CN110614094A - Isobutane dehydrogenation catalyst with carrier of cubic and hexagonal symbiotic pore channel structure with cubic core structure, preparation method and application - Google Patents
Isobutane dehydrogenation catalyst with carrier of cubic and hexagonal symbiotic pore channel structure with cubic core structure, preparation method and application Download PDFInfo
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- CN110614094A CN110614094A CN201810637922.1A CN201810637922A CN110614094A CN 110614094 A CN110614094 A CN 110614094A CN 201810637922 A CN201810637922 A CN 201810637922A CN 110614094 A CN110614094 A CN 110614094A
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- isobutane
- dehydrogenation catalyst
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- isobutane dehydrogenation
- carbon material
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 266
- 239000001282 iso-butane Substances 0.000 title claims abstract description 133
- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 116
- 239000011148 porous material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 63
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000007725 thermal activation Methods 0.000 claims abstract description 8
- 238000007654 immersion Methods 0.000 claims abstract description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
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- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 10
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 10
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013335 mesoporous material Substances 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
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- 101150116295 CAT2 gene Proteins 0.000 description 6
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 6
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 6
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000009827 uniform distribution Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DMKKMGYBLFUGTO-UHFFFAOYSA-N 2-methyloxirane;oxirane Chemical compound C1CO1.C1CO1.CC1CO1 DMKKMGYBLFUGTO-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- 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
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses an isobutane dehydrogenation catalyst with a cubic and hexagonal symbiotic pore channel structure with a cubic core structure as a carrier, and a preparation method and application thereof. The method comprises the following steps: (a) preparing a first contact product; (b) preparing mesoporous carbon material raw powder; (c) carrying out treatment of a demoulding agent; (d) performing thermal activation treatment on the step (c), then performing immersion treatment in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially performing solvent removal treatment, drying and roasting. The method can synthesize the isobutane dehydrogenation catalyst with high catalytic activity by utilizing the silicon source with low cost.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an isobutane dehydrogenation catalyst with a cubic and hexagonal symbiotic pore channel structure and a cubic center structure as a carrier, a preparation method of the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and application of the isobutane dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from an apparatus for producing ethylene by steam cracking of naphtha, the by-product C4 fraction from a refinery Fluid Catalytic Cracking (FCC) apparatus, and the by-product tert-butyl alcohol (TAB) in the synthesis of propylene oxide by the Halcon method.
In recent years, with the development and utilization of downstream products of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of the chemical industry on isobutene, so the research and development work of a new isobutene production technology becomes a hot spot of the chemical industry. Among the most competitive technologies, isobutane dehydrogenation, n-butene skeletal isomerization and isobutene production by a novel FCC unit are known. Among the methods, the research on the reaction for preparing isobutene by directly dehydrogenating isobutane is early, and the industrial production is realized. China has abundant C4 resources, but the chemical utilization rate of C4 fraction is low in China, most of isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resource is an urgent task in the petrochemical research field. Therefore, the isobutene prepared by dehydrogenating isobutane has a great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly comprise two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr2O3、V2O5、Fe2O3、MoO3ZnO, etc., and a composite oxide thereof, such as V-Sb-O, V-Mo-O, Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate, etc. Compared with noble metal catalysts, oxide catalysts are less expensive. However, the catalyst is easy to deposit carbon, and the catalytic activity, selectivity and stability are low. In addition, most oxide catalysts contain components with high toxicity, which is not favorable for environmental protection. The research on dehydrogenation reactions on noble metal catalysts has a long history, and noble metal catalysts have higher activity, better selectivity, and are more environmentally friendly than other metal oxide catalysts. However, the catalyst cost is high due to the expensive price of noble metals, and the performance of such catalysts has not yet reached a satisfactory level.
In order to improve the reaction performance of the catalyst for preparing isobutene by isobutane dehydrogenation, researchers have done a lot of work. Such as: the catalyst performance is improved by changing the preparation method of the catalyst (industrial catalysis, 2014, 22(2): 148-. However, the specific surface area of the currently used carrier is small, which is not beneficial to the dispersion of the active metal component on the surface of the carrier, and is also not beneficial to the diffusion of raw materials and products in the reaction process.
Therefore, how to improve the reaction performance of the isobutane dehydrogenation catalyst is a problem to be solved in the field of preparing isobutene by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of uneven dispersion of noble metal active components and poor catalytic activity and stability of the existing isobutane dehydrogenation catalyst, and provides an isobutane dehydrogenation catalyst with a cubic and hexagonal symbiotic pore channel structure as a carrier, a preparation method thereof, the isobutane dehydrogenation catalyst prepared by the method and application of the isobutane dehydrogenation catalyst in preparing isobutene by isobutane dehydrogenation.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) under the condition of heating, carrying out first contact on phenol, formaldehyde and NaOH, and cooling a product obtained after the first contact to room temperature to obtain a first contact product;
(b) under the condition of heating, carrying out second contact on the first contact product and a template agent, cooling the product obtained after the second contact to room temperature to obtain a second contact product, and then sequentially carrying out centrifugal separation and drying on the second contact product to obtain mesoporous carbon material raw powder;
(c) treating the mesoporous carbon material raw powder with a stripping agent;
(d) and (c) carrying out thermal activation treatment on the mesocarbon material carrier obtained in the step (c), then carrying out immersion treatment in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
A second aspect of the invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
The third aspect of the invention provides an application of the isobutane dehydrogenation catalyst prepared by the method in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the following steps: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
After intensive research, the inventor of the invention finds that the carrier structure (including physical structures such as specific surface area, pore volume and pore size distribution, and chemical structures such as surface acid sites and electronic properties) of the noble metal catalyst not only has important influence on the dispersion degree of active metal components, but also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity and stability, depend both on the catalytic characteristics of the active component and on the characteristics of the catalyst support. In order to reduce the content of noble metal in the catalyst as much as possible and improve the activity and stability of the catalyst at the same time, the preparation process of the carrier is of great importance. Most commercially available activated alumina has too many surface hydroxyl groups and too strong acidity. When the aluminum oxide is used as a carrier to prepare the dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon in the reaction process, and the rapid inactivation is caused.
Compared with the prior art, the isobutane dehydrogenation catalyst prepared by the method provided by the invention has the following advantages:
(1) the method for preparing the isobutane dehydrogenation catalyst provided by the invention has the advantages of simple preparation process, easily controlled conditions and good product repeatability;
(2) the isobutane dehydrogenation catalyst prepared by the method provided by the invention can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of low loading of main active components (namely noble metals), and can effectively reduce the preparation cost of the isobutane dehydrogenation catalyst;
(3) in the isobutane dehydrogenation catalyst prepared by the method provided by the invention, the stability of a Zn center with an oxidized structure under a high-temperature reduction condition is very high, the inactivation of a single Pt component loaded on a carrier can be inhibited, carbon deposition is reduced, a strong acid center on the surface of the carrier is effectively neutralized, the surface of the carrier is free from acidity, and the dispersion degree of the Pt component is improved through a geometric effect, so that the carbon deposition risk in the reaction process of preparing isobutene by anaerobic dehydrogenation of isobutane can be remarkably reduced, the selectivity of a target product is improved, and the stability of the isobutane dehydrogenation catalyst is improved;
(4) the mesoporous molecular sieve material with the spherical shape, the larger specific surface area and the larger pore volume is synthesized by utilizing the silicon source with low cost, which is beneficial to the good dispersion of the noble metal component on the surface of the carrier, thereby ensuring that the isobutane catalyst is not easy to be inactivated due to the agglomeration of active metal particles in the reaction process;
(5) the isobutane dehydrogenation catalyst prepared by the method provided by the invention shows good catalytic performance when used for preparing isobutene by anaerobic dehydrogenation of isobutane, and has the advantages of high isobutane conversion rate, high isobutene selectivity, good catalyst stability and low carbon deposition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction (XRD) spectrum of a mesoporous carbon material of example 1;
FIG. 2 is a nitrogen adsorption and desorption isotherm of the mesoporous carbon material of example 1;
FIG. 3 is a graph showing the pore size distribution of the mesoporous carbon material of example 1;
FIG. 4 is an SEM scanning electron micrograph of the microstructure of the mesoporous carbon material of example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As indicated previously, a first aspect of the present invention provides a process for the preparation of an isobutane dehydrogenation catalyst, the process comprising the steps of:
(a) under the condition of heating, carrying out first contact on phenol, formaldehyde and NaOH, and cooling a product obtained after the first contact to room temperature to obtain a first contact product;
(b) under the condition of heating, carrying out second contact on the first contact product and a template agent, cooling the product obtained after the second contact to room temperature to obtain a second contact product, and then sequentially carrying out centrifugal separation and drying on the second contact product to obtain mesoporous carbon material raw powder;
(c) treating the mesoporous carbon material raw powder with a stripping agent;
(d) and (c) carrying out thermal activation treatment on the mesocarbon material carrier obtained in the step (c), then carrying out immersion treatment in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
In the forming process of the carrier, the mesoporous carbon material with larger specific surface area and pore volume can be synthesized by using commonly available raw materials and adopting simple operation conditions by mainly controlling the dosage of each reaction raw material, the charging sequence and the reaction temperature.
According to the present invention, in order to obtain a mesoporous carbon material having a specific cubic-core cubic and hexagonal intergrowth pore structure, the template is preferably a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene P123, which is commercially available (e.g., from Aldrich, under the trade name P123, with the molecular formula EO 123)20PO70EO20And an average molecular weight Mn of 5800) can be obtained by various conventional methods. When the template is polyoxyethylene-polyoxypropylene-polyoxyethylene, the number of moles of the template is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
According to the present invention, in the step (a), the order of the first contact is not particularly limited, and phenol, formaldehyde and NaOH may be simultaneously mixed, or any two of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the phenol, formaldehyde and NaOH are mixed simultaneously. The conditions of the first contact include: the temperature is 50-100 ℃ and the time is 1-3h, and in order to better facilitate the uniform mixing of the materials, the first contact is preferably carried out under stirring.
According to the invention, in step (b), the second contacting comprises a first heating phase and a second heating phase, preferably the second heating phase has a higher temperature than the first heating phase, in particular,
the conditions of the first heating stage may include: the temperature is 50-65 ℃, the time is 100-150h,
the conditions of the second heating stage may include: the temperature is 66-100 ℃, and the time is 24-100 h.
According to the present invention, the drying conditions may be performed in a drying oven during the formation of the carrier, and the drying conditions may include: the temperature is 25-100 ℃ and the time is 3-5 h.
According to the invention, the method for removing the template agent is generally a calcination method. The conditions for removing the template agent may be selected conventionally in the art, and for example, the conditions for removing the template agent include: raising the temperature from 10-50 deg.C (such as room temperature) to 300-600 deg.C (preferably 350-550 deg.C), most preferably 500 deg.C) at 0.5-5 deg.C per minute, and then maintaining the temperature for 3-20 hours.
According to the present invention, the amounts of the phenol, the formaldehyde, the NaOH and the template can be selected according to the expected skeleton structure of the mesoporous carbon material, and preferably, the molar ratio of the amounts of the phenol, the formaldehyde, the NaOH and the template is 1: 2-10: 200-500: 0.1-5.
According to a specific embodiment of the present invention, the method for forming the carrier may include the steps of: phenol, 20-50 wt% formaldehyde solution and 0.05-0.2mol/L NaOH aqueous solution are mixed according to the following ratio: formaldehyde: the mass ratio of NaOH is 1: 0.5-2: 0.05-0.2, stirring at 50-100 deg.C for 1-3 hours, cooling to 10-45 deg.C (e.g. room temperature), adding a mixed solution of an ethylene oxide-propylene oxide-ethylene oxide triblock copolymer template (e.g. P123, Mn 5800) (under the accession No. 9003-11-6 of the American chemical Abstract) and deionized water at a mass ratio of 1: 5-20, heating to 50-65 ℃, heating and stirring for 100-150 hours, heating to 66-100 ℃, stirring for 24-100 hours, cooling to 10-50 ℃ (such as room temperature), centrifuging to obtain a solid sample, and drying the solid sample in an oven at 25-100 ℃ to obtain the original powder mesoporous material polymer; then, the original powder mesoporous material polymer is heated to 300-600 ℃ from 10-50 ℃ (such as room temperature) in a muffle furnace at the temperature of 0.5-5 ℃ per minute, and then is kept for 3-20 hours, and the template agent is removed to obtain the mesoporous material polymer FDU-14.
According to the present invention, in step (d), in order to remove hydroxyl groups and residual moisture of the mesoporous carbon material, a thermal activation treatment is first required before the mesoporous carbon material supports the metal component, and the conditions of the thermal activation treatment may include: in the presence of nitrogen, the carrier is calcined at the temperature of 300-900 ℃ for 7-10 h.
According to the invention, the metal component loaded on the mesoporous carbon material can be impregnated in a manner that the metal component enters the pore channel of the mesoporous carbon material by virtue of capillary pressure of the pore channel structure of the mesoporous carbon material, and meanwhile, the metal component can be adsorbed on the surface of the mesoporous carbon material until the metal component reaches adsorption balance on the surface of the mesoporous carbon material. The dipping treatment may be a co-dipping treatment or a stepwise dipping treatment. In order to save the preparation cost and simplify the experimental process, the dipping treatment is preferably co-dipping treatment; further preferably, the conditions of the co-impregnation treatment include: the spherical aluminum-containing mesoporous molecular sieve silica gel composite material after thermal activation is mixed and contacted with a solution containing a Pt component precursor and a Zn component precursor, the dipping temperature can be 25-50 ℃, and the dipping time can be 2-6 h.
According to the present invention, the solutions of the Pt component precursor and the Zn component precursor are not particularly limited as long as they are water-soluble, and may be conventionally selected in the art. For example, the Pt component precursor can be H2PtCl6The Zn component precursor may be Zn (NO)3)2。
The concentration of the solution containing the Pt component precursor and the Zn component precursor is not particularly limited in the present invention, and may be conventionally selected in the art, for example, the concentration of the Pt component precursor may be 0.1 to 0.3mol/L, and the concentration of the Zn component precursor may be 0.15 to 1 mol/L.
According to the present invention, the solvent removal treatment can be carried out by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
According to the present invention, in the step (d), the drying may be performed in a drying oven, and the firing may be performed in a muffle furnace. The conditions for the drying and firing are also not particularly limited in the present invention, and may be conventionally selected in the art, for example, the conditions for the drying may include: the temperature is 110-150 ℃ and the time is 3-6 h; the conditions for the firing may include: the temperature is 600 ℃ and 650 ℃, and the time is 5-8 h.
Preferably, in the step (d), the mesocarbon material support, the Pt component precursor and the Zn component precursor are used in amounts such that the prepared isobutane dehydrogenation catalyst contains 98-99.4 wt% of the support, 0.1-0.5 wt% of the Pt component calculated as Pt element, and 0.5-1.5 wt% of the Zn component calculated as Zn element, based on the total weight of the isobutane dehydrogenation catalyst.
In a second aspect, the present invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
According to the invention, the isobutane dehydrogenation catalyst comprises a carrier, and a Pt component and a Zn component which are loaded on the carrier, wherein the carrier is a mesoporous carbon material, the mesoporous carbon material has a cubic and hexagonal intergrowth pore channel structure with a cubic core structure, and the specific surface area of the mesoporous carbon material is 300-450 m-2Pore volume of 0.1-0.5mL/g, and most probable pore diameter of 2-5 nm.
According to the invention, the carrier has a special cubic and hexagonal symbiotic pore channel structure with a cubic core structure, the unique skeleton structure breaks through the limitation of one-dimensional pore channels on molecular transmission, and the mesoporous pore channel structure of the mesoporous carbon material has the advantages of uniform distribution, proper pore size, large pore volume, good mechanical strength and good structural stability, and is beneficial to the good dispersion of metal components in the pore channels. The supported catalyst obtained by using the carrier to support the Pt component and the Zn component has the advantages of the supported catalyst such as high catalytic activity, less side reaction, simple post-treatment and the like, and also has stronger catalytic activity and higher stability, so that the supported catalyst has better dehydrogenation activity and selectivity when being used for isobutane dehydrogenation reaction, and the conversion rate of reaction raw materials is obviously improved.
According to the invention, the specific surface area, pore volume and most probable pore diameter of the support are determined according to the nitrogen adsorption method.
More preferably, the mesoporous carbon material is an ordered mesoporous resin material FDU-14. The FDU-14 has a skeleton composed of phenolic resin and a large number of aromatic rings in the skeleton structure, so that the FDU-14 has strong hydrophobicity and excellent hydrothermal stability. And the FDU-14 has a cubic and hexagonal intergrowth pore channel structure and has larger pore channel size.
According to the invention, the support may have a mode pore size of 2-5nm, preferably 2-4nm, more preferably 3 nm. According to the invention, the specific surface area of the support may be 300-450m2Per g, preferably 350-400m2G, most preferably 375m2(ii) in terms of/g. According to the invention, the pore volume of the support may be between 0.1 and 0.5mL/g, preferably between 0.1 and 0.3mL/g, more preferably 0.2 mL/g. In the present invention, the mode pore diameter, specific surface area and pore volume are measured by a nitrogen adsorption-desorption experiment.
According to the invention, the structural parameters of the mesoporous carbon material are controlled within the range, the mesoporous carbon material is ensured not to be easily agglomerated, and the conversion rate of reaction raw materials in the reaction process of preparing propylene by isobutane dehydrogenation can be improved by using the supported catalyst prepared by the mesoporous carbon material as a carrier. When the specific surface area of the mesoporous carbon material is less than 300m2When the volume/g and/or pore volume is less than 0.1mL/g, the catalytic activity of the supported catalyst prepared by using the supported catalyst is remarkably reduced; when the specific surface area of the mesoporous carbon material is more than 450m2When the volume/g and/or the pore volume is more than 0.5mL/g, the supported catalyst prepared by using the supported catalyst as the carrier is easy to agglomerate in the reaction process of preparing propylene by isobutane dehydrogenation, so that the conversion rate of the reaction raw material in the reaction process of preparing propylene by isobutane dehydrogenation is influenced.
According to the invention, the isobutane dehydrogenation catalyst comprises a carrier, and a Pt component and a Zn component which are loaded on the carrier, wherein the Pt component is an active metal component, and the Zn component is a metal auxiliary agent.
According to the invention, based on the total weight of the isobutane dehydrogenation catalyst, the content of the carrier is 98-99.4 wt%, the content of the Pt component calculated by Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by Zn element is 0.5-1.5 wt%.
According to the present invention, it is preferable that the content of the support is 98.5 to 99.3 wt%, the content of the Pt component is 0.2 to 0.5 wt% in terms of Pt element, and the content of the Zn component is 0.6 to 1.2 wt% in terms of Zn element, based on the total weight of the isobutane dehydrogenation catalyst.
Preferably, the specific surface area of the isobutane dehydrogenation catalyst is 340-375m2Pore volume of 0.07-0.25mL/g, and most probable pore diameter of 2-4 nm.
The third aspect of the invention provides an application of the isobutane dehydrogenation catalyst prepared by the method in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the following steps: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
When the isobutane dehydrogenation catalyst prepared by the method provided by the invention is used for catalyzing isobutane to dehydrogenate to prepare isobutene, the conversion rate of isobutane and the selectivity of isobutene can be greatly improved.
According to the present invention, in order to increase the isobutane conversion rate and prevent the catalyst from coking, it is preferable that the molar ratio of the amount of isobutane to the amount of hydrogen is (0.5-1.5): 1.
the conditions for the dehydrogenation reaction in the present invention are not particularly limited and may be conventionally selected in the art, and for example, the conditions for the dehydrogenation reaction may include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, polyoxyethylene-polyoxypropylene-polyoxyethylene P123, abbreviated as P123, is available from Aldrich and has the formula EO20PO70EO20The average molecular weight Mn was 5800.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on an ASAP2020-M + C adsorption apparatus manufactured by Micromeritics, USA; the specific surface area and the pore volume of the sample are calculated by adopting a BET method; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. Axios-Advanced; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A; the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A; the muffle furnace is manufactured by CARBOLITE corporation, and is of a model CWF 1100; the ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V.
The nitrogen adsorption and desorption experiments of the samples were carried out on a full-automatic physicochemical adsorption analyzer model ASAP 2020M + C manufactured by Micromeritics, USA. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to assay. The BET method is adopted to calculate the specific surface area of the sample, and the BJH model is adopted to calculate the pore volume and the average pore diameter.
The NH3-TPD experiment of the sample was carried out on an AUTOCHEM2920 full-automatic chemisorption instrument, manufactured by Micromeritics, USA. The sample was first reduced at 480 ℃ in an atmosphere of 10% H2-90% Ar for 1 hour. Then heating to 700 ℃ in He atmosphere, staying for 1 hour, cooling to 40 ℃ and adsorbing ammonia gas until saturation. After purging for 1h in He gas atmosphere, the temperature was raised from 40 ℃ to 700 ℃ at a rate of 10 ℃/min, while the ammonia desorption data was recorded using a TCD detector.
The content of each metal component in the prepared dehydrogenation catalyst is determined by calculating the raw material feeding during preparation.
The isobutane conversion was calculated as follows:
isobutane conversion rate ═ amount of isobutane consumed by reaction/initial amount of isobutane × 100%;
the isobutene selectivity was calculated as follows:
isobutene selectivity is the amount of isobutane consumed for the production of isobutene/total consumption of isobutane × 100%;
the isobutene yield was calculated as follows:
the isobutene yield is isobutane conversion × isobutene selectivity × 100%.
Example 1
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Sequentially adding 2.8 g of phenol, 7.1 g of 38 wt% formaldehyde solution and 69 g of 0.1mol/L NaOH aqueous solution into a 250mL single-neck flask, heating and stirring at 72 ℃ for 1.5 hours, cooling to 25 ℃, adding a mixed solution consisting of 6.72 g of P123 and 70 g of deionized water, heating the obtained mixture to 64 ℃, heating and stirring at 64 ℃ for 120 hours, heating to 72 ℃, stirring for 48 hours, cooling to 25 ℃, centrifugally separating the obtained reaction product to obtain a solid product, and drying the obtained solid product in an oven at 80 ℃ for 4 hours; and (3) raising the temperature of the dried solid product from 25 ℃ to 350 ℃ at the rate of 1 ℃ per minute, and preserving the heat for 6 hours to obtain the mesoporous carbon material C1 with the cubic and hexagonal intergrowth pore channel structure with the cubic core structure.
(2) Preparation of isobutane dehydrogenation catalyst
30g of the mesoporous material C1 obtained in the step (1) is calcined at 400 ℃ for 10h under the protection of nitrogen gas for heat activation treatment, and the hydroxyl group and residual moisture of the mesoporous material C1 are removed.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml deionized water to obtain a mixture solutionAnd (2) soaking 10g of the mesoporous carbon material C1 prepared in the step (1) in the mixture solution at 25 ℃ for 5h, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, and drying the solid product in a drying oven at 120 ℃ for 3 h. And then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-1 (based on the total weight of the isobutane dehydrogenation catalyst Cat-1, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
The mesoporous carbon material C1 and the isobutane dehydrogenation catalyst Cat-1 are characterized by an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
FIG. 1 is an X-ray diffraction (XRD) spectrum of the mesoporous carbon material C1, wherein the abscissa is 2 theta, the ordinate is intensity, and the small-angle spectrum peak appearing in the XRD spectrum shows that the mesoporous carbon material C1 has a special cubic and hexagonal intergrowth pore channel structure;
FIG. 2 is a nitrogen desorption isotherm of the mesoporous carbon material C1, wherein the abscissa is relative pressure (p/p)0) The curve shape in fig. 2 is a typical type IV isotherm, demonstrating that the mesoporous carbon material C1 has characteristics of a typical mesoporous material;
FIG. 3 is a graph showing the pore size distribution of the mesoporous carbon material C1, wherein the mesoporous carbon material C1 has a uniform distribution of pore size curves and symmetrical peak shapes;
FIG. 4 is an SEM scanning electron microscope image of the microscopic morphology of the mesoporous carbon material C1, and it can be seen that the microscopic morphology of the mesoporous carbon material C1 is spherical particles of 1-3 μm, and the monodispersity is good.
Table 1 shows the pore structure parameters of the mesoporous carbon material C1 and the isobutane dehydrogenation catalyst Cat-1.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (mL/g) | Pore diameter of the most probable (nm) |
| Mesoporous carbon material C1 | 375 | 0.2 | 3 |
| Catalyst Cat-1 | 370 | 0.14 | 2.7 |
As can be seen from the data of table 1, the mesoporous carbon material C1 as a support has a reduced specific surface area and pore volume after supporting the primary active Pt component and the auxiliary Zn component, which indicates that the primary active Pt component and the auxiliary Zn component enter the inside of the mesoporous carbon material C1 during the supporting reaction.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that the same weight of alumina carrier was used instead of the mesocarbon material C1 in the preparation of the carrier, thereby preparing a carrier D1 and an isobutane dehydrogenation catalyst Cat-D-1, respectively.
Comparative example 2
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that commercially available ES955 silica gel (GRACE company) was used as the support D2 instead of the mesocarbon material C1 in the preparation of the support, thereby preparing a support D2 and an isobutane dehydrogenation catalyst Cat-D-2, respectively.
Comparative example 3
A carrier and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that Zn (NO) was not added during the impregnation process for preparing the isobutane dehydrogenation type catalyst3)2·6H2O, addition of only 0.080g H2PtCl6·6H2And O, only loading a single Pt component on a mesoporous carbon material serving as a carrier by a co-impregnation method to prepare the isobutane dehydrogenation catalyst Cat-D-3, wherein the content of the Pt component is 0.3 wt% calculated by Pt element and the balance is the carrier based on the total weight of the isobutane dehydrogenation catalyst Cat-D-3).
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Sequentially adding 2.8 g of phenol, 23.7 g of 38 wt% formaldehyde solution and 120 g of 0.1mol/L NaOH aqueous solution into a 250mL single-neck flask, heating and stirring at 75 ℃ for 2.5 hours, cooling to 25 ℃, adding a mixed solution consisting of 9.97 g of P123 and 70 g of deionized water, heating the obtained mixture to 60 ℃, heating and stirring at 60 ℃ for 150 hours, heating to 80 ℃, stirring for 36 hours, cooling to 25 ℃, centrifugally separating the obtained reaction product to obtain a solid product, and drying the obtained solid product in an oven at 90 ℃ for 3.5 hours; and (3) raising the temperature of the dried solid product from 25 ℃ to 500 ℃ at the rate of 1 ℃ per minute, and preserving the heat for 4 hours to obtain the mesoporous carbon material C2 with the cubic and hexagonal intergrowth pore channel structure with the cubic core structure.
(2) Preparation of isobutane dehydrogenation catalyst
30g of the mesoporous material C2 obtained in the step (1) is calcined at 400 ℃ for 10h under the protection of nitrogen gas for heat activation treatment, and the hydroxyl group and residual moisture of the mesoporous material C2 are removed.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml deionized water to obtain a mixture solution, and soaking 10g of the mesoporous carbon material C2 prepared in the step (1)Soaking the mixture solution at 25 ℃ for 5 hours, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying box at 120 ℃, drying for 3 hours, then placing the dried product in a muffle furnace at 600 ℃, and roasting for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-2 (based on the total weight of the isobutane dehydrogenation catalyst Cat-2, the content of the Pt component is 0.3 weight percent based on the Pt element, the content of the Zn component is 1 weight percent based on the Zn element, and the balance is a carrier).
Table 2 shows the pore structure parameters of the mesoporous carbon material C2 and the isobutane dehydrogenation catalyst Cat-2.
TABLE 2
| Sample (I) | Specific surface area (m)2/g) | Pore volume (mL/g) | Pore diameter of the most probable (nm) |
| Mesoporous carbon material C2 | 400 | 0.3 | 4 |
| Catalyst Cat-2 | 375 | 0.18 | 3.6 |
As can be seen from the data of table 2, the mesoporous carbon material C2 as the carrier has a reduced specific surface area and pore volume after supporting the primary active Pt component and the auxiliary Zn component, which indicates that the primary active Pt component and the auxiliary Zn component enter the inside of the mesoporous carbon material C2 during the supporting reaction.
Example 3
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Sequentially adding 2.8 g of phenol, 11.6 g of 38 wt% formaldehyde solution and 90 g of 0.1mol/L NaOH aqueous solution into a 250mL single-neck flask, heating and stirring at 70 ℃ for 3 hours, cooling to 25 ℃, adding a mixed solution consisting of 13.3 g of P123 and 70 g of deionized water, heating the obtained mixture to 65 ℃, heating and stirring at 65 ℃ for 110 hours, heating to 75 ℃, stirring for 40 hours, cooling to 25 ℃, centrifugally separating the obtained reaction product to obtain a solid product, and drying the obtained solid product in an oven at 100 ℃ for 3 hours; and (3) raising the temperature of the dried solid product from 25 ℃ to 450 ℃ at the rate of 1 ℃ per minute, and preserving the heat for 5 hours to obtain the mesoporous carbon material C3 with the cubic and hexagonal intergrowth pore channel structure with the cubic core structure.
(2) Preparation of isobutane removal catalyst
30g of the mesoporous material C3 obtained in the step (1) is calcined at 400 ℃ for 10h under the protection of nitrogen gas for heat activation treatment, and the hydroxyl group and residual moisture of the mesoporous material C3 are removed.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the mesoporous carbon material C3 prepared in the step (1) in the mixture solution for 5h at 25 ℃, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying oven at 120 ℃, drying for 3h, then placing in a muffle furnace at 600 ℃, and roasting for 6h to obtain the isobutane dehydrogenation catalyst Cat-3 (based on the total weight of the isobutane dehydrogenation catalyst Cat-3, the content of Pt in terms of Pt is 0.3 wt%, the content of Zn in terms of Zn is 1 wt%, and the balance is a carrier).
Table 3 shows the pore structure parameters of the mesoporous carbon material C3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 3
| Sample (I) | Specific surface area (m)2/g) | Pore volume (mL/g) | Pore diameter of the most probable (nm) |
| Mesoporous carbon material C3 | 350 | 0.1 | 2 |
| Catalyst Cat-3 | 340 | 0.07 | 1.7 |
As can be seen from the data of table 3, the mesoporous carbon material C3 as a support has a reduced specific surface area and pore volume after supporting the primary active Pt component and the auxiliary Zn component, which indicates that the primary active Pt component and the auxiliary Zn component enter the inside of the mesoporous carbon material C3 during the supporting reaction.
Experimental example 1
This example is intended to illustrate the preparation of isobutene using the isobutane dehydrogenation catalyst of the present invention
0.5g of isobutane dehydrogenation catalyst Cat-1 was placed in a fixed bed quartz reactor, and the reaction temperature was controlled to590 ℃, reaction pressure 0.1MPa, isobutane: the molar ratio of hydrogen is 1: 1, the reaction time is 24 hours, and the mass space velocity of the isobutane is 4 hours-1. By Al2O3The reaction product separated by the S molecular sieve column was directly fed into an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis, and the isobutane conversion and isobutene selectivity were obtained as shown in Table 4. After the reaction, the amount of carbon deposition in the isobutane dehydrogenation catalyst Cat-1 was measured using a TGA/DSC1 thermogravimetric analyzer from METTLER-TOLEDO, as shown in table 4.
Experimental examples 2 to 3
Isobutene was prepared by dehydrogenation of isobutane according to the method of experimental example 1, except that isobutane dehydrogenation catalyst Cat-2 and isobutane dehydrogenation catalyst Cat-3 were used instead of isobutane dehydrogenation catalyst Cat-1, respectively. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 4.
Experimental comparative examples 1 to 3
Isobutene was prepared by dehydrogenation of isobutane according to the method of experimental example 1, except that isobutane dehydrogenation catalysts Cat-D-1 to Cat-D-3 were respectively used instead of isobutane dehydrogenation catalyst Cat-1. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 4.
TABLE 4
| Dehydrogenation catalyst | Isobutane conversion rate | Selectivity to isobutene | Amount of carbon deposition | |
| Experimental example 1 | Cat-1 | 22％ | 92％ | 1.1wt％ |
| Experimental example 2 | Cat-2 | 21％ | 91％ | 1.3wt％ |
| Experimental example 3 | Cat-3 | 20％ | 90％ | 1.2wt％ |
| Experimental comparative example 1 | Cat-D-1 | 12.5％ | 71.3％ | 5.3wt％ |
| Experimental comparative example 2 | Cat-D-2 | 17.2％ | 20.5％ | 6.2wt％ |
| Experimental comparative example 3 | Cat-D-3 | 24.5％ | 55.6％ | 3.1wt％ |
It can be seen from table 4 that when the isobutane dehydrogenation catalyst prepared by the method of the present invention is used in the reaction of preparing isobutene by isobutane dehydrogenation, a higher isobutane conversion rate and isobutene selectivity can still be obtained after 24 hours of reaction, which indicates that the isobutane dehydrogenation catalyst of the present invention not only has a better dehydrogenation activity and a high selectivity, but also has an excellent stability and a low carbon deposition amount. In addition, the method for preparing the isobutane dehydrogenation catalyst provided by the invention has the advantages of simple preparation process and lower cost.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method for preparing an isobutane dehydrogenation catalyst, characterized in that the method comprises the following steps:
(a) under the condition of heating, carrying out first contact on phenol, formaldehyde and NaOH, and cooling a product obtained after the first contact to room temperature to obtain a first contact product;
(b) under the condition of heating, carrying out second contact on the first contact product and a template agent, cooling the product obtained after the second contact to room temperature to obtain a second contact product, and then sequentially carrying out centrifugal separation and drying on the second contact product to obtain mesoporous carbon material raw powder;
(c) treating the mesoporous carbon material raw powder with a stripping agent;
(d) and (c) carrying out thermal activation treatment on the mesocarbon material carrier obtained in the step (c), then carrying out immersion treatment in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
2. The method of claim 1, wherein in step (a), the conditions of the first contacting comprise: the temperature is 50-100 ℃, and the time is 1-3 h;
preferably, the molar ratio of the used amounts of the phenol, the formaldehyde, the NaOH and the template is 1: (2-10): (200-500): (0.1-5).
3. The method of claim 1, wherein, in step (b), the second contacting comprises a first heating stage and a second heating stage,
the conditions of the first heating stage include: the temperature is 50-65 ℃, the time is 100-150h,
the conditions of the second heating stage include: the temperature is 66-100 ℃, and the time is 24-100 h.
4. The process of claim 1, wherein, in step (c), the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene;
preferably, the process of stripper plate agent treatment comprises: calcining at 600 ℃ for 3-20 h.
5. The method according to claim 1, wherein in the step (d), the mesocarbon material support, the Pt component precursor and the Zn component precursor are used in such amounts that the support is contained in an amount of 98-99.4 wt%, the Pt component is contained in an amount of 0.1-0.5 wt% in terms of Pt element, and the Zn component is contained in an amount of 0.5-1.5 wt% in terms of Zn element, based on the total weight of the isobutane dehydrogenation catalyst, in the prepared isobutane dehydrogenation catalyst;
preferably, the conditions of thermal activation include: the temperature is 300-900 ℃ and the time is 7-10 h; the conditions of the impregnation treatment include: the temperature is 25-50 ℃ and the time is 2-6 h.
6. An isobutane dehydrogenation catalyst produced by the process of any one of claims 1-5.
7. The isobutane dehydrogenation catalyst according to claim 6, wherein the isobutane dehydrogenation catalyst comprises a carrier, and a Pt component and a Zn component supported on the carrier, wherein the carrier is a mesoporous carbon material, the mesoporous carbon material has a cubic and hexagonal intergrowth pore channel structure with a cubic core structure, and the specific surface area of the mesoporous carbon material is 300-450 m-2Pore volume of 0.1-0.5mL/g, and most probable pore diameter of 2-5 nm.
8. An isobutane dehydrogenation catalyst according to claim 7, wherein the specific surface area of said support is 350-400m2The pore volume is 0.1-0.3mL/g, and the most probable pore diameter is 2-4 nm;
more preferably, the mesoporous carbon material is FDU-14.
9. An isobutane dehydrogenation catalyst according to claim 7, wherein the carrier is present in an amount of 98-99.4 wt%, the Pt component is present in an amount of 0.1-0.5 wt% calculated as Pt element, and the Zn component is present in an amount of 0.5-1.5 wt% calculated as Zn element, based on the total weight of the isobutane dehydrogenation catalyst.
10. Use of the isobutane dehydrogenation catalyst according to any one of claims 6 to 9 in the production of isobutene by the dehydrogenation of isobutane, wherein the method for producing isobutene by the dehydrogenation of isobutane comprises: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
11. Use according to claim 10, wherein the molar ratio of the amount of isobutane to the amount of hydrogen is (0.5-1.5): 1;
preferably, the dehydrogenation reaction conditions include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
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