CN112246275A - Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof - Google Patents
Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof Download PDFInfo
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- alkali metal
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 114
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 239000011701 zinc Substances 0.000 claims abstract description 67
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 47
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 40
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- 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 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- -1 alkali metal salt Chemical class 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract 1
- 239000001294 propane Substances 0.000 description 29
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 25
- 239000011651 chromium Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical group [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 229910001950 potassium oxide Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000013313 FeNO test Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- ZBNJXSZNWZUYCI-UHFFFAOYSA-N octadecyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP([O-])(=O)OCC[N+](C)(C)C ZBNJXSZNWZUYCI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 241000045365 Microporus <basidiomycete fungus> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLNZHTHIPQGEMX-UHFFFAOYSA-N ethane propane Chemical compound CCC.CCC.CC.CC XLNZHTHIPQGEMX-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
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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
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, which comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a second alkali metal exchanged nano micropore SSZ-13 nano zeolite molecular sieve, the pore size distribution is 0.2-0.4nm, the active component is zinc oxide, the auxiliary agent is a first alkali metal oxide, and the mass of zinc in the catalyst isThe weight percentage of the first alkali metal is 1.5-9.5%, and the weight percentage of the first alkali metal is 0.5-2%. The invention adopts the bimetal ZnM after the second alkali metal exchange1/M2S-N catalyst, the M2The S-N has the advantages of excellent hydrothermal stability, strong carbon dioxide adsorption capacity, more surface protonic acid centers, exchangeable cations and the like, and can effectively solve the problem of poor hydrothermal stability of a catalyst carrier in the prior art; the introduction of the first alkali metal enables the particle size of active zinc species on the catalyst to be reduced, the dispersion is more uniform, the selectivity of a target product is improved, the catalytic effect of co-conversion of low-carbon alkane and carbon dioxide is achieved, and the stability in catalytic reaction is improved.
Description
Technical Field
The invention belongs to the technical field of olefin preparation from low-carbon alkane, and particularly relates to a catalyst for preparing olefin from low-carbon alkane through carbon dioxide oxidation and a preparation method thereof.
Background
Carbon dioxide (0.04% of the earth's atmosphere) is an important component of the carbon cycle, which flows throughout the ecosystem in the form of energy and nutrients and is exchanged between the oceans, rocks, soil and biospheres, which are critical to sustaining life on earth. Carbon dioxide is also important in maintaining the earth's temperature through its natural greenhouse effect. However, this environmental benefit is considered to be one of the major causes of global warming. The phenomenon of global warming caused by excessive rise of carbon dioxide content in the atmosphere in the industrial age has become a serious concern for countries in the world. In addition to examining carbon dioxide emission levels, the global scientific community also envisions the use of carbon dioxide as an obvious means of reducing atmospheric carbon dioxide levels. However, carbon dioxide molecules are very stable, and a large number of researches show that hydrogen can effectively activate carbon-oxygen bonds of the carbon dioxide molecules, so that the method is a hot research direction for resource utilization of carbon dioxide. However, the high cost of the industrial hydrogen production technology causes the high cost of raw materials, which reduces the economical efficiency of the carbon dioxide catalytic hydrogenation technology and limits the industrial application thereof. The shale gas revolution has made large quantities of lower alkanes recognized as a key opportunity for potential development of specialized production processes. Shale gas is an abundant and available resource, each of whose components can be utilized directly or as precursors to value-added chemicals and fuels. According to different sources of shale gas, C in the mixture2H6、C3H8And C4H10Up to 15% v/v, wherein C2H6The highest content. In addition, the lower alkanes contain carbon-carbon bonds and can be dehydrogenated to form C2H4、C3H6And C4H8Isomers (each represents C)2＝、C3Is equal to and C4═ e), and 1, 3-butadiene. The demand for these olefins is high because they are important petrochemical feedstocks. However, the traditional ethane propane high-temperature cracking dehydrogenation for preparing ethylene is a strong endothermic process, not only has high reaction temperature (generally higher than 1120K) and needs to be carried out under the condition of negative pressure (dilution by increased amount of superheated steam), but also has great energy consumption, complex operation and very difficult product separation; the conversion rate and the yield are difficult to improve due to the limitation of thermodynamic equilibrium; the carbon deposition on the catalyst is fast, and the catalyst needs to be regenerated repeatedly; the process flow is complex, the scale of equipment and investment is large, and an environment-friendly alternative process with low energy consumption is urgently needed. The co-conversion reaction of the low-carbon alkane and the carbon dioxide helps the alkane dehydrogenation to prepare the olefin by utilizing the weak oxidizability of the carbon dioxide, so that the selectivity of the olefin product can be improved while the reaction temperature is reduced. Meanwhile, the carbon dioxide is subjected to hydrogenation reaction by utilizing abundant hydrogen atoms in alkane molecules to be converted into carbon monoxide, so that the co-conversion of the carbon dioxide and ethane is realized, and certain economic benefit and social benefit are generated.
In recent years, researchers at home and abroad research catalysts for the reaction of preparing olefin by oxidizing low-carbon alkane with carbon dioxide and dehydrogenating the low-carbon alkane.
Journal of inorganic chemistry 2004(08): p.987-9902Oxide C2H6Dehydrogenation to C2H4A catalyst. The experimental result shows that the supporting amount is 1.2mmol/100m2CeO2The catalyst reaction activity is optimal. The reaction conditions are 740 ℃ and 9600h-1，n(C2H6)/n(CO2) When 1:7, C2H6Conversion rate was 36.6%, CO2Initial conversion 23.5%, C2H4The selectivity was 97% and the yield of ethylene was 35.5%. Publications RSC Advances,2016.6(50): p.44195-44204, report that a 5% Cr-ZrO2(P) catalyst has excellent activity. The reaction conditions are 700 ℃, 9000h-1，n(C2H6)/n(CO2) When 1:5, its C2H6The conversion was 47.56％，CO2Initial conversion was 26.05%, C2H4The selectivity was 91%. Published literature, chemical journal, 2003(06): p.875-877, 10% Cr2O3MgO at 700 deg.C for 4500h-1，n(C2H6)/n(CO2) When 1:3, C2H6Conversion was 61.5%, CO2Initial conversion 20.8%, C2H4The selectivity was 97.5%.
Published Chinese Journal of catalysis,2015.36(8): p.1242-1248 CO is reported2Oxide C2H6Dehydrogenation to C2H4The catalyst of (1). The experimental results show that: 3% Cr/NaZSM-5-160 (SiO)2/Al2O3) The catalyst activity is highest. The reaction conditions are 650 ℃, 9000h-1mL/g-cat，n(C2H6)/n(CO2) When 1:5, its C2H6Conversion 65.5%, C2H4Selectivity 75.4%, CO2The conversion was 22.6%. Publication Catalysis Communications 2006.7(9): p.633-638. CO is reported2Oxide C2H6Dehydrogenation to C2H4The catalyst of (1). The experimental results show that: Cr/Ts-1 (SiO)2/TiO2150) the catalyst activity was highest. The reaction conditions are 650 ℃, 9000h-1mL/g-cat，n(C2H6)/n(CO2) When 1:4, its C2H6Conversion was 62.2%, C2H4Selectivity 81%, CO2The conversion was 17.2%. Publication Catalysis Today 2006.115(1-4): p.235-241. CO is reported2Oxide C2H6Dehydrogenation to C2H4The catalyst of (1). The experimental results show that: the Cr/MSU-1 catalyst has the highest activity. The reaction conditions are 700 ℃, 2700h-1mL/g-cat，n(C2H6)/n(CO2) When 1:3, C2H6Conversion 68.1%, C2H4Selectivity 81.7%, CO2The conversion was 55.6%. Studies in Surface Science&Catalysis,2001,136:87-92 CO is reported2Oxidation by oxygenC2H6Dehydrogenation to C2H4The catalyst of (1). The experimental results show that: the catalytic activity of the 6% Cr/AC catalyst is better. The reaction conditions are 650 ℃ and 1200h-1，n(C2H6)/n(CO2) When 1:1, C2H6Conversion rate was 28.9%, CO2Initial conversion 23.5%, C2H4The selectivity was 70.5%. At 600 ℃ for 1200h-1，n(C2H6)/n(CO2) After 4h of reaction under 1:1 conditions, C2H6Conversion rate is reduced from 15.7% to 6.6%, C2H4The yield is reduced from 11.9 percent to 5.8 percent. At this time, CO was used at 700 deg.C2After 1h of regeneration as regenerant, C2H6And C2H4The yield increased to 10.7% and 8.5%, respectively, but the original activity could not be restored.
The publications microporus and mesoporus materials 145(2011)194-199 reported that the Cr-based catalyst supported on Na-ZSM-5 with a smaller crystal size (about 400nm) had good catalytic performance, much higher activity than the catalyst supported on ZSM-5 with a larger crystal size (about 2 um). The high Cr (VI) content in the calcined catalyst is the use of CO2The key point of high catalytic activity in the process of preparing propylene by dehydrogenating propane. In addition, Cr was investigated6+The promoter is in CO2The promotion effect of the HZSM-5 catalyst on ODP reaction in the presence and absence of the catalyst. In CO2In the presence of the catalyst, the initial conversion rates of propane to Cr/HZSM-5-S and Cr/HZSM-5-L were 48.3% and 86.0%, respectively, in CO2In the absence, the initial conversion of propane and selectivity to propylene for Cr/HZSM-5-L were 11.3% and 92.8%, respectively. After 8h of operation, the values of the former catalyst were reduced to 30.1% and 91.8%, respectively, and the values of the latter catalyst were reduced to 8.4% and 94.1%, respectively. The publication Journal of industrial and engineering chemistry 18(2012) 731-736 reports Ga2O3Catalytic performance of the supported HZSM-48 catalyst for ODPC reactions. The propylene yield after varying the Si/Al ratio was similar to the above observations, but Ga having a Si/Al ratio of 1302O3of/HZSM-48The optimum propylene yield was 22.2%. In Ga2O3On HZSM-48, the selectivity for propylene is higher than that for Ga2O3on/HZSM-5, especially in the case of low propane conversions, owing to its weak acidity. But Ga2O3The stability of/HZSM-48 is lower than that of Ga2O3HZSM-5, which may be due to its abundance of weak acid sites and one-dimensional pore structure. Application of published analysis A general 374(2010) 142-149A series of catalysts (S) with ordered cubic structure and high atomic ratio of Cr/SBA-1 and Cr/Si of 0.06 were prepared by adding different amounts of chromium (1-15% wt%) to SBA-1BET>900m2In terms of/g). Their observations with Baek et al confirmed that the activity of the catalyst increased to 4.3 wt% of the optimum loading with increasing Cr content. In another study, the published Journal of catalysis 224(2004)404-416 reported CO2Effect on propane conversion on Cr/MCM-41 catalyst. The results show that Cr-MCM-41 has the highest catalytic activity in the tested M-MCM-41 catalyst, the conversion rate of the synthesized propylene is 30%, and the selectivity is over 90%. As the partial pressure of carbon dioxide increases, the rate of production of carbon monoxide increases with the rate of production of propylene, and the rate of production of hydrogen remains almost constant. In CO2In the presence of (C)3H8Conversion rate of (1) and C3H6The yield of (a) is improved by two times. In the reaction of Cr-MCM-41, in the presence of CO2The activity of the catalyst gradually decreased in the presence and absence, indicating deactivation of the catalyst.
The publications Catalysis communications 39(2013)20-23 investigated a series of Cr prepared by hydrothermal method at 180 ℃2O3-ZrO2Mixed oxides for ODPC reaction. The reaction was carried out at 550 ℃ with 2.5 vol% C3H8、5vol％CO2、N2Is carried out at equilibrium. The initial conversion rate of the catalyst propane prepared by the hydrothermal treatment is 53.3 percent, and the catalyst is conventional Cr2O3-ZrO21.6 times of the catalyst. The enhancement of the activity of the hydrothermally prepared catalyst is mainly due to the surface area of the catalyst and the Cr content6+The concentration is higher than Cr3 +Due to the factIn the reaction, Cr6+The substance is more active. Under the condition of no carbon dioxide, the conversion rate is 76.5 percent within 10min, the selectivity is 60.3 percent, and the TOF is 14.8-104s-1But the conversion and TOF values rapidly dropped to 3% and 0.6-104s-1Within 6h, a selectivity of 97.4% was achieved with 9 wt% coke deposition. However, in the presence of carbon dioxide, the conversion and TOF were from 53.3% and 10.3-104s, respectively, under the same conditions-1Respectively reduced to 27.7% and 5.4-104s-1And within 6h the selectivity increased from 79% to 90.8% with 2.7 wt% coke deposition.
According to the literature report, the supported chromium-based catalyst has excellent catalytic performance in the dehydrogenation reaction of low-carbon alkane. Therefore, the current research on supported catalysts for co-conversion of carbon dioxide and light alkanes mainly focuses on the modification of different carriers with chromium, which mainly include oxide carriers (SiO) having high specific surface area, strong reducibility and improved metal dispersion2、Al2O3、CeO2、ZrO2MgO, etc.) and microporous zeolite molecular sieves with high specific surface areas and three-dimensional topologies (ZSM-5 and MCM-41, MSU-x, SAPO-34, etc.). However, there are also a number of problems in the known literature: for example, water generated during the reaction when the reaction is carried out at a higher reaction temperature may destroy the structure of the catalyst to cause rapid deactivation; CO in the course of the reaction2The conversion rate is low; the Cr-based catalyst is toxic and easily causes environmental pollution. Therefore, the development of high hydrothermal stability and high CO2Conversion and environmentally friendly catalysts are of paramount importance.
Disclosure of Invention
The invention provides a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and a preparation method thereof, aiming at solving the technical problems of poor hydrothermal stability, weak carbon dioxide adsorption capacity and low conversion rate of the existing supported Cr catalyst carrier. The prepared catalyst has strong carbon dioxide adsorption capacity and conversion capacity, and can catalyze the co-conversion reaction of carbon dioxide and low-carbon alkane under mild reaction conditions to obtain higher carbon dioxide, alkane conversion rate and alkene selectivity.
The technical scheme of the invention is as follows:
a catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide is a bimetallic catalytic system of zinc and first alkali metal, and comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a second alkali metal exchanged nano-micropore SSZ-13 zeolite molecular sieve, the pore size distribution is 0.2-0.4nm, the active component is zinc oxide, the auxiliary agent is an oxide of the first alkali metal, the mass fraction of zinc in the catalyst is 1.5-9.5% by weight of zinc, and the mass fraction of the alkali metal in the catalyst is 0.5-2% by weight of the first alkali metal.
The first alkali metal and the second alkali metal are different alkali metals.
Preferably, the first alkali metal is lithium, sodium, potassium, rubidium or cesium; the second alkali metal is lithium, sodium or potassium. Further, the first alkali metal is potassium, namely the auxiliary agent is potassium oxide; the second alkali metal is sodium.
Preferably, the mass fraction of the first alkali metal in the catalyst is 0.5-1.5% based on the weight of the first alkali metal.
The lower alkane is C2H6Or C3H8。
A preparation method of a catalyst for preparing olefin by oxidizing low-carbon paraffin with carbon dioxide comprises the following steps:
s1, carrying out roasting dehydration pretreatment on the carrier;
s2, the carrier is subjected to multiple exchanges with the second alkali metal through impregnation with the second alkali metal solution;
s3 adding the carrier completely exchanged with the second alkali metal to the zinc salt water solution and the first alkali metal salt water
Soaking in the solution at 80 deg.C, and collecting solid;
s4, drying and roasting the solid to obtain the catalyst for preparing olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide.
The volume ratio of the zinc salt aqueous solution and the first alkali metal salt aqueous solution to the carrier is 4.
The mass fraction of the zinc salt aqueous solution is 2-10%, and the mass fraction of the first alkali metal salt aqueous solution is 0.5-2%.
The zinc salt is one of zinc nitrate and zinc acetate, and the first alkali metal salt is nitrate.
The drying temperature is 80-110 ℃, and the drying time is 8-20 h; the roasting temperature is 450-600 ℃, and the roasting time is 12-20 h.
The invention also provides a reaction for preparing olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide by using the catalyst, wherein the reaction conditions are as follows: the reaction temperature is 550-650 ℃, and the reaction space velocity is 3600h-1mL/g-cat, the molar ratio of carbon dioxide to low-carbon alkane in the reaction raw material is 1: 0.1-10.
Preferably, the molar ratio of the carbon dioxide to the light alkane in the reaction raw materials is 1: 1.
The invention has the following beneficial effects:
the catalyst is suitable for the co-conversion of low-carbon alkane and carbon dioxide: (1) the method adopts zinc salt and first alkali metal salt solution to dip a nanoscale second alkali metal SSZ-13 molecular sieve to obtain a zinc and first alkali metal bimetallic catalyst (denoted as ZnM)1/M2S-N). Compared with the micron-scale SSZ-13 molecular sieve, the nano SSZ-13 molecular sieve has higher specific surface area and superior diffusion performance, and can improve the conversion rate of ethane and carbon dioxide. SSZ-13 zeolite molecular sieve made of AlO4And SiO4Tetrahedron are connected end to end via oxygen atom and arranged orderly into ellipsoidal cage with eight-membered ring structure (0.73nm 1.2nm) and three-dimensional cross channel structure with pore size of 0.38nm, and small microporous zeolite and C2H6/CO2The kinetic diameters are close to each other, and the diffusion of molecules in pores can be inhibited by virtue of a pore channel effect, so that reactants are fully reacted, and the conversion rate is improved. (2) Ethane and CO2The molecular structure of the zeolite molecular sieve is relatively stable, the conversion reaction needs to be finished at a relatively high reaction temperature, and water generated in the reaction process can generate a passivation effect on the active center of the zeolite molecular sieve catalyst, so that the catalyst is quickly deactivated, and therefore, the selected zeolite molecular sieve carrier has high hydrothermal stability. The invention adopts bimetal ZnM after alkali metal exchange1/M2S-N catalyst, the M2The S-N has the advantages of excellent hydrothermal stability, stronger carbon dioxide adsorption capacity, more surface protonic acid centers, exchangeable cations and the like, and can effectively solve the problem of poor hydrothermal stability of the catalyst carrier in the prior art. (3) The invention uses zinc oxide as active substance, has no toxicity, is environment-friendly in reaction process, overcomes the defect of toxicity of Cr catalysts, has better dehydrogenation capability, is beneficial to generating a large amount of surface active hydrogen and improves the reaction activity of carbon dioxide. (4) The introduction of the first alkali metal enables the particle size of active zinc species on the catalyst to be reduced, the dispersion is more uniform, the selectivity of a target product is improved, the catalytic effect of co-conversion of low-carbon alkane and carbon dioxide is achieved, and the stability in catalytic reaction is improved.
Drawings
FIG. 1 shows catalytic reaction performance of different Zn loads loaded by micron and nanometer SSZ-13 molecular sieves.
FIG. 2 is C with different Zn loads loaded on micron and nanometer SSZ-13 molecular sieves2H6And CO2Relationship of conversion.
FIG. 3 is an activation energy test.
FIG. 4 is C of Zn/K/NaS-N bimetallic catalytic system after addition of alkali metal K2H6And CO2Relationship of conversion.
FIG. 5 is a stability performance test.
FIG. 6 shows the SEM pictures of Zn/NaS-N and Zn/K/NaS-N catalysts.
Detailed Description
Comparative example 1
Adopting four times of impregnation method to mix Zn (CH) with different qualities3COO)2Respectively dissolving (1.35g, 2.7g, 4.05g and 5.40g) in 24g of deionized water, uniformly stirring, respectively adding 10g of micron Na type SSZ-13 zeolite molecular sieve carrier, stirring for 2h (soaking for 2h) under the condition of 80 ℃ constant temperature water bath, centrifugally separating the obtained mixture, separating the obtained solid, drying at 110 ℃ for 10h, roasting at 540 ℃ for 3h to obtain the catalyst for preparing olefin by oxidizing low carbon alkane with carbon dioxide, wherein the mass fraction of zinc in the catalyst is x% (expressed as Zn by weight)x/NaS-U)。
Comparative example 2
Adopting four times of impregnation method to mix Zn (CH) with different qualities3COO)2Respectively dissolving (1.35g, 2.7g, 4.05g and 5.40g) in 24g of deionized water, uniformly stirring, respectively adding 10g of nano-scale Na type SSZ-13 zeolite molecular sieve carrier, stirring for 2h (soaking for 2h) under the condition of 80 ℃ constant-temperature water bath, centrifugally separating the obtained mixture, separating the obtained solid, drying at 110 ℃ for 10h, roasting at 540 ℃ for 3h to obtain the catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, wherein the mass fraction of zinc in the catalyst is x% (expressed as Zn by weight)x/NaS-N)。
Comparative example 3
2.89g, 5.78g and 8.67g of FeNO are added by a four-time impregnation method3·9H2O solid was dissolved in 12g of deionized water, and after stirring well, 5g of Zn of comparative example 2 was added to each of the solutionsxThe catalyst is prepared by the steps of carrying out stirring on a NaS-N catalyst for 2 hours (soaking for 2 hours) under the condition of 80 ℃ constant-temperature water bath, then carrying out centrifugal separation on the obtained mixture, separating the obtained solid, drying for 10 hours at 110 ℃, and then roasting for 3 hours at 540 ℃, wherein the mass fraction of zinc in the catalyst is 9.18 percent, and the mass fractions of iron are 1.0 percent, 2.0 percent and 3.0 percent respectively (marked as Zn)9.18/Fe1.0/NaS-N、Zn9.18/Fe2.0/NaS-N、Zn9.18/Fe3.0/NaS-N)。
Comparative example 4
By four-fold impregnation, 5.78g of FeNO was added3·9H2Dissolving O solid in 12g deionized water, stirring uniformly, adding 5g NaS-N molecular sieve, stirring for 2h (soaking for 2h) under the condition of 80 ℃ constant-temperature water bath, centrifugally separating the obtained mixture, drying the separated solid at 110 ℃ for 10h, and roasting at 540 ℃ for 3h to obtain the catalyst FexNaS-N; 0.1g of KNO was added by the same method as above, still using a four-fold impregnation method3·9H2Dissolving O solid in 12g deionized water, stirring, and adding 5g of the prepared FexNaS-N catalyst, howeverThen stirring for 2h (soaking for 2h) under the condition of 80 ℃ constant-temperature water bath, then centrifugally separating the obtained mixture, separating the obtained solid, drying for 10h at 110 ℃, and then roasting for 3h at 540 ℃ to obtain the catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, wherein the weight percentage of iron in the catalyst is 8.60 percent and the weight percentage of potassium is 0.76 percent based on the weight of iron and potassium. (denoted as Fe)8.60/K0.76/NaS-N)。
Example 1
Adopting four times of impregnation method to coat KNO with different qualities3The solids (0.2g, 0.3g, 0.4g) were dissolved in 24g of deionized water, and after stirring well, 10g of Zn of comparative example 2 was added to each of the solidsxThe catalyst is prepared by the steps of stirring the catalyst for 2 hours (soaking for 2 hours) under the condition of 80 ℃ constant-temperature water bath, centrifugally separating the obtained mixture, separating the obtained solid, drying for 10 hours at 110 ℃, and roasting for 3 hours at 540 ℃, wherein the mass fraction of zinc in the catalyst is x percent and the mass fraction of potassium in the catalyst is y percent (recorded as Zn) based on the weight of zinc and potassiumx/Ky/NaS-N)。
Example 2
Adopting four times of impregnation method to impregnate LiNO with different masses3The solids (0.2g, 0.3g, 0.4g) were dissolved in 24g of deionized water, and after stirring well, 10g of Zn of comparative example 2 was added to each of the solidsxThe catalyst is prepared by the steps of stirring the catalyst for 2 hours (soaking for 2 hours) under the condition of 80 ℃ constant-temperature water bath, centrifugally separating the obtained mixture, separating the obtained solid, drying for 10 hours at 110 ℃, and roasting for 3 hours at 540 ℃, wherein the mass fraction of zinc in the catalyst is x percent and the mass fraction of lithium in the catalyst is y percent (recorded as Zn) based on the weight of zinc and potassiumx/Liy/NaS-N)。
Example 3
Adopting four times of impregnation method to mix RbNO with different qualities3The solids (0.2g, 0.3g, 0.4g) were dissolved in 24g of deionized water, and after stirring well, 10g of Zn of comparative example 2 was added to each of the solidsxNaS-N catalyst, stirring at 80 deg.C in constant temperature water bath for 2 hr (soaking for 2 hr), centrifuging the obtained mixture, and separatingDrying the obtained solid at 110 ℃ for 10h, and then roasting at 540 ℃ for 3h to obtain the catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide, wherein the mass fraction of zinc in the catalyst is x percent and the mass fraction of lithium is y percent (marked as Zn) based on the weight of zinc and rubidiumx/Rby/NaS-N)。
Example 4
Four times of impregnation method is adopted to prepare different CsNO masses3The solids (0.2g, 0.3g, 0.4g) were dissolved in 24g of deionized water, and after stirring well, 10g of Zn of comparative example 2 was added to each of the solidsxThe catalyst is prepared by the steps of stirring the catalyst for 2 hours (soaking for 2 hours) under the condition of 80 ℃ constant-temperature water bath, centrifugally separating the obtained mixture, separating the obtained solid, drying for 10 hours at 110 ℃, and roasting for 3 hours at 540 ℃, wherein the mass fraction of zinc in the catalyst is x percent and the mass fraction of lithium is y percent (recorded as Zn) based on the weight of zinc and rubidiumx/Csy/NaS-N)。
Example 5
Catalytic effect
Ethane and carbon dioxide are used as reaction raw material gases, and the activity and the selectivity of the catalyst to a target product in the reaction of preparing ethylene by oxidizing ethane and dehydrogenating ethane with carbon dioxide are inspected. The reaction is carried out in a fixed bed reactor. The reaction conditions are as follows: molar ratio of carbon dioxide to ethane 1:1, catalyst: 1g (20-40 mesh), temperature: 550 ℃ -650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis employed an on-line double-check gas chromatograph, a hydrogen ion flame detector (FID detector) and a thermal conductivity detector (TCD detector). The catalytic effect is shown in figure 1, figure 2, figure 4, table 1 and table 2, the nano SSZ-13 carrier can simultaneously improve the conversion rate of ethane and carbon dioxide compared with the micro SSZ-13 carrier by taking zinc oxide as an active component, and Zn is loaded on the basis of the nano SSZ-13 carrier9.18/Fe2.0NaS-N catalytic effect and Zn9.18The catalytic effect of NaS-N is almost the same (Zn)9.18/Fe1.0NaS-N and Zn9.18/Fe3.0Catalytic effect of/NaS-N with Zn9.18The catalytic effect of/NaS-N is almost the same), and after loading potassium, compared with the single metal Zn/NaS-N catalystThe bimetallic Zn/K/NaS-N catalyst can greatly improve the selectivity of ethylene to C2H6/CO2Catalytic effect of co-conversion. As can be seen from fig. 6, the zinc oxide particles were reduced in size by the potassium oxide, and were dispersed more uniformly.
TABLE 1 catalytic Effect of the catalyst with micron and nanometer SSZ-13 supported by single metal Zn
TABLE 2 catalytic Effect of bimetallic Zn/K and Zn/Fe supported nano SSZ-13 catalysts
Example 6
Activation energy test
Ethane and carbon dioxide are used as reaction raw material gases, the ethane conversion rate is controlled to be within 15 percent by adjusting a temperature interval, and Zn in micron and nano scales is inspectedxThe activation energy of the/SSZ-13 catalyst is compared in the reaction of preparing ethylene by oxidizing ethane and dehydrogenating ethane with carbon dioxide.
The reaction is carried out in a fixed bed reactor. The reaction conditions are as follows: molar ratio of carbon dioxide to ethane 1:1, catalyst: 1g (20-40 mesh), temperature: 500-: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis employed a dual-detection on-line gas chromatograph, hydrogen ion flame detector (FID detector) and thermal conductivity detector (TCD detector). The catalyst activation energy is shown in FIG. 3. Can obtain Zn8.67The activation energy of the NaS-N catalyst is lower than that of Zn8.35the/NaS-U catalyst is about 8kJ/mol, which is consistent with the reaction activity result of the micro-catalyst and the nano-catalyst.
Example 7
Stability test
Using ethane and carbon dioxide as reaction raw material gas, and investigating Zn8.35/NaS-U、Zn8.67NaS-N and Zn9.18/K0.74// NaS-N catalyst in carbon dioxideStability in the reaction of ethylene oxide dehydrogenation to produce ethylene. The reaction is carried out in a fixed bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to ethane 1:1, catalyst: 1g (20-40 mesh), temperature: 550 ℃ and 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis employed a dual-detection on-line gas chromatograph, hydrogen ion flame detector (FID detector) and thermal conductivity detector (TCD detector). The catalyst stability performance is shown in figure 5. It is possible to obtain bimetallic Zn/K/NaS-N catalysts with a higher stability, in particular expressed in C, than the monometallic catalysts2H6In the conversion rate, the deactivation rate is obviously lower than that of the Zn/NaS-N catalyst, and simultaneously, the selectivity of ethylene is higher and more stable.
Example 8
Test of reaction Performance between propane and carbon dioxide
Using propane and carbon dioxide as reaction raw material gas, and investigating Zn8.67The activity of the NaS-N catalyst in the reaction of preparing propylene by oxidizing propane and dehydrogenating propane with carbon dioxide and the selectivity of the NaS-N catalyst to a target product. The reaction is carried out in a fixed bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to propane 1:1, catalyst: 1g (20-40 mesh), temperature: 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis was performed by gas chromatography, thermal conductivity detector (TCD detector).
The catalytic effect is shown in Table 3. Zn can be obtained8.67NaS-N has good catalytic effect on ethylene preparation by oxidizing propane with carbon dioxide, and after potassium is further loaded, the potassium oxide enables the particle size of zinc oxide to be smaller and the zinc oxide to be more uniformly dispersed, and then the zinc oxide and the potassium oxide are combined with the catalytic effect on ethylene preparation by oxidizing ethane with carbon dioxide to obtain the zinc oxide8.67Compared with NaS-N, the potassium-loaded catalyst is more favorable for the reaction of preparing ethylene by oxidizing propane with carbon dioxide.
Example 9
Using propane and carbon dioxide as reaction raw material gas, and investigating Zn8.67/K0.74The activity of the NaS-N catalyst in the reaction of preparing propylene by oxidizing propane and dehydrogenating propane with carbon dioxide and the selectivity of the NaS-N catalyst to a target product. Reaction is carried out in the stationaryIn a bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to propane 1:0.1, catalyst: 1g (20-40 mesh), temperature: 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis was performed by gas chromatography, thermal conductivity detector (TCD detector).
Example 10
Using propane and carbon dioxide as reaction raw material gas, and investigating Zn8.67/Li0.74The activity of the NaS-N catalyst in the reaction of preparing propylene by oxidizing propane and dehydrogenating propane with carbon dioxide and the selectivity of the NaS-N catalyst to a target product. The reaction is carried out in a fixed bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to propane 1:10, catalyst: 1g (20-40 mesh), temperature: 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis was performed by gas chromatography, thermal conductivity detector (TCD detector).
Example 11
Using propane and carbon dioxide as reaction raw material gas, and investigating Zn8.67/Rb0.74The activity of the NaS-N catalyst in the reaction of preparing propylene by oxidizing propane and dehydrogenating propane with carbon dioxide and the selectivity of the NaS-N catalyst to a target product. The reaction is carried out in a fixed bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to propane 1:1, catalyst: 1g (20-40 mesh), temperature: 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis was performed by gas chromatography, thermal conductivity detector (TCD detector).
Example 12
Using propane and carbon dioxide as reaction raw material gas, and investigating Zn8.67/Cs0.74The activity of the NaS-N catalyst in the reaction of preparing propylene by oxidizing propane and dehydrogenating propane with carbon dioxide and the selectivity of the NaS-N catalyst to a target product. The reaction is carried out in a fixed bed reactor.
The reaction conditions are as follows: molar ratio of carbon dioxide to propane 1:1, catalyst: 1g (20-40 mesh), temperature: 650 ℃, pressure: 101KPa, space velocity: 3600h-1mL/g-cat. The product analysis was performed by gas chromatography, thermal conductivity detector (TCD detector).
TABLE 3 Zn8.67Catalytic effect of NaS-N catalyst
Claims (9)
1. A catalyst for preparing olefin by oxidizing low-carbon paraffin with carbon dioxide is characterized in that: the catalyst is a zinc and first alkali metal bimetal nano catalytic system and comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a second alkali metal exchanged nano microporous SSZ-13 zeolite molecular sieve, the pore size distribution is 0.2-0.4nm, the active component is zinc oxide, the auxiliary agent is an oxide of a first alkali metal, the mass fraction of zinc in the catalyst is 1.5-9.5% by weight of zinc, and the mass fraction of the first alkali metal in the catalyst is 0.5-2% by weight of the alkali metal.
2. The catalyst for producing olefin by oxidizing lower alkane with carbon dioxide as claimed in claim 1, wherein said first alkali metal is lithium, sodium, potassium, rubidium or cesium; the second alkali metal is lithium, sodium or potassium.
3. The catalyst for producing olefin by oxidizing lower alkane with carbon dioxide as claimed in claim 1, wherein: the mass fraction of the first alkali metal in the catalyst is 0.5-1.5% based on the weight of the first alkali metal.
4. The catalyst for producing olefin by oxidizing lower alkane with carbon dioxide as claimed in claim 1, wherein: the lower alkane is C2H6Or C3H8。
5. The method for preparing the catalyst for preparing olefin by oxidizing low-carbon paraffin with carbon dioxide according to claim 1, which is characterized in that: the method comprises the following steps:
s1, carrying out roasting dehydration pretreatment on the carrier;
s2, the carrier is subjected to multiple exchanges with the second alkali metal through impregnation with the second alkali metal solution;
s3, adding the carrier completely exchanged with the second alkali metal into the zinc salt aqueous solution and the first alkali metal salt aqueous solution, dipping at 80 ℃, and collecting solid;
s4, drying and roasting the solid to obtain the catalyst for preparing olefin by the dehydrogenation of low-carbon alkane oxidized by carbon dioxide.
6. The method of claim 5, wherein the catalyst is prepared by oxidizing a lower alkane with carbon dioxide to obtain an olefin, and the method comprises the following steps: the volume ratio of the zinc salt aqueous solution and the first alkali metal salt aqueous solution to the carrier is 4.
7. The method of claim 5, wherein the catalyst is prepared by oxidizing a lower alkane with carbon dioxide to obtain an olefin, and the method comprises the following steps: the mass fraction of the zinc salt aqueous solution is 2-10%, and the mass fraction of the first alkali metal salt aqueous solution is 0.5-2%.
8. The application of the catalyst of claim 1 in the preparation of olefins by carbon dioxide oxidation of lower alkanes, which is characterized in that: the reaction temperature is 550-650 ℃, and the reaction space velocity is 3600h-1mL/g-cat, the molar ratio of carbon dioxide to low-carbon alkane in the reaction raw material is 1: 0.1-10.
9. The use of the catalyst of claim 8 in the oxidation of lower alkanes to olefins with carbon dioxide, wherein: the molar ratio of carbon dioxide to low-carbon alkane in the reaction raw material is 1: 1.
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