CN109433252A - A kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst and preparation method thereof - Google Patents
A kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst and preparation method thereof Download PDFInfo
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- CN109433252A CN109433252A CN201811453072.6A CN201811453072A CN109433252A CN 109433252 A CN109433252 A CN 109433252A CN 201811453072 A CN201811453072 A CN 201811453072A CN 109433252 A CN109433252 A CN 109433252A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000011701 zinc Substances 0.000 claims abstract description 54
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- 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 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- 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 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000000470 constituent Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 29
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000011149 active material Substances 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011651 chromium Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QYKRDDCDQPHRTK-UHFFFAOYSA-N carbon dioxide;ethoxyethane Chemical compound O=C=O.CCOCC QYKRDDCDQPHRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 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
- 238000010792 warming Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst and preparation method thereof, catalyst includes carrier and active constituent, the carrier is micro-pore zeolite molecular sieve, pore-size distribution is 0.2-0.4nm, the active constituent is zinc ion, with the poidometer of zinc, the mass fraction of zinc is 0.5-15% in catalyst, and the micro-pore zeolite molecular sieve is at least one of SAPO-34 and SSZ-13.Carrier of the present invention has high hydrothermal stability, and high-specific surface area has the advantages that more surface plasmon acid site and exchangeable cations, can effectively solve the problem that the problem of catalyst carrier hydrothermal stability difference in the prior art.The present invention is nontoxic using zinc ion as active material, and has preferable ability of dehydrogenation, is conducive to reaction and generates H2.Zinc ion enough effectively improves catalyst to CO2Adsorption capacity, to improve CO2Conversion ratio and C2H4Selectivity.
Description
Technical field
The invention belongs to prepare ethylene technical field, and in particular to a kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst and
Preparation method.
Background technique
Carbon dioxide is the final oxide of carbon and carbon compound, while being also the most abundant carbon source of nature, is being led
In " greenhouse gases " for causing global warming, CO2Contribution to greenhouse effects is 55%.Thus, carry out to CO2Recycling
The research utilized is most important.H2Source is more convenient, therefore, CO2Catalytic hydrogenation be the hot spot studied at present.However, big at present
Most CO2The reaction condition of catalytic hydrogenation is harsher, and hydrogen producing technology higher cost, this limits CO to a certain extent2It is catalyzed hydrogen
Change technology further applying industrially.Ethane is used as the highest hydrocarbons of hydrogen-carbon ratio in addition to methane, can be used as hydrogen
Donor, catalytic hydrogenation carbon dioxide are CO, same to H2It can be used as important industrial chemicals together as synthesis gas.C2H6Turn after dehydrogenation
Turn to the C of high added value2H4, can produce certain economic value.If being able to achieve CO2And C2H6Cotransformation, one will be generated
Fixed economic benefit and social benefit.
In recent years, domestic and international researcher is to CO2Aoxidize C2H6Dehydrogenation C2H4The catalyst of reaction is studied.
Open source literature Applied Catalysis A:General 196 (2000) 1-8. reports CO2Aoxidize C2H6Dehydrogenation
C processed2H4Catalyst.The results showed that 8%Cr2O3/SiO2The better catalytic activity of catalyst.Reaction condition be 650 DEG C,
3600h-1ML/g-cat, n (C2H6)/n(CO2When)=1:5, C2H6Conversion ratio is 61%, C2H4Selectivity is 91%；C2H4It receives
Rate is 55.5%.Open source literature Catalysis Communications3 (2002) 257-262. reports CO2Aoxidize C2H6It is de-
Hydrogen C2H4Catalyst.The results showed that 5%Cr/H-ZSM-5-1900 (SiO2/Al2O3) catalyst activity highest.Reaction
Condition is 650 DEG C, 6000h-1ML/g-cat, n (C2H6)/n(CO2When)=1:9, C2H6Conversion ratio is 68.2%, C2H4Selection
Property is 69.5%.Open source literature Studies in Surface Science&Catalysis, 2001,136:87-92. are reported
CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst.The results showed that 6%Cr/AC (Activated Carbon) catalyst is urged
Change activity preferably.Reaction condition is 650 DEG C, 1200h-1, n (C2H6)/n(CO2When)=1:1, C2H6Conversion ratio is 28.9%,
CO2Initial conversion is 23.5%, C2H4Selectivity is 70.5%.At 600 DEG C, 1200h-1, n (C2H6)/n(CO2)=1:1 condition
After lower reaction 4h, C2H6Conversion ratio is down to 6.6%, C by 15.7%2H4Yield is down to 5.8% by 11.9%.At this point, at 700 DEG C
Under the conditions of, use CO2After regenerating 1h as regenerative agent, C2H6And C2H4Yield increases respectively to 10.7% and 8.5%, but cannot
Enough it is restored to initial activity.
It is reported above to be all made of Cr series catalysts to carry out CO2Aoxidize C2H6Dehydrogenation C2H4, but Cr series catalysts itself have
It is toxic, do not meet environmentally protective requirement；More importantly above-mentioned catalyst hydrothermal stability itself is poor, and CO2With
C2H6Cotransformation reaction, need just to can be carried out in higher temperature (generally 650 DEG C or more), have during simultaneous reactions aquatic
At under these conditions, above-mentioned catalyst is easy loss of activity due to destructurized.Therefore, for CO2And C2H6Corotation
Change reaction, it is most important to prepare the catalyst that hydrothermal stability is higher, catalytic activity is good.
Summary of the invention
It is asked to solve existing support type Cr catalyst carrier hydrothermal stability difference and the weak technology of carbon dioxide adsorption ability
It inscribes and since Cr uses caused environmental problem, the present invention provides a kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst and its system
Preparation Method.Institute possesses good hydrothermal stability using catalyst；And carbon dioxide and second can be catalyzed under the conditions of 650 DEG C
The cotransformation of alkane reacts, and obtains CO highest so far2And C2H6Conversion ratio；Catalyst itself is nontoxic simultaneously, meets green ring
The requirement of guarantor.
Technical scheme is as follows:
A kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst, including carrier and active constituent, the carrier is micro-pore zeolite
Molecular sieve, pore-size distribution 0.2-0.4nm, the active constituent is zinc ion, with the poidometer of zinc, the quality of zinc in catalyst
Score is 0.5-15%, and the micro-pore zeolite molecular sieve is at least one of SAPO-34 and SSZ-13.
A kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, include the following steps:
A. carrier is subjected to roasting dehydration pre-process；
B. carrier is added in zinc salt solution after 60-80 DEG C of dipping, collects solid；
C. solid is dry, roasting obtains the catalyst of preparing ethene by oxidative dehydrogenation of ethane with carbon dioxide.
The volume ratio of the zinc salt solution and carrier is 0.5-2.
The concentration of zinc salt solution is 0.128-3.84mol/L.
The zinc salt is one or more of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.
The drying temperature is 80-110 DEG C, drying time 8-20h；Maturing temperature is 450-600 DEG C, and calcining time is
2-20h。
The present invention also provides a kind of above-mentioned catalyst to be used for CO2Aoxidize C2H6Dehydrogenation C2H4Reaction, reaction condition are as follows: reaction
Temperature is 550 DEG C -800 DEG C, reaction velocity 1800-100000h-1ML/g-cat, CO in reaction raw materials2With C2H6Molar ratio
For 1-10.
Beneficial effects of the present invention are as follows:
It is suitble to ethane and CO2It is necessary to meet following condition for the molecular sieve of cotransformation: (1) due to reactant and its target product
The molecular dimension of (ethylene, synthesis gas) is smaller, it requires that molecular sieve catalyst has the small hole characteristic of octatomic ring, just advantageous in this way
In by shape selective catalysis transformation raising selectivity of product；(2) ethane and CO2Molecular structure it is relatively stable, conversion reaction
Need the water completed under relatively high reaction temperature, and generated in reaction process can be to the activity of zeolite molecular sieve catalyst
Center generates passivation, and then leads to the rapid deactivation of catalyst, therefore selected zeolite molecular sieve carrier will have high hydro-thermal steady
It is qualitative.The present invention uses pore-size distribution for 0.2-0.4nm, SSZ-13 the and SAPO-34 micropore with chabasie (CHA) structure point
Son sieve.Wherein, SSZ-13 zeolite molecular sieve is by AlO4And SiO4Tetrahedron is end to end by oxygen atom, is arranged in tool in an orderly manner
There are the elliposoidal cage (0.73nm*1.2nm) and three dimensional intersection cellular structure of octatomic ring structure, pore size 0.38nm*
0.38nm.The requirement for not only meeting aperture and high hydrothermal stability simultaneously, also has high-specific surface area (up to 700m2/ g), have
The advantages that more surface plasmon acid site and exchangeable cations.It can effectively solve the problem that catalyst carrier hydro-thermal in the prior art
The problem of stability difference.Zn-ef ficiency is introduced in this carrier to obtain having high ethane and CO2The catalyst of cotransformation ability.More
Further, SSZ-13 micro porous molecular sieve is to CO2With preferable affinity, it is conducive to more CO2Molecule is able to participate ethane
Activation and subsequent transformation reaction in.In addition, the present invention is active material using zinc ion, nontoxic, reaction process is to environment friend
It is good, overcome Cr series catalysts to have the shortcomings that toxicity, and have preferable ability of dehydrogenation, is conducive to reaction and generates H2.Further
Ground, zinc ion enough effectively improve catalyst to CO2Adsorption capacity, to improve CO2Conversion ratio and C2H4Selectivity.
Detailed description of the invention
Fig. 1 is Zn load capacity and CO2And C2H6The relationship of conversion ratio.
Fig. 2 is Zn/SSZ-13 stability test result.
Fig. 3 is Zn/SSZ-13 regenerability test result.
Specific embodiment
Comparative example 1
By the Zn (NO of 3.87g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, 10gZSM-5 zeolite point is added
Then son sieve carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture, point
110 DEG C from obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst, with
The poidometer of zinc, the mass fraction of zinc is 2% (to be denoted as Zn in catalyst2/ZSM-5).By Zn2/ ZSM-5 catalyst in 650 DEG C into
The processing of row water vapor passivation, processing time are 10h, water 3mL/h, the CO after passivation can be obtained2Aoxidize C2H6Dehydrogenation system
C2H4Catalyst, with the poidometer of zinc, the mass fraction of zinc is 2% (to be denoted as Zn in catalyst2/ZSM-5-D)。
Comparative example 2
By the Zn (NO of 3.87g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, the boiling of 10g MCM-22 type is added
Then stone molecular sieve carrier stirs 2h (dipping 2h), later by the centrifugation point of obtained mixture under 80 DEG C of constant temperature ` water bath conditions
From 110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalysis
Agent, with the poidometer of zinc, the mass fraction of zinc (is denoted as Zn for 2% in catalyst2/MCM-22)。
Comparative example 3
By the Zn (NO of 3.87g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, 10gY type zeolite molecules is added
Carrier is sieved, 2h (dipping 2h) is then stirred under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture, separation
110 DEG C of obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst, with zinc
Poidometer, the mass fraction of zinc is 2% (to be denoted as Zn in catalyst2/Y)。
Comparative example 4
By the Cr (NO of 6.77g3)3·9H2O is dissolved in 24g deionized water, after mixing evenly, 10gSSZ-13 zeolite is added
Then molecular sieve carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture,
110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst,
With the poidometer of chromium, the mass fraction of chromium (is denoted as Cr for 2% in catalyst2/SSZ-13)。
Embodiment 1
By the ZnCl of 1.67g2It is dissolved in 24g deionized water, after mixing evenly, 10gSAPO-34 type zeolite molecular sieve is added
Then carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture, separates institute
110 DEG C of solid dry 10h are obtained, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst, with zinc
Poidometer, the mass fraction of zinc is 2% (to be denoted as Zn in catalyst2/SAPO-34)。
Embodiment 2
By 0.68gZn (Ac)2·2H2O、1.83g ZnSO4·7H2O、3.87gZn(NO3)2·6H2O is dissolved in 24g respectively and goes
In ionized water, after mixing evenly, 10gSSZ-13 zeolite molecular sieve carrier is added, is then stirred under the conditions of 80 DEG C of waters bath with thermostatic control
Obtained mixture, is centrifugated, 110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roastings by 2h (dipping 2h) later
CO can be obtained in 3h2Aoxidize C2H6Dehydrogenation C2H4Catalyst, with the poidometer of zinc, the mass fraction difference of zinc in catalyst
(it is denoted as Zn respectively for 0.50%, 1.00%, 2.00%0.5/SSZ-13、Zn1/SSZ-13、Zn2/SSZ-13).By Zn2/SSZ-13
In 650 DEG C of progress water vapor passivation processing, the processing time is 10h, water 3mL/h, the CO after passivation can be obtained2Oxidation
C2H6Dehydrogenation C2H4Catalyst (be denoted as Zn2/SSZ-13-D)。
Embodiment 3
By the Zn (NO of 26.98g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, 10gSSZ-13 zeolite is added
Then molecular sieve carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture,
110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst,
With the poidometer of zinc, the mass fraction of zinc (is denoted as Zn for 10% in catalyst10/SSZ-13)。
Embodiment 4
By the Zn (NO of 26.98g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, addition 5gSSZ-13,
Then 5gSAPO-34 zeolite molecular sieve carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, mixed by what is obtained later
Object centrifuge separation is closed, 110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation
C processed2H4Catalyst, with the poidometer of zinc, the mass fraction of zinc is 10% (to be denoted as Zn in catalyst10/(SSZ-13&SAPO-
34)。
Embodiment 5
By the Zn (NO of 53.12g3)2·6H2O is dissolved in 24g deionized water, after mixing evenly, 10gSSZ-13 zeolite is added
Then molecular sieve carrier stirs 2h (dipping 2h) under the conditions of 80 DEG C of waters bath with thermostatic control, is later centrifugated obtained mixture,
110 DEG C of separating obtained solid dry 10h, then 540 DEG C of roasting 3h, can be obtained CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst,
With the poidometer of zinc, the mass fraction of zinc (is denoted as Zn for 15% in catalyst15/SSZ-13)。
Embodiment 6
Catalytic effect
Using ethane and carbon dioxide as reaction substrate, investigates catalyst and reacted in preparing ethene by oxidative dehydrogenation of ethane with carbon dioxide
In activity and selectivity to target product.Reaction carries out in fixed bed reactors.
Reaction condition are as follows: catalyst: 1g (20-40 mesh), temperature: 650 DEG C, pressure: 101KPa, air speed are as follows: 3600h-1mL/
g-cat.Product analysis uses gas-chromatography, hydrogen ion flame detector.Catalytic effect is shown in Table 1, available: relative to Cr2/
SSZ-13 molecular sieve catalyst, Zn2/ SSZ-13 molecular sieve catalyst has higher CO2And C2H6Conversion capability；Meanwhile relatively
In other Zn supporting molecular sieve catalysts, Zn2/ SSZ-13 molecular sieve has higher CO2And C2H6Conversion capability.Zn2/SSZ-
The CO of 13-D2And C2H6Conversion ratio still maintains a higher level, significantly larger than Zn2/ ZSM-5-D illustrates that Zn/SSZ-13 is gathered around
There is higher hydrothermal stability.
The catalytic effect of 1 catalyst of table
Each material composition (mass fraction) in 2 reaction end gas of table
Embodiment 7
Zn load capacity and CO2And C2H6The relationship of conversion ratio
Using ethane and carbon dioxide as reaction substrate, a series of obtained catalyst of embodiment 2 are investigated in carbon dioxide
Activity in preparing ethene by oxidative dehydrogenation of ethane with reaction and the selectivity to target product.Reaction carries out in fixed bed reactors.
Reaction condition are as follows: catalyst: 1g (20-40 mesh), temperature: 650 DEG C, pressure: 101KPa, air speed are as follows: 3600h-1mL/
g-cat.Product analysis uses gas-chromatography, hydrogen ion flame detector.Zn load capacity and CO2And C2H6The relationship of conversion ratio is shown in
Table 3 and Fig. 1.
The reactivity worth of 3 catalyst of table
Embodiment 8
Zn load capacity and n (H2The relationship of)/n (CO)
Using ethane and carbon dioxide as reaction substrate, a series of obtained catalyst of embodiment 2 are investigated in carbon dioxide
Activity in preparing ethene by oxidative dehydrogenation of ethane with reaction and the selectivity to target product.Reaction carries out in fixed bed reactors.
Reaction condition are as follows: catalyst: 1g (20-40 mesh), temperature: 650 DEG C, pressure: 101KPa, air speed are as follows: 3600h-1mL/
g-cat.Product analysis uses gas-chromatography, hydrogen ion flame detector, thermal conductivity detector (TCD).Zn load capacity and n (H2)/n(CO)
Relationship be shown in Table 4.It is available, there is H by the SSZ-13 molecular sieve that Zn is loaded2It generates, there is preferable ability of dehydrogenation.
Each material composition in 4 reaction end gas of table
Embodiment 9
Stability test
Using ethane and carbon dioxide as reaction substrate, Zn is investigated0.5/ SSZ-13 catalyst is de- in carbon dioxide ethyl oxide
Activity during hydrogen is ethylene reaction produced and the selectivity to target product.Reaction carries out in fixed bed reactors.
Reaction condition are as follows: catalyst: 1g (20-40 mesh), temperature: 650 DEG C, pressure: 101KPa, air speed are as follows: 3600h-1mL/
g-cat.Product analysis uses gas-chromatography, hydrogen ion flame detector.Catalyst stabilization performance is shown in Fig. 2.It is available, for
Zn0.5/ SSZ-13 molecular sieve catalyst, no matter to CO2Conversion ratio, C2H6Conversion ratio or C2H4Selectivity, it is all specific higher
Stablize.
Embodiment 10
Regenerability test
Using ethane and carbon dioxide as reaction substrate, Zn is investigated2/ SSZ-13 catalyst is in carbon dioxide ethyl oxide dehydrogenation
Regenerability in ethylene reaction produced.Reaction carries out in fixed bed reactors.Every reaction 1h, by catalyst in air atmosphere
In, 3h is roasted under the conditions of 540 DEG C of temperature.
Reaction condition are as follows: catalyst: 1g (20-40 mesh), temperature: 650 DEG C, pressure: 101KPa, air speed are as follows: 3600h-1mL/
g-cat.Product analysis uses gas-chromatography, hydrogen ion flame detector.Catalyst regeneration performance is shown in Fig. 3.It is available, regeneration
Zn afterwards2/ SSZ-13 molecular sieve catalyst, CO2Conversion ratio, C2H6Conversion ratio and C2H4It is all up fresh state catalyst
Reactivity worth illustrates Zn2/ SSZ-13 molecular sieve catalyst has good regenerability.
Claims (7)
1. a kind of CO2Aoxidize C2H6Dehydrogenation C2H4Catalyst, including carrier and active constituent, it is characterised in that: the carrier
For micro-pore zeolite molecular sieve, pore-size distribution 0.2-0.4nm, the active constituent is zinc ion, with the poidometer of zinc, catalyst
The mass fraction of middle zinc is 0.5-15%, and the micro-pore zeolite molecular sieve is at least one of SAPO-34 and SSZ-13.
2. a kind of CO as described in claim 12Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, it is characterised in that:
Include the following steps:
A. carrier is subjected to roasting dehydration pre-process；
B. carrier is added in zinc salt solution after 60-80 DEG C of dipping, collects solid；
C. solid is dry, roasting obtains the catalyst of preparing ethene by oxidative dehydrogenation of ethane with carbon dioxide.
3. a kind of CO as claimed in claim 22Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, it is characterised in that:
The volume ratio of the zinc salt solution and carrier is 0.5-2.
4. a kind of CO as claimed in claim 22Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, it is characterised in that:
The concentration of the zinc salt solution is 0.128-3.84mol/L.
5. a kind of CO as claimed in claim 22Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, it is characterised in that:
The zinc salt is one or more of zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.
6. a kind of CO as claimed in claim 22Aoxidize C2H6Dehydrogenation C2H4Catalyst preparation method, it is characterised in that:
Drying temperature is 80-110 DEG C in step C, drying time 8-20h；Maturing temperature is 450-600 DEG C, calcining time 2-
20h。
7. a kind of catalyst described in claim 1 is used for CO2Aoxidize C2H6Dehydrogenation C2H4Reaction, it is characterised in that: reaction item
Part are as follows: reaction temperature is 550 DEG C -800 DEG C, reaction velocity 1800-100000h-1ML/g-cat, CO in reaction raw materials2With C2H6
Molar ratio be 1-10.
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