CN114433222B - Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation and application thereof - Google Patents
Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation and application thereof Download PDFInfo
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- CN114433222B CN114433222B CN202011126565.6A CN202011126565A CN114433222B CN 114433222 B CN114433222 B CN 114433222B CN 202011126565 A CN202011126565 A CN 202011126565A CN 114433222 B CN114433222 B CN 114433222B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 239000002808 molecular sieve Substances 0.000 claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 150000002894 organic compounds Chemical class 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, butylene, methane Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000006069 physical mixture Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 73
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 64
- 238000003756 stirring Methods 0.000 description 62
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 55
- 229910052710 silicon Inorganic materials 0.000 description 55
- 239000010703 silicon Substances 0.000 description 55
- 229910052757 nitrogen Inorganic materials 0.000 description 37
- 239000007787 solid Substances 0.000 description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- 229910052782 aluminium Inorganic materials 0.000 description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 28
- 238000002156 mixing Methods 0.000 description 26
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 26
- 238000001035 drying Methods 0.000 description 25
- 238000005406 washing Methods 0.000 description 25
- 239000002245 particle Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 20
- 230000008021 deposition Effects 0.000 description 19
- 150000002431 hydrogen Chemical class 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- 239000010453 quartz Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940062097 nitrogen 90 % Drugs 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J37/0215—Coating
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, and preparation and application thereof. The catalyst comprises a carbon-coated component (1), and comprises the following components in parts by weight: (1) 90-99 parts of a composition comprising a metal oxide and an ERI type molecular sieve; (2) 1-10 parts of carbon. The preparation method of the catalyst comprises the following steps: preparation of component (1) and carbon coating of component (1). The catalyst is used for preparing low-carbon olefin by carbon dioxide hydrogenation and has CO 2 The single pass conversion is obviously improved, and the selectivity of ethylene and propylene is good.
Description
Technical Field
The invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a catalyst for directly preparing low-carbon olefin (particularly ethylene and propylene) from mixed gas of carbon dioxide and hydrogen and application thereof.
Background
With the rapid growth of global economy, the massive use of fossil fuels, global warming, has been an important environmental issue that humans currently have to face. The traditional carbon capture and sealing only seals carbon dioxide, and can not be reused; and the investment is large and the income is very little. Therefore, development of a carbon dioxide recycling technology is critical.
The low-carbon olefin (ethylene, propylene) is a very important chemical raw material. The olefin can undergo addition reactions such as hydrogenation, halogenation, polymerization and the like to obtain other important raw materials, and downstream products such as plastic products, rubber, fibers and the like in the life of people are ubiquitous in the life of people. The conventional process produces ethylene primarily through steam cracking techniques, while propylene is primarily derived from by-products of the process. Steam cracking is a large energy consumption device in petrochemical industry, the reaction temperature is higher than 800 ℃, water is consumed in a high degree, and the process requires 3 tons of naphtha for producing 1 ton of ethylene, is converted into about 10 tons of crude oil, and completely depends on and consumes a large amount of non-renewable petroleum resources. And carbon dioxide is used as a carbon source, and a hydrogen source generated by clean renewable energy is combined to prepare olefin, so that the aim of carbon dioxide emission reduction is fulfilled, dependence on fossil energy by olefin can be eliminated, and certain economic benefit is generated.
Currently, carbon dioxide hydrogenation catalysts are mostly used for synthesizing methanol, wherein CN103272607B, CN105498756A CN101444731A and the like disclose a series of catalysts and methods for synthesizing methanol by carbon dioxide. Compared with the indirect method of preparing methanol by hydrogenation of carbon dioxide and preparing chemicals by methanol, the one-step method for preparing low-carbon hydrocarbon by carbon dioxide only comprises a carbon dioxide conversion and product separation system, and a methanol separation device, a methanol conversion reaction device and the like in the process can be omitted. The simplification of the whole production device flow can greatly reduce the disposable investment and energy consumption of the device, save the cost and improve the environmental and economic benefits.
CN106423263a discloses a preparation method of a catalyst for preparing low-carbon hydrocarbon by hydrogenation of iron-based carbon dioxide loaded by silicon-aluminum oxide, which adopts an impregnation method to load active components such as Fe, metal auxiliary K, mn and the like, and is applied to hydrogenation reaction of carbon dioxide, so that the direct preparation of low-carbon hydrocarbon by carbon dioxide is realized; however, as the method belongs to a modified Fischer-Tropsch synthesis method, the product is still limited by ASF distribution, and the selectivity of low-carbon hydrocarbon is difficult to break through 60 percent. In addition, the methods disclosed in CN104624194A, CN1127240a and the like have the problem of low selectivity for lower hydrocarbons.
Therefore, a problem to be solved in the one-step method for preparing the low-carbon olefin by hydrogenating the carbon dioxide is how to greatly improve the selectivity of the catalyst.
Disclosure of Invention
The invention aims to solve the defect of low selectivity in the method for preparing low-carbon olefin by hydrogenating carbon dioxide in the prior art, and provides a novel catalyst for preparing low-carbon olefin by hydrogenating carbon dioxide and application thereof. The catalyst is used for preparing low-carbon olefin by carbon dioxide hydrogenation and has CO 2 The single pass conversion is obviously improved, and the selectivity of ethylene and propylene is good.
The invention provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises a carbon-coated component (1), and comprises the following components in parts by weight:
(1) 90-99 parts of a composition comprising a metal oxide and an ERI type molecular sieve;
(2) 1-10 parts of carbon.
In the above technical scheme, the component (1) comprises 20-79 parts of metal oxide and 20-79 parts of ERI type molecular sieve, preferably 35-64 parts of metal oxide and 35-64 parts of ERI type molecular sieve in parts by weight.
In the technical scheme, the metal oxide is a composite oxide and comprises the following chemical general formula XY a O e Wherein X is at least one of Zn and In, and Y is at least one of Zr, cr, ce, mn, ga, al; a has a value in the range of 0 to 4.0, preferably 0.3 to 3.0, and e is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
In the technical scheme, the molecular sieve is selected from silicon-phosphorus-aluminum molecular sieves and SAPO-17. Preferably, in the molecular sieve, siO 2 /Al 2 O 3 The molar ratio is 0.01 to 0.20, preferably 0.01 to 0.10. In the catalyst, the SAPO-17 molecular sieve with preferable silicon-aluminum ratio is used for the reaction of directly preparing the low-carbon olefin (ethylene and propylene) by carbon dioxide hydrogenation, and has better activity and selectivity.
In the above technical solution, in the catalyst, the metal oxide and the ERI type molecular sieve exist in a form independent from each other, such as physical mixing, including particle mixing, powder mixing or ball milling mixing.
In the above embodiments, the catalyst preferably contains 3 to 8 parts by weight of carbon, and more preferably 3 to 6 parts by weight.
The second aspect of the invention provides a preparation method of the catalyst for preparing low-carbon olefin by hydrogenation of carbon dioxide, which comprises the following steps: preparation of component (1) and carbon coating of component (1).
In the technical scheme, the preparation process of the component (1) comprises the following steps: mixing the metal oxide with the ERI type molecular sieve to obtain the component (1).
In the technical scheme, the preparation process of the component (1) coated carbon comprises the following steps: treating component (1) with a gas mixture containing a gas phase organic compound under a non-oxygen atmosphere to obtain the catalyst. The gas phase organic compound can be at least one of methanol, ethanol, propanol, formaldehyde, acetaldehyde, propionaldehyde, formic acid, acetic acid, dimethyl ether, methyl formate, ethylene, propylene, butylene, methane, ethane, propane, butane, acetylene, propyne and butadiene. The content of the gas phase organic compound in the gas phase organic compound is more than 1%, preferably1% to 20%, more preferably 5% to 15%, and further may contain a non-oxygen inorganic gas (such as at least one of carbon monoxide, hydrogen, nitrogen, argon, helium) and the inert gas content is 99% or less, preferably 80% to 99%, more preferably 85% to 95%. The treatment conditions were as follows: the GHSV of the mixed gas is 800-5000 h -1 The temperature is 350-450 ℃, the pressure is 0.1-4.0 MPa, and the treatment time is 1-5 h.
The third aspect of the invention provides a method for directly preparing low-carbon olefin by hydrogenating carbon dioxide, comprising the following steps: the raw material containing carbon dioxide and hydrogen is contacted with the catalyst to react, and a product containing low-carbon olefin is obtained.
In the above technical scheme, the low-carbon olefin is ethylene and propylene.
In the technical scheme, a fixed bed reactor is adopted.
In the technical scheme, the hydrogenation reaction process conditions are as follows: the reaction temperature is 340-460 ℃, the reaction pressure is 0.5-7.0 MPa, and CO 2 ：H 2 (molar ratio) =1: (0.4-3.0), GHSV 1000-8000 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is preferably 380 to 420 ℃.
Compared with the prior art, the catalyst disclosed by the invention is prepared by covering carbon on a mixture comprising metal oxide and a specific ERI type molecular sieve, wherein the specific ERI molecular sieve pore structure is more suitable for generating C2-C3 hydrocarbon products, under the condition of hydrogen, alkene generated by carbon-carbon coupling can be subjected to secondary hydrogenation on oxygen holes on the surface of the oxide and strong acid sites of the molecular sieve to generate alkane, and after the catalyst is covered with carbon by adopting special treatment, the hydrogenation active site exposure on the catalyst is reduced, the generation of alkane is greatly inhibited, and therefore, the catalyst can be used in the reaction of directly preparing low-carbon alkene (ethylene and propylene) by carbon dioxide hydrogenation, the activity is obviously improved, and the selectivity is good.
Drawings
FIG. 1 is an XRD pattern of the SAPO-17 molecular sieve obtained in example 1,
FIG. 2 is an XRD pattern of the SAPO-17 molecular sieve obtained in example 7.
Detailed Description
The invention is further illustrated by the following examples.
In the invention, XRD adopts a Bruker D8 type diffractometer, a Cu-K alpha ray source is used, the working voltage is 40kV, the current is 40mA, the scanning range is 5-45 degrees, the scanning step length is 0.01 degrees, and the scanning speed is 4 degrees/min.
In the present invention, carbon dioxide conversion means the reactor outlet CO 2 Consumption of (2) and reactor inlet CO 2 In mole percent of the amount of (2), wherein the reactor outlet CO 2 Is the consumption of CO at the inlet of the reactor 2 Is related to the amount of CO at the outlet of the reactor 2 Is a difference in the amount of (c).
In the present invention, the selectivity of ethylene and propylene refers to the mole percent of carbon content of ethylene and propylene in the product relative to the carbon content of all organic hydrocarbon products.
[ example 1 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a certain amount of silicon source is added to make the silicon-aluminum ratio of the obtained product be 0.05 (SiO 2 /Al 2 O 3 Molar ratio) for two hours, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water to be neutral, separating to obtain solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hoursWhen the SAPO-17 (0.05) molecular sieve is obtained.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 2 ]
The InZrOx oxide is prepared as follows:
according to In: zr=1: 1 in a molar ratio of indium nitrate to zirconium nitrate in 200mL of water, stirring thoroughly, and stirring for 10min after all dissolution. The (NH) was then added In the stoichiometric amount (i.e., 1.0X1 molar amount+2.0XZr molar amount) of the complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing InZrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 3 ]
The ZnZrOx oxide is prepared as follows:
according to Zn: cr=1: 1 in a molar ratio of zinc nitrate to zirconium nitrate in 200mL of water, stirring thoroughly, and stirring for 10min after all dissolution. Then the (NH) is added in accordance with the stoichiometric amount of complete precipitation (i.e. 1.0XZn mol+2 XZr mol) 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. While dripping, continuously stirring, and maintaining the temperature of the solution at 70deg.CStirring was continued for 3 hours after the end of the dropwise addition, the resulting precipitate was filtered and washed with water to neutrality, dried in an oven at 80℃for 12 hours, and then calcined at 500℃for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnZrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 4 ]
The ZnAlOx oxide is prepared as follows:
according to Zn: al=1: 1 molar ratio of zinc nitrate to nitric acidAluminum was dissolved in 200mL of water and stirred well, and stirring was continued for 10min after all dissolution. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0X10. Times. Zn mol+1.5XAl mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnAlOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 Is of the volume of (2)The ratio is 1:3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 5 ]
The ZnCrAlOx oxide is prepared as follows:
according to Zn: cr: al=1: 0.9: zinc nitrate, chromium nitrate and aluminum nitrate were dissolved in 200mL of water at a molar ratio of 0.1, and stirred well, and after all dissolution, stirring was continued for 10min. The (NH) was then added in the stoichiometric amount for complete precipitation (i.e., 1.0 XZn molar amount+1.5 XCr molar amount+1.5 XAl molar amount) 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrAlOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 6 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. The solution was stirred continuously while being added dropwise, and the temperature of the solution was maintained at 70 ℃, stirring was continued for 3 hours after the completion of the addition, the obtained precipitate was filtered and washed with water to neutrality, dried in an oven at 80 ℃ for 12 hours, and then calcined at 500 ℃ for 1 hour.
SAPO-17 (0.02) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.02 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.02) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.02) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.5%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 7 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. The solution was stirred continuously while being added dropwise, and the temperature of the solution was maintained at 70 ℃, stirring was continued for 3 hours after the completion of the addition, the obtained precipitate was filtered and washed with water to neutrality, dried in an oven at 80 ℃ for 12 hours, and then calcined at 500 ℃ for 1 hour.
SAPO-17 (0.035) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and adding a certain amount of silicon source to make silicon-aluminum ratio in the productIs 0.035 (in SiO) 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.035) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.035) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.4%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 8 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. The solution was stirred continuously while being added dropwise, and the temperature of the solution was maintained at 70 ℃, stirring was continued for 3 hours after the completion of the addition, the obtained precipitate was filtered and washed with water to neutrality, dried in an oven at 80 ℃ for 12 hours, and then calcined at 500 ℃ for 1 hour.
SAPO-17 (0.1) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.1 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.1) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.1) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 4.7%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 9 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere, and was switched to an organic mixture (methanol 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 4.9%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 10 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 15%, nitrogen 85%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 4.5%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adoptsStainless steel reactor lined with quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 11 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 1, zinc nitrate and chromium nitrate were dissolved in 200mL of water, and the mixture was stirred sufficiently, and after the dissolution was continued for 10 minutes. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
treating the catalyst composition at 400 deg.c in inert atmosphere for 2 hr, and switching to organic mixed gas (methanol 5%, dimethyl ether 5%, nitrogen 90%) with gas space velocity of 3000 hr -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 5.2%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 12 ]
The ZnCrMnOx oxide is prepared as follows:
according to Zn: cr: mn=1: 0.9: zinc nitrate, chromium nitrate and manganese nitrate were dissolved in 200mL of water at a molar ratio of 0.1, and stirred well, and after all dissolution, stirring was continued for 10min. Then the solution was subjected to precipitation of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol+1 XMn mol) 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio), stirring for two hours until uniformity, crystallizing at 200 ℃ for 72 hours to obtain solidWashing with deionized water to neutrality, separating to obtain solid, oven drying, and calcining at 550deg.C in muffle furnace for 6 hr to obtain SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrMnOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 13 ]
The ZnAlGaOx oxide is prepared as follows:
according to Zn: al: ga=1: 0.9: zinc nitrate, aluminum nitrate and gallium nitrate were dissolved in 200mL of water at a molar ratio of 0.1, and stirred well, and after all dissolution, stirring was continued for 10min. The (NH) was then added in the stoichiometric amount for complete precipitation (i.e., 1.0XZn molar amount+1.5XAl molar amount+1.5XGa molar amount) 4 ) 2 CO 3 Dissolve in 150mL of water and stir thoroughly until completely dissolved. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source is added in an amount such that the silicon to aluminum ratio in the product is 0.05 (in terms of SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnAlGaOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 14 ]
The ZnCrOx oxide is prepared as follows:
according to Zn: cr=1: 2, zinc nitrate and chromium nitrate are dissolved in 200mL of water according to the molar ratio, and the mixture is fully stirred, and the stirring is continued for 10min after the complete dissolution. The solution was then purified to obtain a solution of (NH) in the stoichiometric amount (i.e., 1.0XZn mol+1.5XCr mol) for complete precipitation 4 ) 2 CO 3 Dissolving in 150mL water, and stirring thoroughlyAnd (5) partially dissolving. The two solutions were simultaneously added dropwise to 20mL of water at a rate ratio of 4:3. Continuously stirring while dripping, maintaining the temperature of the solution at 70 ℃, continuously stirring for 3 hours after dripping, filtering the obtained precipitate, washing with water to be neutral, putting into an 80 ℃ oven for drying for 12 hours, and then roasting at 500 ℃ for 1 hour.
SAPO-17 (0.05) was prepared as follows:
silicon sol, aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as a silicon source, an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a certain amount of silicon source is added to make the silicon-aluminum ratio of the obtained product be 0.05 (SiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until uniformity, crystallizing for 72 hours at 200 ℃, washing the obtained solid with deionized water until neutrality, separating the obtained solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.05) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 15 ]
Taking the calcined oxide and molecular sieve in the example 1, crushing, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:2 to prepare the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 5.1%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa,1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
[ example 16 ]
Taking the calcined oxide and molecular sieve in the example 1, crushing, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 2:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 5%, nitrogen 95%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 2.5%.
The catalyst composition evaluation was carried out on a fixed bed microreactor. The reactor adopts a stainless steel reactor lined with a quartz tube. The catalyst composition is treated in a reactor with pure nitrogen for 2 hours under normal pressure and 400 ℃ and then is switched into a mixed gas of carbon dioxide and hydrogen, CO 2 And H is 2 The volume ratio of (1): 3, at 400 ℃,3.0MPa，1200h -1 The reaction was carried out for 2 hours at a space velocity, and the reaction product was monitored on line by gas chromatography, and the reaction results are shown in Table 1.
Examples 17 to 20
Taking the calcined oxide and molecular sieve in the example 1, crushing, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.05) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then was changed to an organic mixture (ethylene 5%, nitrogen 95%) and the other treatment conditions were as shown in Table 2.
The reaction conditions were the same as in example 1, and the results are shown in Table 2.
Examples 21 to 22
The catalyst treated in example 1 was treated with pure nitrogen at 400 ℃ under normal pressure in a reactor for 2 hours, then switched to a mixed gas of carbon dioxide and hydrogen, the reaction conditions are shown in table 3, the reaction time is 2 hours, the reaction product is monitored on line by gas chromatography, and the reaction result is shown in table 3.
Comparative example 1
The catalyst composition is prepared by adopting ZnCrOx prepared in the embodiment 1 as an oxide and SAPO-34 as a molecular sieve, crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing the ZnCrOx and the SAPO-34 molecular sieve particles according to the mass ratio of 1:1.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 2%, nitrogen 98%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.7%.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 2
The catalyst composition is prepared by adopting ZnCrOx prepared in the embodiment 1 as an oxide and SAPO-17 as a molecular sieve, crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 molecular sieve particles according to the mass ratio of 1:1. The catalyst composition was directly reacted without treatment under the same conditions as in example 1, and the results are shown in Table 1.
[ comparative example 3 ]
ZnCrOx prepared in example 1 is used as the oxide.
AlPO-17 (0) was prepared as follows:
aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, stirring for two hours to uniformity, crystallizing at 200 ℃ for 72 hours, washing the obtained solid with deionized water to neutrality, separating to obtain solid, drying, and roasting in a muffle furnace at 550 ℃ for 6 hours to obtain the AlPO-17 (0) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and AlPO-17 (0) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 15%, nitrogen 85%) at a gas space velocity of 3000h -1 The reaction temperature is 430 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.8%.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
[ comparative example 4 ]
ZnCrOx prepared in example 1 is used as the oxide.
SAPO-17 (0.4) was prepared as follows:
aluminum isopropoxide, phosphoric acid and cyclohexylamine are respectively used as an aluminum source, a phosphorus source and a template agent, and the molar ratio of Al 2 O 3 ∶P 2 O 5 In the ratio of cyclohexylamine to H 2 O=1:1:1:40, and a silicon source was added in an amount such that the silicon to aluminum ratio in the resulting product was 0.4 (in orderSiO 2 /Al 2 O 3 Molar ratio) and stirring for two hours until the mixture is uniform, crystallizing the mixture for 72 hours at 200 ℃, washing the obtained solid with deionized water until the solid is neutral, separating the solid to obtain solid, drying the solid, and roasting the solid in a muffle furnace at 550 ℃ for 6 hours to obtain the SAPO-17 (0.4) molecular sieve.
Crushing the roasted oxide and molecular sieve, tabletting and forming to 20-40 meshes, and uniformly mixing ZnCrOx and SAPO-17 (0.4) molecular sieve particles according to a mass ratio of 1:1 to obtain the catalyst composition.
The catalyst treatment process is as follows:
the catalyst composition was treated at 400℃for 2 hours under an inert atmosphere and then switched to an organic mixture (ethylene 2%, nitrogen 98%) at a gas space velocity of 3000h -1 The reaction temperature is 400 ℃, the reaction pressure is 0.1MPa, the treatment is carried out for 2 hours, and the carbon deposition amount is 3.7%.
The reaction conditions were the same as in example 1, and the results are shown in Table 1.
Table 1 reaction results for each of examples and comparative examples
TABLE 2 reaction results for examples 17-20
TABLE 3 reaction results for examples 21-22
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. The catalyst for preparing the low-carbon olefin by hydrogenating the carbon dioxide comprises the following components in parts by weight:
(1) 90-99 parts of a composition comprising a metal oxide and an ERI type molecular sieve;
(2) 1-10 parts of carbon;
The metal oxide is a composite metal oxide and comprises the following chemical general formula XY a O e Wherein X is at least one of Zn and In, and Y is at least one of Zr, cr, ce, mn, ga, al; the value range of a is 0-4.0, and e is the total number of oxygen atoms required for meeting the valence of each element in the catalyst; the molecular sieve is selected from SAPO-17, siO 2 /Al 2 O 3 The molar ratio is 0.01-0.20;
the preparation method of the catalyst comprises the following steps: preparing the component (1) and coating carbon with the component (1), wherein the preparation process of the component (1) coating carbon comprises the following steps: treating component (1) with a gas mixture containing a gaseous organic compound in a non-oxygen atmosphere to obtain the catalyst; the gas phase organic compound is at least one of methanol, ethanol, propanol, formaldehyde, acetaldehyde, propionaldehyde, formic acid, acetic acid, dimethyl ether, methyl formate, ethylene, propylene, butylene, methane, ethane, propane, butane, acetylene, propyne and butadiene; in the gas phase organic compound-containing mixed gas, the content of the gas phase organic compound is more than 1 percent; the treatment conditions were as follows: the GHSV of the mixed gas is 800-5000 h -1 The temperature is 350-450 ℃, the pressure is 0.1-4.0 MPa, and the treatment time is 1-5 h.
2. The catalyst according to claim 1, wherein the component (1) comprises 20 to 79 parts of a metal oxide and 20 to 79 parts of an ERI type molecular sieve.
3. The catalyst according to claim 1, wherein the component (1) comprises 35 to 64 parts of a metal oxide and 35 to 64 parts of an ERI type molecular sieve.
4. The catalyst of claim 1 wherein a has a value in the range of 0.3 to 3.0.
5. The catalyst of claim 1, wherein SiO in the SAPO-17 molecular sieve is 2 /Al 2 O 3 The molar ratio is 0.01-0.10.
6. The catalyst of claim 1 wherein the metal oxide and ERI type molecular sieve are present in the catalyst in a physical mixture.
7. The catalyst according to claim 1, wherein the catalyst contains 3 to 8 parts by weight of carbon.
8. The catalyst according to claim 1, wherein the catalyst contains 3 to 6 parts by weight of carbon.
9. A method for preparing the catalyst for preparing light olefins by hydrogenating carbon dioxide according to any of claims 1 to 8, comprising: preparation of component (1) and carbon coating of component (1).
10. The method according to claim 9, wherein the gas phase organic compound content in the gas phase organic compound-containing mixture is 1% to 20% in the preparation of the component (1) coated carbon.
11. The method according to claim 10, wherein the gas phase organic compound content in the gas phase organic compound-containing mixture is 5% to 15% in the preparation of the component (1) coated carbon.
12. A method for directly preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises the following steps: the raw material containing carbon dioxide and hydrogen is contacted with the catalyst for preparing low-carbon olefin by hydrogenation of carbon dioxide according to any one of claims 1-8 to react, and a product containing low-carbon olefin is obtained.
13. The process of claim 12 wherein the lower olefins are ethylene and propylene; a fixed bed reactor was used.
14. The method according to claim 12, wherein the hydrogenation reaction is carried out under the following process conditions: the reaction temperature is 340-460 ℃, the reaction pressure is 0.5-7.0 MPa, and CO 2 And H is 2 The molar ratio is 1: (0.4-3.0), GHSV 1000-8000 h -1 。
15. The process according to claim 14, wherein the reaction temperature is 380 to 420 ℃.
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