CN112337468A - 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 93
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 66
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 62
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 39
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 150000003624 transition metals Chemical class 0.000 claims abstract description 24
- 238000005342 ion exchange Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 238000007654 immersion Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 238000001354 calcination Methods 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 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
- 230000007547 defect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 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
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000007605 air drying Methods 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
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 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
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 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
- 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
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 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
- 238000007334 copolymerization reaction 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
- 230000009849 deactivation Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction 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
- 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
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000011049 filling Methods 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
- 239000005457 ice water Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011068 loading 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
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- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 239000006200 vaporizer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Abstract
The invention discloses an olefin isomerization catalyst and a preparation method and application thereof, and the catalyst comprises the following steps: step 1, roasting a precursor of aluminum oxide; step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnation solution to complete 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 immersion liquid contains a main group element precursor, and the second immersion liquid contains a transition metal precursor. The catalyst obtained by the method has higher selectivity and higher product yield, and the catalyst is not easy to inactivate.
Description
Technical Field
The invention relates to an olefin isomerization catalyst, a preparation method and application thereof, in particular to a metal modified oxide catalyst for light linear 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, can be used as a high-octane blending component of gasoline, can also be used for producing copolymerization and homopolymerization rubber and high polymer plastics, and can be synthesized into various deep processing chemicals due to the special framework structure of the isoolefine. In addition, isoolefine is an important fine chemical raw material, and plays a great role in the industries of pesticides, medicines, spices, foods and the like.
The methods for producing isoolefine are various, the prior industrial application is mainly an ether cracking method and a linear chain olefine 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 gasoline refining4、C5、C6The full and reasonable utilization of the fraction is the best way for producing isoolefine.
The skeletal isomerization reaction of olefin needs to be carried out under the catalysis of an acid catalyst, the key point of research and development lies in the development of a high-efficiency catalyst, and the catalyst for the skeletal isomerization reaction of olefin mainly comprises three catalysts, namely an oxide catalyst, a halide catalyst and a molecular sieve catalyst. Compared with halide catalysts which are easy to deactivate and harm the environment and molecular sieve catalysts which are complex in manufacturing process and high in manufacturing cost, oxide catalysts have the advantages of wide sources, low price and the like. However, current research is focused on molecular sieve catalysts and few patents are published on oxide catalysts for skeletal isomerization of linear olefins.
US5817907 provides an olefin skeletal isomerization method, and the catalyst used is a pretreated molecular sieve with the pore diameter of 0.4-0.8 nm, such as SAPO-11, SAPO-31, EU-1, OMEGA, Nu-10, Nu-86, Nu-87, ferrierite, ZSM-23, ZSM-12 and the like. The pretreatment makes coke deposit in the molecular sieve pore channels to block micropores, thereby improving the selectivity and experimental stability of isoolefine.
US5849975 discloses a heterogeneous C4-C6The olefin preparation process adopts SSZ-32 molecular sieve with alkali metal and alkali earth metal exchanged in Si/Al ratio of 20:1-40:1 as catalyst.
U.S. Pat. No. 5,5463160 describes the use of zeolites having a pore size of 0.42 to 0.6nm and having intersecting channels with 10-and 8-membered rings to catalyze skeletal isomerization of linear olefins, which are characterized by the selective isomerization of n-pentene to 2-methylbutene.
US9414861 discloses a process for the preparation of an isomerization catalyst which is effective for the skeletal isomerization 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 monoacid, inorganic acid and at least one diacid, using alumina as binder, mixing, granulating and roasting.
US9811115 discloses a C4-C15The olefin isomerization method comprises the first step of separating C4-C15The olefin raw material and the aromatic compound are subjected to alkylation reaction and then dealkylation, and the product contains isoolefin with different skeleton distribution corresponding to the raw material, so that the yield of the isoolefin obtained by the method is low.
CN1827565A and CN101376617A disclose a method for preparing C6And C6+A process for skeletal isomerization of olefin features that the catalyst used is beta zeolite containing Si (1-20 wt.%) and Mg (0.1-3.5 wt.%), and when it is used in skeletal isomerization of olefin, the multi-branched product is obtained in high yield.
CN1109039A discloses a C4-C20The preparation method of catalyst for skeletal isomerization reaction of olefin includes the first soaking and modifying alumina with one or two kinds of organic siloxane, and the subsequent heat treatment to obtain the catalyst acting on n-C during skeletal isomerization reaction of pentene5 ＝Conversion of about 70%, isomerization selectivity of about 75%, i-C5 ＝The yield was about 50%.
Based on the oxide catalyst for the skeletal isomerization of linear olefins, which is disclosed at present, the selectivity and the yield of isomerized olefins are to be improved, and other molecular sieve catalysts disclosed 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, and a preparation method and application thereof, so as to overcome the defects of poor selectivity, low yield of isomerized olefin and easy inactivation of the catalyst of the olefin isomerization catalyst in the prior art.
In order to overcome the defects, the invention provides a preparation method of an olefin isomerization catalyst, which comprises the following steps:
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnation solution to complete 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 immersion liquid contains a main group element precursor, and the second immersion liquid contains a transition metal precursor.
The preparation method of the olefin isomerization catalyst comprises the following steps of preparing a precursor of alumina, wherein the precursor of the alumina is silicon-containing gibbsite or pseudo-boehmite, and the mass content of silicon in the precursor of the alumina 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 200m2G to 400m2/g。
The preparation method of the olefin isomerization catalyst comprises the following steps of (1) preparing a main group element precursor, wherein the main group element in the main group element precursor is boron and/or phosphorus; the transition metal in the transition metal precursor is any one of Co, Ni, Mo, Cu, Ti and V, or the combination of two or more of Co, Ni, Mo, Cu, Ti and V.
The preparation method of the olefin isomerization catalyst comprises the following steps of (1) preparing a main group element precursor, 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 step 1 of roasting at the temperature of 400-700 ℃ for 1-10 hours.
The preparation method of the olefin isomerization catalyst comprises the following steps of (1) soaking at the temperature of 40-100 ℃ for 2-6 hours in the step (2); the step 2 is constant-temperature impregnation, 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) enabling the temperature of ion exchange in the step (3) to be 40-100 ℃, and enabling the time of the ion exchange to be 2-6 h; in the step 3, ion exchange is carried out by constant-temperature dipping, 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 object, the present invention also provides a catalyst obtained by the above method for preparing an olefin isomerization catalyst.
In order to achieve the above object, the present invention further provides an olefin isomerization method using the above catalyst as a catalyst and containing C5And/or C6The hydrocarbon mixture of the linear olefin is used as a raw material to carry out olefin isomerization reaction, wherein C in the hydrocarbon mixture5And/or C6The mass content of the linear chain 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:
the invention takes alumina as a catalyst main body, sequentially modifies main group elements and metal elements, modulates the acid amount, the acid strength and the acid type of the catalyst through the modification of the main group elements, thereby improving the activity of the catalyst, and regulates the acid distribution on the surface of the catalyst through the modification of the metal, thereby improving the framework isomerization selectivity of the catalyst. The catalyst obtained by the method has higher selectivity and higher product yield, and the catalyst is not easy to inactivate.
Drawings
FIG. 1 shows NH of alumina before and after boron modification3-a TPD spectrum;
FIG. 2 shows alumina NH containing Si 0%, 1%, 5%, 5.5%, 23%3-a TPD spectrum;
FIG. 3 is a graph of NH modified with boron for alumina of different silicon content3-a TPD spectrum;
FIG. 4 shows NH of modified alumina before and after ion exchange3-TPD spectrum.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The invention provides a preparation method of an olefin isomerization catalyst, which comprises the following steps:
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnation solution to complete 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 immersion liquid contains a main group element precursor, and the second immersion liquid contains a transition metal precursor.
Wherein, the precursor of the alumina can be silicon-containing gibbsite or pseudo-boehmite, the preferred mass content of silicon in the precursor of the alumina is more than 0 percent and less than or equal to 23 percent, the preferred pore volume is more than or equal to 0.4mL/g, and the preferred BET specific surface area is 200m2G to 400m2(ii) in terms of/g. The calcination temperature of the alumina precursor may be 0-700 ℃.
And roasting the alumina precursor, and then adding the calcined alumina precursor into a first dipping solution for dipping, wherein the first dipping solution contains a main group 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 loading of main group elements in the impregnated alumina should be 1-5mg/g alumina. In the present invention, the impregnation method is not particularly limited, and the impregnation may be carried out in an equal volume, an excess amount, or the like. In addition, the dipping is preferably carried out at the constant temperature of 40-100 ℃ under continuous stirring, the dipping time is preferably 2-6 hours, then the drying is carried out for 5-12 hours at the temperature of 100-150 ℃ in a forced air drying oven or an infrared drying oven, and finally the modified alumina is obtained by constant-temperature roasting for 1-24 hours at the temperature of 400-700 ℃ in a muffle furnace.
In this step, the main group element such as B forms a boron aluminum surface compound with the surface of alumina, thereby increasing the acid center number and acid strength of alumina, and further increasing the isomerization conversion rate of linear olefins. FIG. 1 shows NH of alumina before and after boron modification3TPD spectrum, as can be seen from FIG. 1, after the alumina surface is loaded with 5.5% by mass and 9% by mass of boron, the acid strength and acid amount of the alumina surface are obviously changed, a strong acid peak appears in the range of 300 ℃ to 500 ℃, and the peak area of a weak acid peak in the range of 100 ℃ to 300 ℃ is obviously increased, so that the linear olefin conversion rate of the isomerization catalyst of the invention is obviously increased.
In addition, while different amounts of silicon are generally present in the alumina precursor, which can increase the acidity of the alumina, the alumina with different silicon contents has different acidity and thus different isomerization conversions of linear olefins. FIG. 2 shows alumina NH containing Si 0%, 1%, 5%, 5.5%, 23%3TPD spectrum, from FIG. 2 it can be seen that the aluminas with different silicon contents have different acidsAnd (4) sex. The invention can eliminate the influence caused by different silicon contents through the main group element modification step, and FIG. 3 shows NH modified by boron on alumina with different silicon contents3TPD spectrum, as can be seen from FIG. 3, the boron-modified aluminas with different silicon contents have comparable acid strengths.
Then, the modified alumina is added into a second solution for ion exchange, the second solution contains a transition metal precursor, the transition metal is preferably one or a combination of two or more of Co, Ni, Mo, Cu, Ti and V, and the transition metal precursor is soluble salt of the transition metal, such as nitrate, acetate and the like. The concentration of the second solution is preferably 0.001-1 mol/L. The ion exchange process is preferably carried out at the constant temperature of 40-100 ℃ without stirring, the ion exchange time is preferably 2-6h, and then the catalyst is washed by deionized water, dried and roasted for 1-6h at the temperature of 450-700 ℃ in a muffle furnace to obtain the olefin isomerization catalyst.
The invention adopts the ion exchange method to modify the transition metal, can control the load of the exchanged transition metal, and can remove the main group elements which do not have chemical reaction with the surface of the alumina through the ion exchange. As shown in Table 1, after ion exchange, the content of boron is reduced from 28.0% to 14.1%, and the load is reduced by half, so that the selectivity of the double-element modified alumina catalyst is greatly improved.
TABLE 1 XRF analysis results of boron and aluminum in modified alumina before and after ion exchange
Furthermore, the acidity distribution of the surface of the double-element modified alumina was also changed by ion exchange, and FIG. 4 shows NH of the modified alumina before and after ion exchange3TPD spectrum, as shown in FIG. 4, after ion exchange, the alumina showed a distinct strong acid peak at 500-800 deg.C and a distinct reduced peak area of a weak acid peak at 100-500 deg.C.
In conclusion, the olefin reaction activity of the alumina is improved through the modification of the main group elements, and the skeletal isomerization selectivity and the carbon deposition resistance of the oxide catalyst are improved through the transition metal auxiliary agent. The pore size distribution of the prepared double-element modified alumina linear olefin skeletal isomerization catalyst measured by a nitrogen adsorption-desorption experiment is that pores with the pore size of less 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 of more 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% of silicon, and roasting the pseudo-boehmite in a muffle furnace at the constant temperature of 400-700 ℃ for 1-10 hours to obtain gamma-Al with good crystal form2O3。
(2) Soaking and modifying the alumina obtained in the step (1) in a main group element solution at a constant temperature of 40-100 ℃ for 2-6 hours under continuous stirring, then drying in a forced air drying box or an infrared drying box at a temperature of 100-150 ℃ for 5-12 hours, and finally roasting in a muffle furnace at a 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 the temperature of 40-100 ℃ for 2-6h, stirring continuously, washing with deionized water, drying, and roasting in a muffle furnace at the temperature of 450-700 ℃ for 1-6h to obtain the transition metal modified alumina catalyst.
The conditions for the use of the catalyst are preferably: the reaction raw material preferably contains C5、C6Hydrocarbon mixture of linear olefins, wherein the content of linear olefins is 10% -30%; the reactor is preferably a one-stage or multi-stage fixed bed reactor; the dosage of the catalyst is preferably 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-1Preferably 2-4h-1
Under the reaction conditions, the catalyst has the advantages of high straight-chain olefin conversion rate of over 80 percent, skeletal isoolefin yield of over 60 percent, high selectivity of over 80 percent, 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 1.0 m%, and roasting at 600 ℃ for 4h to obtain gamma-Al2O3(ii) a Then 62.9g of boric acid is weighed, 100mL of distilled water is used for preparing a boric acid aqueous solution, and 50g of gamma-Al is added2O3Placing in the boric acid water solution, soaking for 2 hours at a constant temperature of 100 ℃ under continuous stirring, and drying for 12 hours in a blast drying oven at 120 ℃. Finally, the catalyst 1 with the boron content of 11.0w percent is obtained by constant temperature roasting for 2 hours in a muffle furnace at the temperature of 600 ℃.
Example 1
50mL of a solution having a nickel element content of 0.011mol/L was prepared using nickel nitrate hexahydrate and distilled water, and 10g of the catalyst in 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 having a cobalt element content of 0.033mol/L was prepared using cobalt nitrate hexahydrate and distilled water, and 10g of the catalyst in 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 having a cobalt element content of 0.056mol/L was prepared using cobalt nitrate hexahydrate and distilled water, and 10g of the catalyst in 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 having a nickel element content of 0.067mol/L was prepared using nickel nitrate hexahydrate and distilled water, and 10g of the catalyst in 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 the 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, in which the content of 1-hexene is 10%, and the reaction is implemented on a continuous flowing fixed bed microreactor, and the reaction is implementedThe upper part and the lower part of the reactor are filled with quartz sand, the catalyst is ground to 40-60 meshes, the filling amount is 2mL, and hydrogen is used for purging the catalyst before reaction. Pumping the reaction raw material into high-purity H by using SZB-1 type double-plunger micro-metering pump2(99.999%) as carrier gas, the raw material enters a vaporizer for vaporization before entering the reactor, the vaporization temperature is 150 ℃, the reaction temperature is 400 ℃, the pressure is 0.4MPa, and the volume space velocity of the carrier gas is 3600h-1The liquid weight hourly space velocity (LHSV) of the raw material is 12.0h-1And the cooling temperature of the reaction product in ice water bath is 3-5 ℃.
The reaction raw materials and products are analyzed by 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 stationary liquid, the length of the column is 50m, the diameter of the column is 0.2mm, the initial temperature of the column is 303K, the final temperature is 433K, the heating rate is 4K/min, a FID detector and carrier gas are nitrogen, and an N2000 chromatographic workstation is adopted for data analysis.
The experimental sample analysis 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:
the relative mass percent of a certain substance is equal to the mass percent of a certain substance in the liquid/the mass percent of the n-heptane in the liquid multiplied by 100 percent
Skeletal isomerization performance of the catalyst from C6The straight olefin conversion X, the skeletal isomerization hexene yield Y and the skeletal isomerization selectivity S were used as evaluation indices.
In the formula M1、M2Respectively as n-C in the raw material and the product6 ＝Relative mass percentage of (a); m3、M4Respectively i-C in the raw material and the product6 ＝Relative mass percentage of (c).
The above catalyst was used for the skeletal isomerization of 1-hexene and the experimental results are shown in table 2.
TABLE 2 isomerization results of catalyst samples
As can be seen from Table 2, the invention improves the skeletal isomerization selectivity and the carbon deposition resistance of the oxide catalyst and improves the yield of the isoolefin through the modification of the main group elements and the ion exchange of the transition metal auxiliary agent.
The present invention is capable of other embodiments, and various changes and modifications may be made 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 preparation method of an olefin isomerization catalyst is characterized by comprising the following steps:
step 1, roasting a precursor of aluminum oxide;
step 2, impregnating the alumina obtained by roasting in the step 1 with a first impregnation solution to complete 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 immersion liquid contains a main group element precursor, and the second immersion liquid contains a transition metal precursor.
2. The olefin of claim 1The preparation method of the isomerization catalyst is characterized in that the precursor of the alumina is silicon-containing gibbsite or pseudo-boehmite, and the mass content of silicon in the precursor of the alumina 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 200m2G to 400m2/g。
3. The method of claim 1, wherein the main group element in the main group element precursor is boron and/or phosphorus; the transition metal in the transition metal precursor is any one of Co, Ni, Mo, Cu, Ti and V, or the combination of two or more of Co, Ni, Mo, Cu, Ti and V.
4. The method of 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 the olefin isomerization catalyst as claimed in claim 1, wherein the calcination temperature in the step 1 is 400-700 ℃ and the calcination time is 1-10 hours.
6. The method for preparing the olefin isomerization catalyst according to claim 1, wherein the impregnation in the step 2 is performed at a temperature of 40 to 100 ℃ for 2 to 6 hours; the step 2 is constant-temperature impregnation, 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 the olefin isomerization catalyst according to claim 1, wherein the temperature of the ion exchange in the step 3 is 40 to 100 ℃, and the time of the ion exchange is 2 to 6 hours; in the step 3, ion exchange is carried out by constant-temperature dipping, 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. The catalyst obtained by the process for producing an olefin isomerization catalyst according to any one of claims 1 to 7.
9. A process for isomerizing olefins, which comprises using the catalyst of claim 8 as a catalyst and C5And/or C6The hydrocarbon mixture of the linear olefin is used as a raw material to carry out olefin isomerization reaction, wherein C in the hydrocarbon mixture5And/or C6The mass content of the linear chain olefin is 10-30%.
10. The olefin isomerization process of claim 9 wherein the isomerization reaction temperature is 300--1。
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