of basically less than 50 percent. Therefore, developing a catalyst with higher linear olefin conversion and isomerization selectivity can greatly improve the light fraction utilization rate, and is one of important ways for improving the economic benefits of petrochemical industry.
Disclosure of Invention
The invention mainly aims to provide an olefin skeleton isomerization oxide catalyst and a preparation method thereof, which are used for overcoming the defects of low reaction activity, poor selectivity, low catalyst stability and the like of the olefin skeleton isomerization catalyst in the prior art.
In order to achieve the above object, the preparation method of the olefin skeleton isomerization oxide catalyst of the present invention comprises the steps of:
step 1, roasting an alumina-silica composite oxide;
step 2, impregnating the composite oxide obtained in the step 1 with impregnating solution to finish modification, and then drying and roasting to obtain an olefin skeleton isomerization oxide catalyst precursor;
step 3, soaking and washing the catalyst precursor obtained in the step 2 by deionized water, and then drying and roasting to obtain the olefin skeleton isomerization oxide catalyst;
wherein the impregnating solution contains a group IIIA element precursor.
The invention relates to a preparation method of an olefin skeleton isomerization oxide catalyst, wherein the alumina-silica composite oxide comprises the following steps ofThe mass content of silicon is more than 1.0% and less than or equal to 23%; the pore volume of the alumina-silica composite oxide is more than or equal to 0.4mL/g, and the BET specific surface area is 200m 2 /g to 400m 2 /g。
The invention relates to a preparation method of an olefin skeleton isomerization oxide catalyst, wherein the III A element in the III A element precursor is boron and/or phosphorus.
The invention relates to a preparation method of an olefin skeleton isomerization oxide catalyst, wherein the group IIIA element precursor is boric acid and/or phosphoric acid.
The preparation method of the olefin skeleton isomerization oxide catalyst provided by the invention comprises the steps of roasting at 400-700 ℃ for 1-10 hours in the step 1.
The preparation method of the olefin skeleton isomerization oxide catalyst comprises the following steps of soaking at 40-100 ℃ for 2-6 hours; the soaking in the step 2 is constant temperature soaking, and stirring is continuously carried out.
The preparation method of the olefin skeleton isomerization oxide catalyst provided by the invention comprises the steps of drying at 100-150 ℃ for 5-12 hours, roasting at 400-700 ℃ for 1-24 hours in step 2.
The preparation method of the olefin skeleton isomerization oxide catalyst provided by the invention comprises the following steps of: soaking in constant temperature deionized water at 40-90deg.C for 1-10 hr, filtering, and washing.
The preparation method of the olefin skeleton isomerization oxide catalyst provided by the invention comprises the steps of drying at 100-150 ℃ for 5-12 hours, roasting at 400-700 ℃ for 1-24 hours in step 3.
In order to achieve the aim, the invention also provides a catalyst obtained by the preparation method of the olefin skeleton isomerization oxide catalyst.
The catalyst of the invention, wherein the mass content of the III A element in the catalyst is 1-20%.
The invention has the beneficial effects that:
the invention uses alumina-silicon dioxide composite oxide as main body, through modification of III A element, the surface acid distribution of alumina-silicon dioxide composite oxide is modulated, which is more suitable for straight-chain olefin isomerization reaction, and through soaking and washing with deionized water, excessive III A element which causes cracking and coking is removed, and the acid distribution is further regulated, finally the light olefin skeleton isomerization catalyst with high activity, high selectivity and high stability is obtained.
The preparation method of the catalyst has low cost and is environment-friendly, and has great industrial development value.
Drawings
FIG. 1 shows ammonia temperature programmed desorption (NH) of a composite oxide containing 1%, 5%, 5.5%, 23% silicon 3 -TPD) map;
FIG. 2 is a schematic representation of NH modified with boron to composite oxides of varying silicon content 3 -TPD profile;
FIG. 3 is NH of alumina before and after boron modification 3 -TPD profile;
FIG. 4 shows ammonia temperature programmed desorption (NH) of the catalysts of examples 4 and 6 of the present invention 3 -TPD) curve.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The invention discloses a preparation method of an olefin skeleton isomerization oxide catalyst, which comprises the following steps:
step 1, roasting an alumina-silica composite oxide;
step 2, impregnating the composite oxide obtained in the step 1 with impregnating solution to finish modification, and then drying and roasting to obtain an olefin skeleton isomerization oxide catalyst precursor;
step 3, soaking and washing the catalyst precursor obtained in the step 2 by deionized water, and then drying and roasting to obtain the olefin skeleton isomerization oxide catalyst;
wherein the impregnating solution contains a group IIIA element precursor.
The alumina has lower isomerization activity, and the existence of the silicon dioxide improves the acidity of the composite oxide, thereby improving the isomerization activity of the catalyst to olefin.
The invention firstly calcines the alumina-silicon dioxide composite oxide, the calcination temperature is 400-700 ℃, and the calcination time is 1-10 hours. Wherein the mass content of silicon in the alumina-silica composite oxide is more than 1.0% and less than or equal to 23%; the pore volume of the alumina-silica composite oxide is more than or equal to 0.4mL/g, and the BET specific surface area is 200m 2 /g to 400m 2 /g。
The baked composite oxide is added into impregnating solution for impregnation, the impregnating solution contains a group III A element precursor, the main group element is boron and/or phosphorus, and the main group element precursor is preferably boric acid and/or phosphoric acid. The concentration of the impregnating solution and the impregnating method are not particularly limited in the present invention, as long as the mass content of the group IIIA element in the obtained catalyst is 1 to 20%, and the impregnating method may be, for example, isovolumetric impregnation, overdose impregnation or the like. The soaking temperature in the step 2 is 40-100 ℃, and the soaking time is 2-6 hours; the impregnation is preferably constant temperature impregnation and is continuously stirred. The drying temperature is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 400-700 ℃, and the roasting time is 1-24 hours.
Although the presence of silicon can increase the acidity of the composite oxide, different silicon contents have different acidity and also different isomerization conversion to linear olefins. FIG. 1 shows ammonia temperature programmed desorption (NH) of a composite oxide containing 1%, 5%, 5.5%, 23% silicon 3 -TPD) map. Fig. 1 shows that the composite oxides with different silicon contents have different acidic profiles. The invention can eliminate shadows caused by different silicon contents through the main group element modification stepFIG. 2 is a graph of NH modified with boron to composite oxides of varying silicon content 3 TPD spectra, which show that after modification with boron, the acidity of the composite oxide is significantly changed, substantially eliminating the effect of the difference in silicon content.
In this step, the main group element is, for example, B, which forms a boron aluminum surface compound with the alumina surface, thereby increasing the acid center number and acid strength of the alumina and further increasing the linear olefin isomerization conversion. FIG. 3 is NH of alumina before and after boron modification 3 The TPD spectrum, as can be seen from fig. 3, shows that after the composite oxide surface is loaded with 5.5% and 9% of boron, the surface acidity strength and acid amount are obviously changed, strong acid peaks appear in the range of 300-500 ℃, and the weak acid peak area in the range of 100-300 ℃ is obviously increased, so that the conversion rate of the linear olefin of the isomerization catalyst is obviously increased.
Then, soaking and washing the catalyst precursor obtained in the step 2 by deionized water, and then drying and roasting to obtain the olefin skeleton isomerization oxide catalyst. Wherein, the conditions of soaking and washing are as follows: soaking in constant temperature deionized water at 40-90deg.C for 1-10 hr, filtering, and washing. The drying temperature is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 400-700 ℃, and the roasting time is 1-24 hours.
In the step, deionized water is used for soaking and washing the catalyst precursor, so that substances which cause the isomerization selectivity of the linear olefin to be reduced are further removed, and a new acid distribution is reconstructed.
In summary, the invention takes the alumina-silica composite oxide as the main body of the catalyst, and carries out inorganic matter modification and ion supporting water treatment on the catalyst to generate the final catalyst, and the inorganic matter modification and ion supporting water soaking washing can change the acid quantity, acid strength and acid type of the catalyst, thereby improving the skeletal isomerism selectivity of the catalyst.
The preferred technical scheme of the invention can be expressed as follows:
silicon content of 1-23 m, pore volume of more than or equal to 0.4mL/g and BET specific surface area of 200m 2 /g to 400m 2 After roasting the alumina-silica composite oxide of/g at 0-700 ℃, one or two main group elements are used for modifying the alumina, and the preferable main group elements are boron and phosphorus elements, which account for 1-20 m% of the catalyst, and then roasting at 500-800 ℃. Then the isomerization catalyst is prepared by soaking the mixture in deionized water at the temperature of 40-90 ℃ for 1-10 hours in a sealing way, filtering the mixture, and roasting the obtained sample at the temperature of 400-700 ℃ again. The pore size distribution measured by nitrogen adsorption-desorption experiments of the prepared main group element modified alumina linear olefin skeleton isomerization catalyst is that pores with the pore size smaller than 10nm account for 60-80%, pores with the pore size of 10-20 nm account for 20-30%, and pores with the pore size larger than 20nm account for 10-20%.
The technical scheme of the invention can be further preferably as follows:
(1) Taking a certain amount of alumina-silica composite oxide with silicon content of 1-23 m percent, and roasting the alumina-silica composite oxide in a muffle furnace at a constant temperature of 400-700 ℃ for 1-10 hours to obtain the roasted composite oxide.
(2) Soaking and modifying the composite oxide obtained in the step (1) in the main group element solution at the constant temperature of 40-100 ℃ under continuous stirring for 2-6 hours, drying for 5-12 hours in a blast drying box or an infrared drying box at the temperature of 100-150 ℃, and finally roasting in a muffle furnace at the constant temperature of 400-700 ℃ for 1-24 hours to obtain the main group element modified oxide.
(3) Soaking the main group element modified oxide obtained in the step (2) in deionized water at 40-90 ℃ in a sealing way for 1-10 hours at the same temperature, filtering, and roasting the obtained sample at the constant temperature of 400-700 ℃ for 1-12 hours again to obtain the main group element modified catalyst. The application conditions of the catalyst are preferably as follows: the reaction raw material preferably contains C 5 、C 6 Hydrocarbon mixtures of linear olefins, wherein the linear olefins are present in an amount of 20% to 60%; the reactor is preferably a one-stage or multi-stage fixed bed reactor; the reaction temperature is preferably 300-500 ℃, the reaction pressure is preferably 0.2-0.5MPa, and the weight hourly space velocity is preferably 2-4h -1 。
Under the above reaction conditions, the catalyst has the advantages of high linear olefin conversion rate of more than 60%, skeleton isomerism olefin yield of more than 50%, selectivity of more than 90%, high stability and good technical effect.
The invention is further illustrated by the following specific examples.
Example 1
100g of an alumina-silica composite oxide with a silicon content of 1.0m% is weighed, and the composite oxide is obtained by roasting for 4 hours at 600 ℃ to obtain a catalyst 1.
Example 2
100g of an alumina-silica composite oxide with the silicon content of 23.0m% is weighed and baked for 4 hours at 600 ℃ to obtain the catalyst 2.
Example 3
31.45g of boric acid was weighed, 80mL of distilled water was used to prepare an aqueous boric acid solution, 50g of the sample obtained in example 1 was placed in the aqueous boric acid solution, immersed for 2 hours at a constant temperature of 100℃with continuous stirring, and then dried for 12 hours at 120℃in a forced air drying oven. Finally, roasting for 12 hours in a muffle furnace at a constant temperature of 700 ℃ to obtain the catalyst 3 with the boron content of 5.5 w%.
Example 4
100mL of deionized water at 40℃was measured, 50g of the sample obtained in example 3 was placed in an aqueous solution, immersed in the aqueous solution at a constant temperature of 40℃for 2 hours under a sealed condition, washed, and dried in a forced air drying oven at 120℃for 6 hours. Finally roasting for 4 hours in a muffle furnace at a constant temperature of 550 ℃ to obtain the boron modified catalyst 4 after water treatment.
Example 5
14.3g of boric acid was weighed, 60mL of distilled water was used to prepare an aqueous boric acid solution, 50g of the sample obtained in example 2 was placed in the aqueous boric acid solution, immersed for 2 hours at a constant temperature of 100℃with continuous stirring, washed, and dried in a forced air drying oven at 120℃for 12 hours. Finally, roasting for 12 hours in a muffle furnace at a constant temperature of 700 ℃ to obtain the catalyst 5 with the boron content of 5.1 w%.
Example 6
150mL of deionized water at 40℃was measured, 50g of the sample obtained in example 5 was placed in an aqueous solution, immersed in the aqueous solution at a constant temperature of 60℃for 2 hours under a sealed condition, washed, and dried in a forced air drying oven at 120℃for 4 hours. Finally, roasting for 2 hours in a muffle furnace at a constant temperature of 600 ℃ to obtain the boron modified catalyst 6 after water treatment.
FIG. 4 shows ammonia temperature programmed desorption (NH) of the catalysts of examples 4 and 6 of the present invention 3 TPD) curve, FIG. 4 shows that the acid distribution of the catalyst of the invention is obviously changed after the catalyst is soaked and washed by deionized water, and strong acid centers are formed, which is beneficial to the isomerization reaction of linear olefins and improves the isomerization selectivity.
Example 7
The catalysts obtained in all examples were evaluated under the same evaluation conditions as follows:
the skeletal isomerization reaction raw material is a mixture of 1-hexene and n-heptane, wherein the content of 1-hexene is 20%, the reaction is carried out on a continuously flowing fixed bed micro-reactor, quartz sand is filled in the upper part and the lower part of the reactor, the catalyst is ground to 40-60 meshes, and hydrogen is used for purging the catalyst before the reaction. The reaction temperature is 400 ℃, the pressure is 0.4MPa, and the volume space velocity of carrier gas is 3600h -1 The weight hourly space velocity of the raw material is 11.5h -1 。
And the analysis of the experimental sample adopts an internal standard method, n-heptane in the raw materials is used as an internal standard, and the relative mass percentage in the data calculation processing process is the mass percentage of different substances relative to the n-heptane.
The calculation formula is as follows:
mass percent of something relative to mass percent of something in the liquid/mass percent of n-heptane in the liquid x 100%
The skeletal isomerization performance of the catalyst is represented by C 6 The linear olefin conversion X, the skeletal isomerism hexene yield Y and the skeletal isomerism selectivity S were used as evaluation indexes.
M in the formula 1 、M 2 Respectively n-C in raw materials and products 6 ＝ Is a relative mass percent of (c); m is M 3 、M 4 i-C in the raw materials and the products respectively 6 ＝ Is a relative mass percent of (c).
The experimental results for the catalysts of examples 1-6 are shown in Table 1.
TABLE 1 isomerization results for catalyst samples
As can be seen from Table 1, the invention improves the skeletal isomerization selectivity of the oxide catalyst and improves the yield of the isoolefin through the modification of the main group element and the soaking and washing of the ion supporting water.
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 (9)
1. A process for preparing an olefin skeletal isomerization oxide catalyst, the process comprising the steps of:
step 1, roasting an alumina-silica composite oxide, wherein the roasting temperature is 400-700 ℃;
step 2, impregnating the composite oxide obtained in the step 1 with impregnating solution to finish modification, and then drying and roasting to obtain an olefin skeleton isomerization oxide catalyst precursor; the roasting temperature is 400-700 ℃;
step 3, soaking and washing the catalyst precursor obtained in the step 2 by deionized water, and then drying and roasting to obtain the olefin skeleton isomerization oxide catalyst; the roasting temperature is 400-700 ℃;
wherein the impregnating solution comprises boron and/or phosphorus precursors; the mass content of silicon in the alumina-silica composite oxide is more than 1.0% and less than or equal to 23%;
the conditions for soaking and washing the catalyst precursor by deionized water in the step 3 are as follows: soaking in constant temperature deionized water at 40-90deg.C for 1-10 hr, and washing.
2. The method for preparing an olefin skeleton isomerization oxide catalyst according to claim 1, wherein the alumina-silica composite oxide has a pore volume of 0.4mL/g or more and a BET specific surface area of 200m 2 /g to 400m 2 /g。
3. The method for preparing an olefin skeletal isomerization oxide catalyst of claim 1, wherein the boron and/or phosphorus precursor is boric acid and/or phosphoric acid.
4. The process for preparing an olefin skeletal isomerization oxide catalyst of claim 1, wherein the calcination in step 1 is carried out for a period of 1 to 10 hours.
5. The method for preparing an olefin skeletal isomerization oxide catalyst according to claim 1, wherein the temperature of the impregnation in the step 2 is 40-100 ℃ and the time of the impregnation is 2-6 hours; the soaking in the step 2 is constant temperature soaking, and stirring is continuously carried out.
6. The method for preparing an olefin skeletal isomerization oxide catalyst according to claim 1, wherein the drying temperature in the step 2 is 100-150 ℃, the drying time is 5-12 hours, and the calcination time is 1-24 hours.
7. The method for preparing an olefin skeletal isomerization oxide catalyst according to claim 1, wherein the drying temperature in the step 3 is 100-150 ℃, the drying time is 5-12 hours, and the calcination time is 1-24 hours.
8. A catalyst obtained by the process for producing an olefin skeletal isomerization oxide catalyst of any one of claims 1 to 7.
9. The catalyst according to claim 8, wherein the mass content of boron and/or phosphorus in the catalyst is 1-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910738903.2A CN112337454B (en) | 2019-08-09 | 2019-08-09 | Olefin skeleton isomerisation oxide catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910738903.2A CN112337454B (en) | 2019-08-09 | 2019-08-09 | Olefin skeleton isomerisation oxide catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112337454A CN112337454A (en) | 2021-02-09 |
| CN112337454B true CN112337454B (en) | 2023-07-25 |
Family
ID=74367813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910738903.2A Active CN112337454B (en) | 2019-08-09 | 2019-08-09 | Olefin skeleton isomerisation oxide catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112337454B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307552A (en) * | 1998-07-15 | 2001-08-08 | 切夫里昂菲利普化学有限责任公司 | Method of isomerizing alpha-olefins to linear internal olefins with minimal skeletal isomerization using nickel supported on silica/aluminia catalysts |
| CN103566968A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Alkene isomerization catalyst and preparation method thereof |
| CN103566975A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | N-alkene isomerization catalyst and preparation method thereof |
| CN103769208A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorusmodified SAPO-11 molecular sieve based catalyst and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8895795B2 (en) * | 2010-02-05 | 2014-11-25 | Uop Llc | Acid washed silica supported catalysts and their use in olefin metathesis |
-
2019
- 2019-08-09 CN CN201910738903.2A patent/CN112337454B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307552A (en) * | 1998-07-15 | 2001-08-08 | 切夫里昂菲利普化学有限责任公司 | Method of isomerizing alpha-olefins to linear internal olefins with minimal skeletal isomerization using nickel supported on silica/aluminia catalysts |
| CN103566968A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Alkene isomerization catalyst and preparation method thereof |
| CN103566975A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | N-alkene isomerization catalyst and preparation method thereof |
| CN103769208A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Phosphorusmodified SAPO-11 molecular sieve based catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| C5直链烯烃骨架异构化催化剂的制备及其性能;王亭亭等;《化工进展》;20111231;第30卷;第143-146页 * |
| Effects of particle size on catalytic conversion of ethanol to propylene over H-ZSM-5 catalysts-Smaller is better;Xia, W，et al.;《CATALYSIS COMMUNICATIONS》;20160105;第27-33页 * |
| 不同分子筛上1-己烯骨架异构化反应性能的研究;曹中扬等;《燃料化学学报》;20180731;第848-855页 * |
| 碳二加氢催化剂用球形氧化铝载体制备及性能研究;刘鹏程;《中国硕士学位论文全文数据库（电子期刊）》;20071115(第5期);第23,35-38页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112337454A (en) | 2021-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization | |
| RU2469792C2 (en) | Method of preparing silicoaluminophosphate (sapo) molecular sieves, catalysts, containing thereof, and methods of catalytic dehydration with application of said catalysts | |
| CN111482199A (en) | Olefin cracking catalyst, preparation method thereof and olefin cracking method | |
| US10835894B1 (en) | Methods for producing mesoporous zeolite multifunctional catalysts for upgrading pyrolysis oil | |
| EA020083B1 (en) | Dehydration of alcohols on crystalline silicates | |
| EA019181B1 (en) | Dehydration of alcohols in the presence of an inert component | |
| KR20190105086A (en) | Dual Catalytic Processes and Systems for Propylene Production | |
| CN105983435A (en) | Butane isomerization catalyst and preparation method and application thereof | |
| WO2018092840A1 (en) | METHOD FOR PRODUCING p-XYLENE | |
| CN106215970A (en) | The modification processing method of HZSM 5 molecular sieve catalyst and application | |
| CN111167509A (en) | Carbon tetraolefin cracking catalyst, preparation method thereof and catalytic cracking method | |
| CN107282102B (en) | Preparation method of metal-loaded molecular sieve catalyst | |
| Patel et al. | Effect of the addition of Sn to zirconia on the acidic properties of the sulfated mixed oxide | |
| Zhao et al. | Effect of calcination temperature on structure, composition and properties of S 2 O 8 2−/ZrO 2 and its catalytic performance for removal of trace olefins from aromatics | |
| US3529033A (en) | Catalytic conversion | |
| CN116514626B (en) | Method for preparing trimerization product by high-selectivity oligomerization of isobutene | |
| Shimura et al. | Preparation of NiOx/SiO2–Al2O3 catalysts by a homogenous precipitation method and their catalytic activity for ethylene oligomerization | |
| CN112337454B (en) | Olefin skeleton isomerisation oxide catalyst and preparation method thereof | |
| CN112337468B (en) | Olefin isomerization catalyst and preparation method and application thereof | |
| CN103657708A (en) | Catalyst for aromatization and quality modification of catalytic gasoline | |
| CN109485064B (en) | Method for preparing mordenite by using waste MTP catalyst and application of waste MTP catalyst | |
| CN109796028B (en) | Method for preparing silicoaluminophosphate molecular sieve, silicoaluminophosphate molecular sieve and method for preparing olefin from methanol | |
| CN109569703B (en) | Catalyst for producing gasoline component from naphtha and methanol, preparation method and application | |
| CN111943803B (en) | Method for synthesizing exo-tetrahydrodicyclopentadiene | |
| KR20200066436A (en) | Nickel-based Oligomerization Catalysts and Method for Oligomerizing Light Olefins Using the Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |