CN112337468B - Olefin isomerization catalyst and preparation method and application thereof - Google Patents
Olefin isomerization catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 60
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 58
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000005342 ion exchange Methods 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000009849 deactivation Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 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
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007603 infrared drying Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- -1 C 6 Hydrocarbon Chemical class 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
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005457 ice water Substances 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
- 238000005457 optimization 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
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining 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
- 239000012266 salt solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/30—Ion-exchange
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an olefin isomerization catalyst, a preparation method and application thereof, comprising the following steps: step 1, roasting an alumina precursor; step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnating solution to finish modification, and then drying and roasting; step 3, adding the modified alumina obtained in the step 2 into a second solution for ion exchange, and then washing, drying and roasting to obtain an olefin isomerization catalyst; wherein the first impregnating solution contains a main group element precursor, and the second solution contains a transition metal precursor. The catalyst obtained by the method has higher selectivity, higher product yield and difficult deactivation.
Description
Technical Field
The invention relates to an olefin isomerization catalyst and a preparation method and application thereof, in particular to a metal modified oxide catalyst for light straight-chain olefin skeletal isomerization and a preparation method and application thereof.
Background
The isoolefine is an important chemical product, can be etherified to produce tertiary alkyl ether, is used as a high-octane blending component of gasoline, and can also be used for producing copolymerized and homo-polymerized rubber and high-polymer plastics, and various further processing chemicals can be synthesized due to the special skeleton structure of the isoolefine. In addition, the isoolefin 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 main methods for industrial application at present are an ether cracking method and a straight-chain olefin skeleton isomerization method, wherein the isomerization method has the advantages of simple operation, reasonable process equipment, low energy consumption, environmental protection and the like, has high economic benefit, and can also realize the byproduct C in the gasoline refining 4 、C 5 、C 6 The full and reasonable utilization of the fraction is the best way for producing the isoolefin.
The skeletal isomerization reaction of olefin needs to be carried out under the catalysis of an acid catalyst, the key of research and development is the development of an efficient catalyst, and the catalysts for skeletal isomerization reaction of olefin mainly comprise three types of oxide catalysts, halide catalysts and molecular sieve catalysts. Compared with a halide catalyst which is easy to deactivate and is harmful to the environment, a molecular sieve catalyst which is complex in manufacturing process and high in manufacturing cost, and an oxide catalyst has the advantages of wide sources, low cost and the like. However, current research focuses on molecular sieve catalysts and few patents disclose oxide catalysts for skeletal isomerization of linear olefins.
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 isomerisation catalysts which are effective in the skeletal isomerisation of linear olefins to methyl branched isoolefins. The catalyst is prepared by modifying zeolite with 10 membered ring and pore size of 0.42-0.7nm with at least one monobasic acid, inorganic acid and at least one dibasic acid, using alumina as binder, mixing, granulating and roasting.
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%.
Based on the oxide catalyst for the skeletal isomerization of the linear olefin, which is disclosed at present, the selectivity and the yield of the isoolefin are to be improved, and the disclosed other molecular sieve catalysts also have the defects of low selectivity and easy deactivation, the invention aims to prepare the light olefin skeletal isomerization catalyst with high activity, high selectivity and high stability.
Disclosure of Invention
The invention mainly aims to provide an olefin isomerization catalyst, a preparation method and application thereof, and aims to overcome the defects of poor selectivity, low yield of isoolefin and easy deactivation of the catalyst in the prior art.
In order to overcome the above drawbacks, the present invention provides a method for preparing an olefin isomerization catalyst, comprising the steps of:
step 1, roasting an alumina precursor;
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnating solution to finish modification, and then drying and roasting;
step 3, adding the modified alumina obtained in the step 2 into a second solution for ion exchange, and then washing, drying and roasting to obtain an olefin isomerization catalyst;
wherein the first impregnating solution contains a main group element precursor, and the second solution contains a transition metal precursor.
The invention relates to a preparation method of an olefin isomerization catalyst, wherein a precursor of aluminum oxide is silicon-containing gibbsite or pseudo-boehmite, and the mass content of silicon in the precursor of aluminum oxide is more than 0% and less than or equal to 23%; the pore volume of the precursor of the alumina 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 isomerization catalyst, wherein main group elements in a main group element precursor are boron and/or phosphorus; the transition metal in the transition metal precursor is any one of Co, ni, mo, cu, ti and V, and two or more of the transition metals are combined.
The invention relates to a preparation method of an olefin isomerization catalyst, wherein the main group element precursor is boric acid and/or phosphoric acid; the transition metal precursor is soluble salt of the transition metal, and the concentration of the transition metal in the second solution is 0.001-1 mol/L.
The preparation method of the olefin isomerization 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 isomerization catalyst comprises the 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 drying temperature in the step 2 is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 400-700 ℃, and the roasting time is 1-24 hours.
The preparation method of the olefin isomerization catalyst comprises the following steps of (1) carrying out ion exchange at a temperature of 40-100 ℃ for 2-6 hours; the ion exchange in the step 3 is constant temperature soaking, and stirring is continuously carried out; the drying temperature in the step 3 is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 450-700 ℃, and the roasting time is 1-6 hours.
In order to achieve the above purpose, the invention also provides a catalyst obtained by the preparation method of the olefin isomerization catalyst.
In order to achieve the above object, the present invention further provides a process for isomerizing olefins, which comprises reacting the above catalyst with a catalyst containing C 5 And/or C 6 Wherein C in the hydrocarbon mixture is used as raw material for olefin isomerization reaction 5 And/or C 6 The mass content of the linear olefin is 10-30%.
The olefin isomerization method of the invention, wherein the isomerization reaction temperature is 300-500 ℃, the isomerization reaction pressure is 0.2-0.5MPa, and the weight hourly space velocity is 1-35h -1 。
The invention has the beneficial effects that:
according to the invention, alumina is used as a catalyst main body, main group elements and metal elements are modified in sequence, and the acid quantity, the acid strength and the acid type of the catalyst are modified and modulated by the main group elements, so that the activity of the catalyst is improved, and then the acid distribution on the surface of the catalyst is regulated by metal modification, so that the skeletal isomerism selectivity of the catalyst is improved. The catalyst obtained by the method has higher selectivity, higher product yield and difficult deactivation.
Drawings
FIG. 1 is NH of alumina before and after boron modification 3 -TPD profile;
FIG. 2 shows 0%, 1%, 5%, 5.5%, 23% NH of alumina containing silicon 3 -TPD profile;
FIG. 3 is a graph of NH modified with boron for alumina of varying silicon content 3 -TPD profile;
FIG. 4 is NH of modified alumina before and after ion exchange 3 -TPD profile.
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 provides a preparation method of an olefin isomerization catalyst, which comprises the following steps:
step 1, roasting an alumina precursor;
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnating solution to finish the first modification, and then drying and roasting;
step 3, adding the modified alumina obtained in the step 2 into a second solution for ion exchange, and then washing, drying and roasting to obtain an olefin isomerization catalyst;
wherein the first impregnating solution contains a main group element precursor, and the second solution contains a transition metal precursor.
Wherein the precursor of the alumina can be gibbsite or pseudo-boehmite containing silicon, the mass content of silicon in the precursor of the alumina is preferably more than 0% and less than or equal to 23%, the preferred pore volume is more than or equal to 0.4mL/g, and the preferred BET specific surface area is 200m 2 /g to 400m 2 And/g. The firing temperature of the alumina precursor may be from 0 to 700 ℃.
The alumina precursor is roasted and then added into a first impregnating solution for impregnation, wherein the first impregnating solution contains a main group element precursor, and the main group element precursor is preferably boric acid and/or phosphoric acid. The loading of the main group element in the alumina after impregnation should be 1-5mg/g alumina. The impregnation method is not particularly limited in the present invention, and may be equal volume impregnation, excessive impregnation, or the like. In addition, the dipping is preferably carried out at a constant temperature of 40-100 ℃ under continuous stirring, the dipping time is preferably 2-6 hours, then the dipping is dried for 5-12 hours at 100-150 ℃ in a blast drying oven or an infrared drying oven, and finally the dipping is baked for 1-24 hours at a constant temperature of 400-700 ℃ in a muffle furnace, so as to obtain the modified alumina.
In this step, the main group element such as B forms a boroaluminum 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. 1 is NH of alumina before and after boron modification 3 The TPD spectrum, as can be seen from FIG. 1, after the alumina surface is loaded with 5.5% and 9% of boron, the acid strength and acid amount of the alumina surface are obviously changed, strong acid peaks appear in the range of 300-500 ℃, and the peak area of weak acid peaks in the range of 100-300 ℃ are obviously increased, so that the conversion rate of the linear olefin of the isomerization catalyst is obviously increased.
In addition, different amounts of silicon are typically present in the alumina precursor, which can increase the acidity of the alumina, but alumina with different silicon content has different acidity and further different isomerization conversion of its linear olefins. FIG. 2 shows 0%, 1%, 5%, 5.5%, 23% NH of alumina containing silicon 3 TPD spectra, it can be seen from fig. 2 that aluminas with different silicon contents have different acidity. The invention can eliminate the influence caused by different silicon contents by the main group element modification step, and FIG. 3 is NH modified by boron on alumina with different silicon contents 3 TPD spectra, as can be seen from fig. 3, after boron modification, the alumina with different silicon content has comparable acid strength.
Then, the modified alumina is added into a second solution for ion exchange, wherein the second solution contains a transition metal precursor, and the transition metal is preferably one, two or more than two of Co, ni, mo, cu, ti and V, and the transition metal precursor is a soluble salt of the transition metal, such as nitrate, acetate and the like. The concentration of the second solution is preferably 0.001 to 1mol/L. The ion exchange process is preferably carried out at a constant temperature of 40-100 ℃ with continuous stirring, the ion exchange time is preferably 2-6h, and then deionized water is used for washing, drying and roasting for 1-6h in a muffle furnace at 450-700 ℃ to obtain the olefin isomerization catalyst.
The invention adopts the ion exchange method to modify the transition metal so as to control the load capacity of the exchanged transition metal, and simultaneously can remove the main group elements which do not chemically react with the surface of the alumina through ion exchange. As shown in Table 1, the boron content is reduced from 28.0% to 14.1% after ion exchange, and the loading is reduced by half, so that the selectivity of the dual-element modified alumina catalyst is greatly improved.
TABLE 1 XRF analysis of boron and aluminum in modified alumina before and after ion exchange
Moreover, the acidic distribution of the surface of the dual element modified alumina was also changed by ion exchange, FIG. 4 is NH of the modified alumina before and after ion exchange 3 The TPD spectrum, as shown in figure 4, shows that after ion exchange, the alumina has obvious strong acid peak in 500-800 deg.c and weak acid peak area in 100-500 deg.c.
In summary, the invention improves the olefin reaction activity of the alumina through the modification of the main group element, and the transition metal auxiliary agent improves the skeletal isomerism selectivity and the carbon deposit resistance of the oxide catalyst. The pore size distribution measured by nitrogen adsorption-desorption experiments of the prepared dual-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 specific optimization steps of the catalyst are as follows:
(1) Taking a certain amount of pseudo-boehmite containing 0-23 m percent of silicon, and roasting for 1-10 hours at the constant temperature of 400-700 ℃ in a muffle furnace to obtain gamma-Al with good crystal form 2 O 3 。
(2) Soaking and modifying the alumina 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 in a blast drying oven or an infrared drying oven at the temperature of 100-150 ℃ for 5-12 hours, 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 catalyst.
(3) And (3) carrying out ion exchange on the catalyst powder obtained in the step (2) in a transition metal salt solution at 40-100 ℃ for 2-6 hours, continuously stirring, washing with deionized water, drying, and roasting in a muffle furnace at 450-700 ℃ for 1-6 hours to obtain the transition metal modified alumina 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 should be present in an amount of 10% to 30%; the reactor is preferably a one-stage or multi-stage fixed bed reactor; the catalyst is preferably used in an amount of 0.1-0.5mL, the reaction temperature is preferably 300-500 ℃, the reaction pressure is preferably 0.2-0.5MPa, and the weight hourly space velocity is 1-35h -1 Preferably 2 to 4 hours -1
Under the above reaction conditions, the catalyst has the advantages of high linear olefin conversion rate of more than 80%, skeleton isomerism olefin yield of more than 60%, selectivity of more than 80%, high stability and good technical effect.
The invention is further illustrated by the following specific examples.
Comparative example 1
Weighing 50g of pseudo-boehmite with silicon content of 1.0m percent, and roasting for 4 hours at 600 ℃ to obtain gamma-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Then, 62.9g of boric acid was weighed, 100mL of distilled water was used to prepare an aqueous boric acid solution, and 50g of gamma-Al was used as the above 2 O 3 Placing the mixture in the aqueous solution of boric acid, soaking the mixture in the solution for 2 hours at a constant temperature of 100 ℃ under continuous stirring, and drying the mixture in a forced air drying oven at 120 ℃ for 12 hours. Finally atRoasting in a muffle furnace at 600 ℃ for 2 hours to obtain the catalyst 1 with 11.0w% boron content.
Example 1
50mL of a solution containing 0.011mol/L of nickel element was prepared using nickel nitrate hexahydrate and distilled water, and 10g of the catalyst of comparative example 1 was placed in the solution, ion-exchanged at 40℃for 4 hours, washed, dried, and calcined at 500℃for 3 hours to obtain catalyst 2.
Example 2
50mL of a solution containing 0.033mol/L of cobalt element was prepared using cobalt nitrate hexahydrate and distilled water, and 10g of the catalyst of comparative example 1 was placed in the solution, reacted at 40℃for 4 hours, washed, dried, and calcined at 500℃for 3 hours to obtain catalyst 3.
Example 3
50mL of a solution containing 0.056mol/L of cobalt element was prepared using cobalt nitrate hexahydrate and distilled water, and 10g of the catalyst of comparative example 1 was placed in the solution, reacted at 40℃for 4 hours, washed, dried, and calcined at 500℃for 3 hours to obtain catalyst 4.
Example 4
50mL of a solution containing 0.067mol/L of nickel element was prepared using nickel nitrate hexahydrate and distilled water, and 10g of the catalyst of comparative example 1 was placed in the solution, reacted at 40℃for 4 hours, washed, dried, and calcined at 500℃for 3 hours to obtain catalyst 5.
The catalysts obtained in all examples and comparative 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 10%, 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, the filling amount is 2mL, and hydrogen is used for purging the catalyst before the reaction. The reaction raw material is pumped by a SZB-1 double-plunger micro metering pump, and high-purity H 2 (99.999%) is used as carrier gas, the raw materials are gasified in a gasifier before entering the reactor, the gasification temperature is 150 ℃, the reaction temperature is 400 ℃, the pressure is 0.4MPa, and the volume space velocity of the carrier gas is 3600h -1 The weight hourly space velocity (LHSV) of the feed solution was 12.0h -1 The cooling temperature of the ice water bath of the reaction product is 3-5 ℃.
The reaction raw materials and the products are analyzed by using a Beijing analytical instrument factory SP-3420 type gas chromatograph, a hydrogen flame detector is adopted, a chromatographic column is an elastic quartz capillary chromatographic column taking OVE as a fixed liquid, the column length is 50m, the diameter is 0.2mm, the initial temperature of the column is 303K, the final temperature is 433K, the heating rate is 4K/min, the FID detector is adopted, the carrier gas is nitrogen, and an N2000 chromatographic workstation is adopted for data analysis.
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 catalyst is used for skeletal isomerization reaction of 1-hexene, and experimental results are shown in table 2.
TABLE 2 isomerization results for catalyst samples
As can be seen from Table 2, the invention improves the skeletal isomerism selectivity and the carbon deposit resistance of the oxide catalyst and improves the yield of the isoolefin through the modification of main group elements and the ion exchange of the transition metal auxiliary agent.
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 process for preparing an olefin isomerization catalyst, comprising the steps of:
step 1, roasting an alumina precursor;
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnating solution to finish modification, and then drying and roasting;
step 3, adding the modified alumina obtained in the step 2 into a second solution for ion exchange, and then washing, drying and roasting to obtain an olefin isomerization catalyst;
the first impregnating solution comprises a main group element precursor, the second solution comprises a transition metal precursor, and main group elements in the main group element precursor are boron and/or phosphorus; the mass content of silicon in the precursor of the aluminum oxide is more than 0% and less than or equal to 23%.
2. The method for preparing an olefin isomerization catalyst according to claim 1, wherein the precursor of alumina is silicon-containing gibbsite or pseudo-boehmite; the pore volume of the precursor of the alumina is more than or equal to 0.4mL/g, and the BET specific surface area is 200m 2 /g to 400m 2 /g。
3. The method for producing an olefin isomerization catalyst according to claim 1, wherein the transition metal in the transition metal precursor is any one of Co, ni, mo, cu, ti and V, or a combination of two or more.
4. The method for producing an olefin isomerization catalyst according to claim 1, wherein the main group element precursor is boric acid and/or phosphoric acid; the transition metal precursor is soluble salt of the transition metal, and the concentration of the transition metal in the second solution is 0.001-1 mol/L.
5. The method for preparing an olefin isomerization catalyst according to claim 1, wherein the temperature of calcination in step 1 is 400-700 ℃ and the time of calcination is 1-10 hours.
6. The method for preparing an olefin isomerization 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; the drying temperature in the step 2 is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 400-700 ℃, and the roasting time is 1-24 hours.
7. The method for preparing an olefin isomerization catalyst according to claim 1, wherein the ion exchange temperature in the step 3 is 40-100 ℃ and the ion exchange time is 2-6 hours; the ion exchange in the step 3 is constant temperature soaking, and stirring is continuously carried out; the drying temperature in the step 3 is 100-150 ℃, the drying time is 5-12 hours, the roasting temperature is 450-700 ℃, and the roasting time is 1-6 hours.
8. A catalyst obtainable by the process for the preparation of an olefin isomerisation catalyst as claimed in any of claims 1 to 7.
9. A first partA process for isomerizing olefins comprising the step of containing C by using the catalyst according to claim 8 as a catalyst 5 And/or C 6 Wherein C in the hydrocarbon mixture is used as raw material for olefin isomerization reaction 5 And/or C 6 The mass content of the linear olefin is 10-30%.
10. The olefin isomerization process according to claim 9, wherein the isomerization reaction temperature is 300-500 ℃, the isomerization reaction pressure is 0.2-0.5MPa, and the weight hourly space velocity is 1-35h -1 。
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