CN114011425B - Dual-function catalyst and preparation method and application method thereof - Google Patents
Dual-function catalyst and preparation method and application method thereof Download PDFInfo
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- CN114011425B CN114011425B CN202111493033.0A CN202111493033A CN114011425B CN 114011425 B CN114011425 B CN 114011425B CN 202111493033 A CN202111493033 A CN 202111493033A CN 114011425 B CN114011425 B CN 114011425B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 65
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010926 purge Methods 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 48
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 30
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 19
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- OAQPVOXRGWEZQS-UHFFFAOYSA-N O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] OAQPVOXRGWEZQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 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 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000001361 adipic acid Substances 0.000 abstract description 3
- 235000011037 adipic acid Nutrition 0.000 abstract description 3
- 230000018109 developmental process Effects 0.000 abstract description 2
- 206010037544 Purging Diseases 0.000 description 32
- 238000006555 catalytic reaction Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229910001960 metal nitrate Inorganic materials 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 238000010408 sweeping Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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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
- B01J23/002—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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- 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
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of catalysts. The invention provides a double-function catalyst, which is prepared into a series of perovskite composite materials La by adjusting the feeding mole ratio of various metal salts x A 1‑ x Fe y M 1‑y O 3 And then the double-function catalyst is prepared by modification of alkali metal compounds. The invention also provides a method for preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains, which comprises the steps of placing the prepared bifunctional catalyst in a fixed bed reactor, and activating the catalyst after air is introduced at a set temperature; introducing nitrogen to purge the reaction tube; cyclohexane and nitrogen are mixed and then introduced into a reactor to contact with a catalyst for oxidative dehydrogenation reaction; and after the reaction is finished, introducing air to complete the regeneration of the bifunctional catalyst. The development and application of the novel technology for efficiently preparing cyclohexene by oxidative dehydrogenation of cyclohexane chemical chains can effectively solve the bottleneck of cyclohexene productivity which hinders the green process popularization of producing caprolactam and adipic acid by cyclohexene routes.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a bifunctional catalyst, and a preparation method, application and an application method thereof.
Background
Cyclohexene is an important organic intermediate and is widely applied to industries such as textile, pharmacy, automobiles, pesticides, food and the like. Can be used as raw materials for preparing adipic acid, cyclohexyl formic acid, cyclohexene oxide and the like; are commonly used in the petroleum industry as extractants, stabilizers for high octane gasoline, and the like.
There are many technical methods for producing cyclohexene industrially. There are conventionally methods for dehydration of cyclohexanol, dehydrohalogenation of halogenated cyclohexane, and the like. As cyclohexanol, halogenated cyclohexane and alkali metal or alkaline earth metal with high cost are used as raw materials, the production process is complex and the cost is high. The benzene liquid phase partial hydrogenation method is a preferred method for producing cyclohexene recently, and has the advantages of short flow, fewer steps and the like compared with the traditional processes such as cyclohexane dehydrogenation, cyclohexanol dehydration and the like. However, benzene hydrogenation is extremely unfavorable to cyclohexene production in thermodynamics, and cyclohexane is extremely easy to be completely hydrogenated. The current industrial technical index is only set to S40 > 80%. The method has low production efficiency and high separation energy consumption, and adopts the noble metal ruthenium black catalyst and Zn salt auxiliary agent as a catalytic system. Meanwhile, in order to prevent the noble metal Ru catalyst from being deactivated, the method has high requirements on the purity of raw material benzene and high production cost. Although researchers at home and abroad are continuously researching a more efficient benzene partial hydrogenation catalytic system, the contradiction between the reaction conversion rate and the cyclohexene selectivity is difficult to solve all the time.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a bifunctional catalyst, and a preparation method, application and an application method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a bifunctional catalyst which is prepared from the following raw materials in parts by mass: 7 to 8 parts of lanthanum nitrate, 0.8 to 1.2 parts of alkaline earth metal precursor, 7.5 to 8.5 parts of ferric nitrate, 0.2 to 0.9 part of transition metal precursor and 0.4 to 0.6 part of alkali metal compound.
Preferably, the lanthanum nitrate is lanthanum nitrate hexahydrate; the ferric nitrate is ferric nitrate nonahydrate;
the alkaline earth metal precursor comprises strontium nitrate, magnesium nitrate hexahydrate or calcium nitrate tetrahydrate;
the transition metal precursor comprises ammonium metavanadate, cobalt nitrate hexahydrate or molybdenum nitrate pentahydrate;
the alkali metal compound comprises lithium carbonate or potassium carbonate.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) Mixing lanthanum nitrate, alkaline earth metal precursor, ferric nitrate, transition metal precursor, complexing agent, water and dihydric alcohol to obtain sol;
(2) Sequentially drying and roasting the sol to obtain a composite material;
(3) And mixing the composite material, the alkali metal compound and water, and sequentially drying and roasting to obtain the bifunctional catalyst.
Preferably, the complexing agent in the step (1) is citric acid, and the dihydric alcohol is ethylene glycol;
the mass ratio of the lanthanum nitrate to the complexing agent is 7-8: 20-24 parts;
the dosage ratio of the lanthanum nitrate to the water is 7-8 g: 180-220 mL;
the mass ratio of the lanthanum nitrate to the dihydric alcohol is 7-8: 9.5 to 10.5;
the mixing mode is heating and stirring, the heating rate of the heating and stirring is 4-6 ℃/min, the target temperature of the heating and stirring is 75-85 ℃, the rotating speed of the heating and stirring is 1400-1600 rpm, and the stirring time after the heating and stirring reaches the target temperature is 7-9 h.
Preferably, the drying in the step (2) is vacuum drying, the temperature of the vacuum drying is 70-90 ℃, the vacuum degree of the vacuum drying is-0.12-0.08 MPa, and the time of the vacuum drying is 10-12 h;
the roasting is to sequentially perform first roasting and second roasting;
the temperature rising rate of the first roasting is 8-12 ℃/min, the target temperature of the first roasting is 440-460 ℃, and the roasting time after the first roasting reaches the target temperature is 1-1.2 h;
the target temperature of the second roasting is 940-960 ℃, the temperature rising rate from the first roasting target temperature to the second roasting target temperature is 8-12 ℃/min, and the roasting time after the second roasting reaches the target temperature is 7.8-8.2 h.
Preferably, the ratio of the lanthanum nitrate to the water in the step (3) is 7-8 g: 180-220 mL;
the mixing mode is stirring, the rotating speed of the stirring is 450-550 rpm, and the stirring time is 2.8-3.2 h;
the drying temperature is 75-85 ℃, the drying vacuum degree is-0.12 to-0.08 MPa, and the drying time is 10-12 h;
the temperature rising rate of the roasting is 8-12 ℃/min, the target temperature of the roasting is 880-920 ℃, and the roasting time after the roasting reaches the target temperature is 7.5-8.5 h.
The invention also provides application of the bifunctional catalyst in preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains.
A method for preparing cyclohexene by cyclic oxidative dehydrogenation of a cyclohexane chemical chain, which comprises the following steps:
placing the bifunctional catalyst in a fixed bed reactor, setting the temperature, and introducing air to activate the catalyst; introducing nitrogen to purge the reactor;
introducing nitrogen carrying cyclohexane into a reactor to start oxidative dehydrogenation reaction; after the reaction is finished, nitrogen is introduced to purge the reactor again, and air is introduced to complete the regeneration of the bifunctional catalyst.
Preferably, the set temperature is 740-760 ℃, the air ventilation time is 2-4 min, and the activation time is 50-70 min;
the flow rate of the purging is 20-40 mL/min, the purging time is 2-4 min, and the purging temperature is 740-760 ℃.
Preferably, the volume ratio of the cyclohexane to the nitrogen is 6.5-7.5: 1, a step of;
the temperature of the oxidative dehydrogenation reaction is 500-650 ℃, the gas flow rate of the oxidative dehydrogenation reaction is 20-40 mL/min, and the reaction volume space velocity of the oxidative dehydrogenation reaction is 1200-2400 h -1 。
The invention provides a double-function catalyst, which is prepared into a series of perovskite composite materials La by adjusting the feeding mole ratio of various metal salts x A 1-x Fe y M 1-y O 3 And then the double-function catalyst is prepared by modification of alkali metal compounds. The alkaline earth metal precursor (A) is strontium nitrate, magnesium nitrate hexahydrate or calcium nitrate tetrahydrate, the transition metal precursor (M) is ammonium metavanadate, cobalt nitrate hexahydrate or molybdenum nitrate pentahydrate, and the alkali metal compound is lithium carbonate or potassium carbonate; the perovskite oxide modified by the alkali metal salt is used as a catalyst for cyclohexane chemical chain oxidative dehydrogenation (CL-ODH), so that the use of noble metals is avoided, and the cost of the catalyst is reduced; according to the perovskite oxide, perovskite oxides with different lattice oxygen contents and activities can be obtained by changing the metal element type at the A, B position, and other metal atoms are adopted to partially replace atoms at the A or B position in the lattice, so that lattice defects can be generated, and the lattice oxygen content can be regulated; the perovskite structure may allow some elements to exist in an abnormal valence state or allow active metals to exist in a mixed valence state, thereby exhibiting more excellent catalytic activity. The invention also provides a method for preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains, which comprises the steps of placing the prepared bifunctional catalyst in a fixed bed reactor, and activating the catalyst after air is introduced at a set temperature; introducing nitrogen to purge the reaction tube; cyclohexane and nitrogen are mixed and then introduced into a reactor to contact with a catalyst for oxidative dehydrogenation reaction; and after the reaction is finished, nitrogen is sequentially introduced to purge the reactor again, and air is introduced to complete the regeneration of the bifunctional catalyst. The development and application of the novel technology for efficiently preparing cyclohexene by oxidative dehydrogenation of cyclohexane chemical chains can effectively solve the problem of cyclohexene productivity bottleneck which hinders the popularization of green technology for producing caprolactam and adipic acid by cyclohexene routes, and the alkane chemical chain oxidative dehydrogenation is used as a novel clean and efficient technology for preparing olefin, and has extremely high research value and application prospect.
Detailed Description
The invention provides a bifunctional catalyst which is prepared from the following raw materials in parts by mass: 7 to 8 parts of lanthanum nitrate, 0.8 to 1.2 parts of alkaline earth metal precursor, 7.5 to 8.5 parts of ferric nitrate, 0.2 to 0.9 part of transition metal precursor and 0.4 to 0.6 part of alkali metal compound
In the present invention, the lanthanum nitrate is 7 to 8 parts, preferably 7.2 to 7.8 parts, more preferably 7.4 to 7.6 parts.
In the present invention, the alkaline earth metal precursor is 0.8 to 1.2 parts, preferably 0.9 to 1.1 parts, more preferably 0.95 to 1.05 parts.
In the present invention, the iron nitrate is 7.5 to 8.5 parts, preferably 7.6 to 8.4 parts, more preferably 7.8 to 8.2 parts.
In the present invention, the transition metal precursor is 0.2 to 0.9 part, preferably 0.3 to 0.8 part, more preferably 0.5 to 0.6 part.
In the present invention, the alkali metal compound is 0.4 to 0.6 part, preferably 0.44 to 0.56 part, more preferably 0.48 to 0.52 part.
In the present invention, the lanthanum nitrate is preferably lanthanum nitrate hexahydrate; the ferric nitrate is preferably ferric nitrate nonahydrate.
In the present invention, the alkaline earth metal precursor preferably comprises strontium nitrate, magnesium nitrate hexahydrate, or calcium nitrate tetrahydrate.
In the present invention, the transition metal precursor preferably comprises ammonium metavanadate, cobalt nitrate hexahydrate, or molybdenum nitrate pentahydrate.
In the present invention, the alkali metal compound preferably contains lithium carbonate or potassium carbonate.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) Mixing lanthanum nitrate, alkaline earth metal precursor, ferric nitrate, transition metal precursor, complexing agent, water and dihydric alcohol to obtain sol;
(2) Sequentially drying and roasting the sol to obtain a composite material;
(3) And mixing the composite material, the alkali metal compound and water, and sequentially drying and roasting to obtain the bifunctional catalyst.
In the present invention, the complexing agent in the step (1) is preferably citric acid, and the dihydric alcohol is preferably ethylene glycol.
In the invention, the mass ratio of the lanthanum nitrate to the complexing agent is preferably 7-8: 20 to 24, more preferably 7.2 to 7.8:21 to 23, more preferably 7.4 to 7.6:21.5 to 22.5.
In the invention, the dosage ratio of the lanthanum nitrate to the water is preferably 7-8 g:180 to 220mL, more preferably 7.2 to 7.8g:190 to 210mL, more preferably 7.4 to 7.6g: 195-205 mL.
In the invention, the mass ratio of the lanthanum nitrate to the dihydric alcohol is preferably 7-8: 9 to 11, more preferably 7.2 to 7.8:9.6 to 10.4, more preferably 7.4 to 7.6:9.8 to 10.2.
In the invention, firstly, lanthanum nitrate, alkaline earth metal precursor, ferric nitrate, transition metal precursor and water are mixed and stirred; the stirring time is preferably 50 to 70 minutes, more preferably 55 to 65 minutes, and still more preferably 58 to 62 minutes; the stirring speed is preferably 400 to 600rpm, more preferably 450 to 550rpm, and even more preferably 480 to 520rpm; and obtaining the metal nitrate mixed solution after stirring.
In the invention, the metal nitrate mixed solution and the complexing agent are mixed and stirred; the stirring time is preferably 30 to 40 minutes, more preferably 32 to 38 minutes, and still more preferably 34 to 36 minutes; the stirring speed is preferably 800 to 1200rpm, more preferably 900 to 1100rpm, still more preferably 950 to 1050rpm; after the stirring is finished, adding dihydric alcohol to stir in the next step.
In the invention, the mixing mode is preferably heating and stirring, and the heating rate of the heating and stirring is preferably 4-6 ℃/min, more preferably 4.4-5.6 ℃/min, and even more preferably 4.8-5.2 ℃/min; the target temperature for heating and stirring is preferably 75 to 85 ℃, more preferably 76 to 84 ℃, and even more preferably 78 to 82 ℃; the rotational speed of the heating and stirring is preferably 1400 to 1600rpm, more preferably 1440 to 1560rpm, and still more preferably 1480 to 1520rpm; the stirring time after the temperature rise and stirring reaches the target temperature is preferably 7 to 9 hours, more preferably 7.5 to 8.5 hours, and still more preferably 7.8 to 8.2 hours.
In the present invention, the drying in the step (2) is preferably vacuum drying, and the temperature of the vacuum drying is preferably 70 to 90 ℃, more preferably 74 to 86 ℃, and even more preferably 78 to 82 ℃; the vacuum degree of the vacuum drying is preferably-0.12 to-0.08 MPa, more preferably-0.11 to-0.09 MPa, and even more preferably-0.105 to-0.095 MPa; the time for the vacuum drying is preferably 10 to 12 hours, more preferably 10.5 to 11.5 hours, and still more preferably 10.8 to 11.2 hours.
In the present invention, the firing is preferably performed sequentially by first firing and second firing;
in the present invention, the temperature rise rate of the first firing is preferably 8 to 12 ℃/min, more preferably 9 to 11 ℃/min, still more preferably 9.5 to 10.5 ℃/min; the target temperature of the first firing is preferably 440 to 460 ℃, more preferably 445 to 455 ℃, and even more preferably 448 to 452 ℃; the baking time after the first baking reaches the target temperature is preferably 1 to 1.2 hours, more preferably 1.04 to 1.16 hours, and still more preferably 1.08 to 1.12 hours.
In the present invention, the target temperature of the second firing is preferably 940 to 960 ℃, more preferably 945 to 955 ℃, still more preferably 948 to 952 ℃; the temperature rise rate from the first firing target temperature to the second firing target temperature is preferably 8 to 12 ℃/min, more preferably 9 to 11 ℃/min, still more preferably 9.5 to 10.5 ℃/min; the baking time after the second baking reaches the target temperature is preferably 7.8 to 8.2 hours, more preferably 7.9 to 8.1 hours, and still more preferably 7.95 to 8.05 hours.
In the invention, the ratio of the lanthanum nitrate to the water in the step (3) is preferably 7-8 g:180 to 220mL, more preferably 7.2 to 7.8g:190 to 210mL, more preferably 7.4 to 7.6g: 195-205 mL.
In the present invention, the composite material and water are mixed first, preferably by stirring at a rotation speed of preferably 400 to 600rpm, more preferably 450 to 550rpm, still more preferably 480 to 520rpm; the stirring time is preferably 20 to 40 minutes, more preferably 24 to 36 minutes, and still more preferably 28 to 32 minutes. And obtaining a mixed system after the stirring is finished.
In the present invention, the mixing system and the alkali metal compound are mixed, preferably by stirring at a rotation speed of preferably 450 to 550rpm, more preferably 460 to 540rpm, still more preferably 480 to 520rpm; the stirring time is preferably 2.8 to 3.2 hours, more preferably 2.9 to 3.1 hours, and still more preferably 2.95 to 3.05 hours; after the stirring is finished, standing is carried out, wherein the standing time is preferably 1.8-2.2 h, more preferably 1.9-2.1 h, and even more preferably 1.95-2.05 h; after the completion of standing, a mixture was obtained, which was dried in the next step.
In the present invention, the drying temperature is preferably 75 to 85 ℃, more preferably 76 to 84 ℃, and even more preferably 78 to 82 ℃; the vacuum degree of the drying is preferably-0.12 to-0.08 MPa, more preferably-0.11 to-0.09 MPa, and even more preferably-0.105 to-0.095 MPa; the drying time is preferably 10 to 12 hours, more preferably 10.5 to 11.5 hours, and still more preferably 10.8 to 11.2 hours.
In the present invention, the temperature rise rate of the calcination is preferably 8 to 12 ℃/min, more preferably 9 to 11 ℃/min, still more preferably 9.5 to 10.5 ℃/min; the target temperature for the calcination is preferably 880 to 920 ℃, more preferably 890 to 910 ℃, and even more preferably 895 to 905 ℃; the baking time after the baking reaches the target temperature is preferably 7.5 to 8.5 hours, more preferably 7.6 to 8.4 hours, and still more preferably 7.8 to 8.2 hours.
In the present invention, the refining is preferably performed after the baking is finished, the refining mode is preferably ball milling, and the ball milling speed is preferably 400-600 rpm, more preferably 450-550 rpm, and even more preferably 480-520 rpm; the time for the ball milling is preferably 1.8 to 2.2 hours, more preferably 1.9 to 2.1 hours, and still more preferably 1.95 to 2.05 hours. And after the ball milling is finished, the bifunctional catalyst is obtained.
The invention also provides application of the bifunctional catalyst in preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains.
A method for preparing cyclohexene by cyclic oxidative dehydrogenation of a cyclohexane chemical chain, which comprises the following steps:
placing the bifunctional catalyst in a fixed bed reactor, setting the temperature, and introducing air to activate the catalyst; introducing nitrogen to purge the reactor;
introducing nitrogen carrying cyclohexane into a reactor to start oxidative dehydrogenation reaction; after the reaction is finished, nitrogen is introduced to purge the reactor again, and air is introduced to complete the regeneration of the bifunctional catalyst.
In the present invention, the set temperature is preferably 740 to 760 ℃, more preferably 745 to 755 ℃, and even more preferably 748 to 752 ℃; the time for introducing the air is preferably 2 to 4 minutes, more preferably 2.5 to 3.5 minutes, and even more preferably 2.8 to 3.2 minutes; the flow rate of the air is preferably 20-40 mL/min, more preferably 25-35 mL/min, and even more preferably 28-32 mL/min; the activation is performed after the air is introduced, and the activation time is preferably 50 to 70 minutes, more preferably 55 to 65 minutes, and even more preferably 58 to 62 minutes.
In the present invention, the flow rate of the purge is preferably 20 to 40mL/min, more preferably 25 to 35mL/min, still more preferably 28 to 32mL/min; the purging time is preferably 2 to 4 minutes, more preferably 2.5 to 3.5 minutes, and still more preferably 2.8 to 3.2 minutes; the temperature of the purging is preferably 740 to 760 ℃, more preferably 745 to 755 ℃, and even more preferably 748 to 752 ℃.
In the present invention, the volume ratio of cyclohexane to nitrogen is preferably 6.5 to 7.5:1, more preferably from 6.6 to 7.4:1, more preferably from 6.8 to 7.2:1.
in the invention, the nitrogen carries cyclohexane to be contacted with the catalyst after being introduced into the reactor, wherein the contact temperature is preferably 500-650 ℃, more preferably 550-600 ℃, and even more preferably 560-590 ℃; the flow rate of the contacted gas is preferably 20 to 40mL/min, more preferably 25 to 35mL/min, and even more preferably 28 to 32mL/min; the reaction volume space velocity of the contact is preferably 1200-2400 h -1 More preferably 1400 to 2200 hours -1 More preferably 1600 to 2000 hours -1 The contact time is preferably 4 to 6 minutes, more preferably 4.4 to 5.6 minutes, and still more preferably 4.8 to 5.2 minutes.
In the invention, nitrogen is adopted for secondary purging after the contact is finished, and the flow rate of the secondary purging is preferably 20-40 mL/min, more preferably 25-35 mL/min, and even more preferably 28-32 mL/min; the time of the secondary purging is preferably 2 to 4min, more preferably 2.5 to 3.5min, and still more preferably 2.8 to 3.2min; the temperature of the secondary purging is preferably 500 to 650 ℃, more preferably 550 to 600 ℃, still more preferably 560 to 590 ℃, and the time of the secondary purging is preferably 2 to 4min, more preferably 2.4 to 3.6min, still more preferably 2.8 to 3.2min.
In the present invention, the contact and the secondary purge are one cycle, and the number of repetitions of the cycle is preferably 3 to 4.
In the invention, the oxidative dehydrogenation reaction is started after the contact and the secondary purging are finished, wherein the temperature of the oxidative dehydrogenation reaction is preferably 500-650 ℃, more preferably 550-600 ℃, and even more preferably 560-590 ℃; the gas flow rate of the oxidative dehydrogenation reaction is preferably 20-40 mL/min, more preferably 25-35 mL/min, and even more preferably 28-32 mL/min; the reaction volume space velocity of the oxidative dehydrogenation reaction is 1200-2400 h -1 More preferably 1400 to 2200 hours -1 More preferably 1600 to 2000 hours -1 The oxidative dehydrogenation time is preferably 4 to 6 minutes, more preferably 4.4 to 5.6 minutes, and still more preferably 4.8 to 5.2 minutes.
In the invention, nitrogen is introduced to carry out purging again after the oxidative dehydrogenation reaction is finished, wherein the flow rate of the purging again is preferably 20-40 mL/min, more preferably 25-35 mL/min, and even more preferably 28-32 mL/min; the time for the re-purging is preferably 5 to 6min, more preferably 5.2 to 5.8min, and still more preferably 5.4 to 5.6min; the temperature of the secondary purging is preferably 500-650 ℃, more preferably 550-600 ℃, and even more preferably 560-590 ℃; introducing air after purging is finished, and regenerating the catalyst at the same flow rate and temperature; the regeneration time is preferably 2.5 to 3.5 minutes, more preferably 2.6 to 3.4 minutes, and still more preferably 2.8 to 3.2 minutes.
In the invention, the oxygen carrier in the perovskite oxide modified by alkali metal salt can be oxidized and regenerated in the air, and the catalyst carbon deposit is removed while the lattice oxygen is supplemented; and a large amount of heat carried after regeneration can be directly supplied to the dehydrogenation reaction, so that the process energy consumption is reduced.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
7.32g of lanthanum nitrate hexahydrate, 0.89g of strontium nitrate, 7.69g of ferric nitrate nonahydrate and 0.79g of molybdenum nitrate pentahydrate are taken to be dissolved in 200mL of water, and stirred for 60min at the rotation speed of 500rpm to obtain a metal nitrate mixed solution; mixing the metal nitrate mixed solution with 22.21g of citric acid, and stirring for 35min at a speed of 1000 rpm; mixing with 9.84g of ethylene glycol after stirring, heating to 80 ℃ at a heating rate of 5 ℃/min, stirring while heating, and continuing stirring for 8 hours after reaching 80 ℃ at a stirring speed of 1500rpm to obtain sol.
Drying the sol for 11 hours at 80 ℃ and minus 0.1MPa, heating the solid matters obtained by drying to 450 ℃ at a heating rate of 10 ℃/min, and roasting for 1 hour after reaching 450 ℃ to finish the first roasting; after the first roasting is finished, continuously heating to 950 ℃ at a heating rate of 10 ℃/min, and roasting for 8 hours after reaching 950 ℃ to finish the second roasting to obtain the perovskite type composite material La 0.8 Sr 0.2 Fe 0.9 Mo 0.1 O 3 。
Dissolving the obtained composite material in 200mL of water, and stirring for 30min at a rotation speed of 500rpm to obtain a mixed system; stirring the mixed system and 0.5g of lithium carbonate for 3 hours at a rotation speed of 500rpm, and standing for 2 hours after stirring to obtain a mixture; drying the mixture for 11 hours at 80 ℃ and minus 0.1MPa to obtain a solid substance; heating the solid substance to 900 ℃ at a heating rate of 10 ℃/min, and roasting for 8 hours after the solid substance reaches 900 ℃; ball milling for 2 hours at 500rpm after roasting to obtain the perovskite composite material Li modified by alkali metal compounds 2 CO 3 /La 0.8 Sr 0.2 Fe 0.9 Mo 0.1 O 3 A bifunctional catalyst.
The dual-function catalyst prepared in the embodiment is subjected to cyclohexane chemical chain cyclic oxidative dehydrogenation to prepare cyclohexene, 5g of the catalyst prepared in the embodiment is placed in a fixed bed reactor, air is introduced at a set temperature of 750 ℃ for 3min, the flow rate of the air is the same as the flow rate during catalysis, and the catalyst is activated at 750 ℃ for 60min after the air introduction is finished; then introducing nitrogen to purge for 3min, wherein the flow rate of purging is the same as the flow rate during catalysis; with nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7:1, the contact time is 5min, and the contact temperature, the gas flow rate and the reaction volume space velocity are the same as the parameters during oxidative dehydrogenation; after the contact is finished, introducing nitrogen and secondarily sweeping for 3min, wherein the flow rate, the temperature and the reaction volume airspeed of the secondary sweeping are the same as parameters in catalysis; the contact and the secondary purging were repeated 3 times, and the oxidative dehydrogenation reaction was started after the completion of the above.
With nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7:1, controlling the temperature of oxidative dehydrogenation to be 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, the gas flow rate of the oxidative dehydrogenation to be 30mL/min, and the reaction volume space velocity of the oxidative dehydrogenation to be 1200h respectively -1 、1500h -1 、1800h -1 、2100h -1 、2400h -1 The oxidative dehydrogenation time was 5min and the catalytic results are recorded in table 1.
After the catalysis is finished, introducing nitrogen at the same temperature and flow rate for purging again, wherein the purging time is 5min, introducing air, and maintaining for 3min at the same temperature and flow rate to obtain the regenerated catalyst.
As can be seen from table 1, the conversion rate generally increased with increasing temperature, and the cyclohexene selectivity showed a rule of increasing and then decreasing; the conversion and selectivity generally decrease with increasing volumetric space velocity. At an oxidative dehydrogenation temperature of 600 ℃ and a volume space velocity of 1500h -1 Under the condition of (1), the conversion rate is up to 49.70%, the selectivity of cyclohexene can be up to 87.70%, and the catalyst has good catalytic efficiency.
TABLE 1 catalytic results
Example 2
7.90g of lanthanum nitrate hexahydrate, 1.16g of magnesium nitrate hexahydrate, 8.29g of ferric nitrate nonahydrate and 0.27g of ammonium metavanadate are taken and dissolved in 220mL of water, and the mixture is stirred for 50min at the rotation speed of 600rpm to obtain a metal nitrate mixed solution; mixing the metal nitrate mixed solution with 23.95g of citric acid, and stirring for 40min at a speed of 1000 rpm; after the stirring was completed, 10.61g of ethylene glycol was mixed, the temperature was raised to 78℃at a temperature-raising rate of 4℃per minute, stirring was performed while the temperature was raised, the stirring speed was 1450rpm, and stirring was continued for 7.5 hours after the temperature reached 78℃to obtain a sol.
Drying the sol for 12 hours at 78 ℃ and minus 0.12MPa, heating the solid matters obtained by drying to 450 ℃ at a heating rate of 8 ℃/min, and roasting for 1 hour after reaching 450 ℃ to finish the first roasting; after the first roasting is finished, continuously heating to 950 ℃ at a heating rate of 8 ℃/min, and roasting for 8 hours after reaching 950 ℃ to finish the second roasting to obtain the perovskite type composite material La 0.8 Mg 0.2 Fe 0.9 V 0.1 O 3 。
Dissolving the obtained composite material in 190mL of water, and stirring at 600rpm for 40min to obtain a mixed system; stirring the mixed system and 0.5g of lithium carbonate at a rotation speed of 550rpm for 3.2 hours, and standing for 2.2 hours after stirring is finished to obtain a mixture; drying the mixture for 12 hours at 85 ℃ and minus 0.11MPa to obtain a solid substance; heating the solid substance to 920 ℃ at a heating rate of 12 ℃/min, and roasting for 8.5h after the solid substance reaches 920 ℃; ball milling for 2.2 hours at 550rpm after roasting to obtain the perovskite composite material Li modified by alkali metal compounds 2 CO 3 /La 0.8 Mg 0.2 Fe 0.9 V 0.1 O 3 A bifunctional catalyst.
The dual-function catalyst prepared in the embodiment is subjected to cyclohexane chemical chain cyclic oxidative dehydrogenation to prepare cyclohexene, 5g of the catalyst prepared in the embodiment is placed in a fixed bed reactor, air is introduced at a set temperature of 760 ℃ for 3.5min, the flow rate of the air is the same as the flow rate during catalysis, and the catalyst is activated at 760 ℃ for 65min after the air introduction is finished; then introducing nitrogen to purge for 3.5min, wherein the flow rate of purging is the same as the flow rate during catalysis; with nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7.5:1, the contact time is 4min, and the contact temperature, the gas flow rate and the reaction volume space velocity are the same as the parameters during oxidative dehydrogenation; after the contact is finished, introducing nitrogen and secondarily sweeping for 3min, wherein the flow rate, the temperature and the reaction volume airspeed of the secondary sweeping are the same as parameters in catalysis; the contact and the secondary purging were repeated 4 times, and the oxidative dehydrogenation reaction was started after the completion of the above.
With nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7.5:1, controlling the temperature of oxidative dehydrogenation to be 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, the gas flow rate of the oxidative dehydrogenation to be 30mL/min, and the reaction volume space velocity of the oxidative dehydrogenation to be 1200h respectively -1 、1500h -1 、1800h -1 、2100h -1 、2400h -1 The oxidative dehydrogenation time was 5min and the catalytic results are recorded in table 2.
After the catalysis is finished, introducing nitrogen at the same temperature and flow rate for purging again, wherein the purging time is 5min, introducing air, and maintaining for 2.5min at the same temperature and flow rate to obtain the regenerated catalyst.
As can be seen from Table 2, in this example, when the oxidative dehydrogenation temperature is 650℃and the volume space velocity is 1500h -1 Under the condition of (2), the conversion rate is up to 49.72%; when the oxidative dehydrogenation temperature is 600 ℃ and the volume space velocity is 1200h -1 Under the condition of (2), the selectivity of cyclohexene can reach 80.92%, and the catalyst has good catalytic efficiency.
TABLE 2 catalytic results
Example 3
Dissolving 7.76g of lanthanum nitrate hexahydrate, 1.05g of calcium nitrate tetrahydrate, 8.14g of ferric nitrate nonahydrate and 0.65g of cobalt nitrate hexahydrate in 180mL of water, and stirring at 600rpm for 70min to obtain a metal nitrate mixed solution; mixing the metal nitrate mixed solution with 23.53g of citric acid, and stirring for 35min at a speed of 1000 rpm; mixing with 10.42g of ethylene glycol after stirring, heating to 75 ℃ at a heating rate of 6 ℃/min, stirring while heating, and continuing stirring for 9h after reaching 75 ℃ at a stirring speed of 1400rpm to obtain sol.
Drying the sol for 10 hours at 90 ℃ and minus 0.08MPa, heating the solid matters obtained by drying to 460 ℃ at a heating rate of 8 ℃/min, and roasting for 1.1 hour after the solid matters reach 460 ℃ to finish the first roasting; after the first roasting is finished, continuously heating to 940 ℃ at a heating rate of 8 ℃/min, and roasting for 7.8 hours after the temperature reaches 940 ℃ to finish the second roasting to obtain the perovskite type composite material La 0.8 Ca 0.2 Fe 0.9 Co 0.1 O 3 。
Dissolving the obtained composite material in 190mL of water, and stirring at 600rpm for 35min to obtain a mixed system; stirring the mixed system and 0.5g of lithium carbonate for 3.1h at a rotation speed of 550rpm, and standing for 1.9h after stirring is finished to obtain a mixture; drying the mixture for 10 hours at 75 ℃ and-0.105 MPa to obtain a solid substance; heating the solid substance to 910 ℃ at a heating rate of 9 ℃/min, and roasting for 7.5h after the solid substance reaches 910 ℃; ball milling for 2.2 hours at 600rpm after roasting to obtain the perovskite composite material Li modified by alkali metal compounds 2 CO 3 /La 0.8 Ca 0.2 Fe 0.9 Co 0.1 O 3 A bifunctional catalyst.
The dual-function catalyst prepared in the embodiment is subjected to cyclohexane chemical chain cyclic oxidative dehydrogenation to prepare cyclohexene, and 5g of the catalyst prepared in the embodiment is taken and placed in a fixed bed reactor; introducing air at a set temperature of 755 ℃ for 4min, wherein the flow rate of the air is the same as that of the catalyst during catalysis, and activating the catalyst at 755 ℃ for 70min after the air is introduced; then introducing nitrogen to purge for 4min, wherein the flow rate of purging is the same as the flow rate during catalysis; with nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 6.5:1, the contact time is 5min, and the contact temperature, the gas flow rate and the reaction volume space velocity are the same as the parameters during oxidative dehydrogenation; after the contact is finished, introducing nitrogen and secondarily sweeping for 4min, wherein the flow rate, the temperature and the reaction volume airspeed of the secondary sweeping are the same as parameters in catalysis; the contact and the secondary purging were repeated 4 times, and the oxidative dehydrogenation reaction was started after the completion of the above.
With nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 6.5:1, controlling the temperature of the oxidative dehydrogenation to be 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, the gas flow rate of the oxidative dehydrogenation to be 40mL/min, and the reaction volume space velocity of the oxidative dehydrogenation to be 1200h respectively -1 、1500h -1 、1800h -1 、2100h -1 、2400h -1 The oxidative dehydrogenation time was 5min and the catalytic results are recorded in table 3.
After the catalysis is finished, introducing nitrogen at the same temperature and flow rate for purging again, wherein the purging time is 5min, introducing air, and maintaining for 3.5min at the same temperature and flow rate to obtain the regenerated catalyst.
As can be seen from Table 3, in this example, when the oxidative dehydrogenation temperature is 600℃and the volume space velocity is 1500h -1 Under the condition of (2), the conversion rate is up to 48.88%; the selectivity of cyclohexene can reach 77.55%, and the catalyst has good catalytic efficiency.
TABLE 3 catalytic results
Example 4
7.74g of lanthanum nitrate hexahydrate, 1.15g of magnesium nitrate hexahydrate, 8.12g of ferric nitrate nonahydrate and 0.83g of molybdenum nitrate pentahydrate are taken to be dissolved in 210mL of water, and stirred for 70min at the rotation speed of 480rpm to obtain a metal nitrate mixed solution; mixing the metal nitrate mixed solution with 23.47g of citric acid, and stirring for 40min at 1150 rpm; mixing with 10.4g of ethylene glycol after stirring, heating to 85 ℃ at a heating rate of 6 ℃/min, stirring while heating, and continuing stirring for 8 hours after reaching 82 ℃ at a rotating speed of 1555rpm to obtain sol.
Drying the sol for 12 hours at 78 ℃ and minus 0.1MPa, heating the solid matters obtained by drying to 450 ℃ at the heating rate of 10 ℃/min, and roasting for 1.2 hours after reaching 450 ℃ to finish the first roasting; after the first roasting is finished, continuously taking the temperature of 10 DEG CHeating the temperature at the heating rate of/min to 950 ℃, and roasting for 7.8 hours after the temperature reaches 950 ℃ to finish the second roasting to obtain the perovskite composite material La 0.8 Mg 0.2 Fe 0.9 Mo 0.1 O 3 。
Dissolving the obtained composite material in 220mL of water, and stirring at 600rpm for 40min to obtain a mixed system; stirring the mixed system and 0.5g of potassium carbonate for 3.1h at a rotation speed of 550rpm, and standing for 1.9h after stirring is finished to obtain a mixture; drying the mixture for 12 hours at the temperature of 85 ℃ and the pressure of minus 0.095MPa to obtain a solid substance; heating the solid substance to 910 ℃ at a heating rate of 11 ℃/min, and roasting for 8.2h after the solid substance reaches 910 ℃; ball milling for 2.2 hours at the rotating speed of 555rpm after the roasting is finished, and obtaining the perovskite composite material K modified by the alkali metal compound 2 CO 3 /La 0.8 Mg 0.2 Fe 0.9 Mo 0.1 O 3 A bifunctional catalyst.
The dual-function catalyst prepared in the embodiment is subjected to cyclohexane chemical chain cyclic oxidative dehydrogenation to prepare cyclohexene, and 5g of the catalyst prepared in the embodiment is taken and placed in a fixed bed reactor; introducing air for 3min at the set temperature of 752 ℃, wherein the flow rate of the air is the same as the flow rate during catalysis, and activating the catalyst for 60min at the temperature of 752 ℃ after the air is introduced; then introducing nitrogen to purge for 4min, wherein the flow rate of purging is the same as the flow rate during catalysis; with nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7:1, the contact time is 5min, and the contact temperature, the gas flow rate and the reaction volume space velocity are the same as the parameters during oxidative dehydrogenation; after the contact is finished, introducing nitrogen and secondarily sweeping for 4min, wherein the flow rate, the temperature and the reaction volume airspeed of the secondary sweeping are the same as parameters in catalysis; the contact and the secondary purging were repeated 3 times, and the oxidative dehydrogenation reaction was started after the completion of the above.
With nitrogen as carrier gas, the volume ratio of cyclohexane to nitrogen is 7:1, controlling the temperature of oxidative dehydrogenation to be 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, the gas flow rate of the oxidative dehydrogenation to be 30mL/min, and the reaction volume space velocity of the oxidative dehydrogenation to be 1200h respectively -1 、1500h -1 、1800h -1 、2100h -1 、2400h -1 Oxidative dehydrogenation time is 5min, and the catalytic result is recordedIn table 4.
After the catalysis is finished, introducing nitrogen at the same temperature and flow rate for purging again, wherein the purging time is 5min, introducing air, and maintaining for 3min at the same temperature and flow rate to obtain the regenerated catalyst.
As can be seen from Table 4, in this example, when the oxidative dehydrogenation temperature is 650℃and the volume space velocity is 1500h -1 Under the condition of (2), the conversion rate is as high as 39.62%; when the oxidative dehydrogenation temperature is 600 ℃ and the volume space velocity is 1200h -1 Under the condition of (2), the selectivity of cyclohexene can reach 74.82 percent, and the catalyst has good catalytic efficiency.
TABLE 4 catalytic results
From the above examples, the present invention provides a bifunctional catalyst. According to the invention, the perovskite oxide modified by alkali metal salt is used as a catalyst for cyclohexane chemical chain oxidative dehydrogenation (CL-ODH), so that the use of noble metals is avoided, and the cost of the catalyst is reduced; the catalyst can provide lattice oxygen for the reaction, and avoid alkane and O 2 The potential safety hazard is eliminated; the method for preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains can be carried out under higher alkane partial pressure, so that the reaction conversion rate is further improved; the oxygen carrier in the perovskite oxide modified by alkali metal salt can be oxidized and regenerated in the air, and the catalyst carbon deposit is removed while the lattice oxygen is supplemented; the perovskite oxide modified by alkali metal salt can directly supply dehydrogenation reaction after oxidation and regeneration, thereby reducing process energy consumption and further expanding the application of the perovskite metal oxide in the field of catalysis.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The application of the bifunctional catalyst in preparing cyclohexene by cyclic oxidative dehydrogenation of cyclohexane chemical chains is characterized in that the bifunctional catalyst is prepared from the following raw materials in parts by mass: 7 to 8 parts of lanthanum nitrate, 0.8 to 1.2 parts of alkaline earth metal precursor, 7.5 to 8.5 parts of ferric nitrate, 0.2 to 0.9 part of transition metal precursor and 0.4 to 0.6 part of alkali metal compound;
the lanthanum nitrate is lanthanum nitrate hexahydrate; the ferric nitrate is ferric nitrate nonahydrate;
the alkaline earth metal precursor comprises strontium nitrate, magnesium nitrate hexahydrate or calcium nitrate tetrahydrate;
the transition metal precursor comprises ammonium metavanadate, cobalt nitrate hexahydrate or molybdenum nitrate pentahydrate;
the alkali metal compound comprises lithium carbonate or potassium carbonate;
a series of perovskite type composite materials La are prepared by adjusting the feeding mole ratio of various metal salts x A 1-x Fe y M 1-y O 3 And then the double-function catalyst is prepared by modification of alkali metal compounds.
2. The use according to claim 1, comprising the steps of:
(1) Mixing lanthanum nitrate, alkaline earth metal precursor, ferric nitrate, transition metal precursor, complexing agent, water and dihydric alcohol to obtain sol;
(2) Sequentially drying and roasting the sol to obtain a composite material;
(3) And mixing the composite material, the alkali metal compound and water, and sequentially drying and roasting to obtain the bifunctional catalyst.
3. The use according to claim 2, wherein the complexing agent in step (1) is citric acid and the glycol is ethylene glycol;
the mass ratio of the lanthanum nitrate to the complexing agent is 7-8: 20-24 parts;
the dosage ratio of the lanthanum nitrate to the water is 7-8 g: 180-220 mL;
the mass ratio of the lanthanum nitrate to the dihydric alcohol is 7-8: 9.5 to 10.5;
the mixing mode in the step (1) is heating and stirring, the heating rate of the heating and stirring is 4-6 ℃/min, the target temperature of the heating and stirring is 75-85 ℃, the rotating speed of the heating and stirring is 1400-1600 rpm, and the stirring time after the heating and stirring reaches the target temperature is 7-9 h.
4. The use according to claim 2 or 3, wherein the drying in step (2) is vacuum drying, the temperature of the vacuum drying is 70-90 ℃, the vacuum degree of the vacuum drying is-0.12 to-0.08 MPa, and the time of the vacuum drying is 10-12 hours;
the roasting in the step (2) is sequentially performed with first roasting and second roasting;
the temperature rising rate of the first roasting is 8-12 ℃/min, the target temperature of the first roasting is 440-460 ℃, and the roasting time after the first roasting reaches the target temperature is 1-1.2 h;
the target temperature of the second roasting is 940-960 ℃, the temperature rising rate from the first roasting target temperature to the second roasting target temperature is 8-12 ℃/min, and the roasting time after the second roasting reaches the target temperature is 7.8-8.2 h.
5. The use according to claim 4, wherein the ratio of lanthanum nitrate to water in step (3) is 7 to 8g: 180-220 mL;
the mixing mode in the step (3) is stirring, the stirring rotating speed is 450-550 rpm, and the stirring time is 2.8-3.2 h;
the drying temperature in the step (3) is 75-85 ℃, the vacuum degree of the drying in the step (3) is-0.12 to-0.08 MPa, and the drying time in the step (3) is 10-12 h;
the temperature rising rate of the roasting in the step (3) is 8-12 ℃/min, the target temperature of the roasting in the step (3) is 880-920 ℃, and the roasting time after the roasting in the step (3) reaches the target temperature is 7.5-8.5 h.
6. A method for preparing cyclohexene by cyclic oxidative dehydrogenation of a cyclohexane chemical chain, which is characterized by comprising the following steps:
placing the bifunctional catalyst of any one of claims 1-5 in a fixed bed reactor, setting the temperature, and introducing air to activate the catalyst; introducing nitrogen to purge the reactor;
introducing nitrogen carrying cyclohexane into a reactor to start oxidative dehydrogenation reaction; after the reaction is finished, nitrogen is introduced to purge the reactor again, and air is introduced to complete the regeneration of the catalyst.
7. The method of claim 6, wherein the set temperature is 740-760 ℃, the air-in time is 2-4 min, and the activation time is 50-70 min;
the flow rate of the purging is 20-40 mL/min, the purging time is 2-4 min, and the purging temperature is 740-760 ℃.
8. The method according to claim 6 or 7, wherein the volume ratio of cyclohexane to nitrogen is 6.5 to 7.5:1, a step of;
the temperature of the oxidative dehydrogenation reaction is 500-650 ℃, the gas flow rate of the oxidative dehydrogenation reaction is 20-40 mL/min, and the reaction volume space velocity of the oxidative dehydrogenation reaction is 1200-2400 h -1 。
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