CN108579797A - A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure - Google Patents
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- QMGSCCRUAVAONE-UHFFFAOYSA-N zinc zirconium Chemical compound [Zn].[Zn].[Zn].[Zr] QMGSCCRUAVAONE-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KDHWZXMNULXDFH-UHFFFAOYSA-N [Zn].[Zr] Chemical group [Zn].[Zr] KDHWZXMNULXDFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019647 acidic taste Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003407 synthetizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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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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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ZnO ZrO2The preparation method of 5 catalyst with core-casing structure of@ZSM, including：ZnO‑ZrO2The preparation of powder：By feed molar proportioning n (TEOS)：n(NaAlO2)：n(TPAOH)：n(H2O)=40‑360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be add to deionized water, persistently stir evenly, stir aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO ZrO2:ZSM 5 is 1:8‑8:1 by ZnO ZrO2Powder is put into be continued to stir evenly into the system, in 170 190 DEG C of 36 48h of hydro-thermal reaction of homogeneous reactor, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 500 600 DEG C roasting 3h be made.Catalyst produced by the present invention is in CO2Add hydrogen through the ZnO ZrO of carbon dioxide conversion and selectivity of light olefin can be improved in preparing light olefins from methanol two-step process simultaneously2The preparation method of 5 catalyst with core-casing structure of@ZSM.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of ZnO-ZrO2The preparation side of@ZSM-5 catalyst with core-casing structure
Method.
Background technology
Zinc zirconium (ZnO-ZrO2) two-component catalyst is CO2The anti-sintering stability of catalytic hydrogenation methanol synthetizing technology and anti-
Sulphur ability is relatively strong and preferably a kind of metal oxide catalyst of effect.ZSM-5 molecular sieve is by SiO4And AlO4Tetrahedron list
Member is staggered to the micropore Si-Al molecular sieve of three dimensional intersection pore passage structure, enriches adjustable B Acidities, compared with Gao Bibiao because it has
The features such as area and unique microcellular products shape-selective function, it is widely used in methanol oxidation cracking producing light olefins technique（MTO）.According to
This, carries out coupling by metal oxide and acidic molecular sieve and prepares difunctional nucleocapsid catalyst, and be applied to CO2Add hydrogen through methanol
It is CO in producing light olefins technique2Hydrogenation low-carbon alkene technique new structure Catalyst Design open one it is new
Path.And existing composite catalyst active component is random distribution, and structure only provides open reactive environment, it is even more important
It is, it is very poor as the anti-sintering stability of the distributed architecture of active component using Conventional nano copper particle, it cannot effectively solve CO2Hydrogen is added to pass through
CO in preparing light olefins from methanol two-step process2Synthesizing methanol by hydrogenating technique and methanol oxidation convert producing light olefins technological requirement
Differential responses generate and the contradictory problems of dissociation conversion environment condition, cause existing composite catalyst catalytic effect still bad.
Invention content
The purpose of the present invention is to provide one kind in CO2Add hydrogen through can be carried simultaneously in preparing light olefins from methanol two-step process
The ZnO-ZrO of high carbon dioxide conversion ratio and selectivity of light olefin2The preparation method of@ZSM-5 catalyst with core-casing structure.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of ZnO-ZrO of the present invention2The preparation method of@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0 molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h, levigate to be made
The ZnO-ZrO of 200-400 mesh2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 40-360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added
It into deionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:
ZSM-5 is 1:8-8:1 by ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 170-190 DEG C of homogeneous reactor
Hydro-thermal reaction 36-48h is cooled to room temperature, centrifuges, deionized water is washed, absolute ethyl alcohol washs, 120 DEG C of dry 12h, 500-600
DEG C roasting 3h, finally obtained ZnO-ZrO2@ZSM-5 catalyst with core-casing structure.
Compared with prior art, the present invention there is apparent advantageous effect, as can be known from the above technical solutions：Prepare it is a kind of with
Meso-porous ZnO-ZrO2For nuclear phase, micropore ZSM-5 is the new type structure of hud catalyst of shell phase, nuclear phase ZnO-ZrO2Construction promote
Zinc zirconium forms solid-solution structures, and then generates more Lacking oxygens and special surface L acid-base property, improves CO2Conversion ratio；Nuclear phase ZrO2With
Shell phase ZSM-5 is formed suitable for L-B acid concerted catalysis center, and the Dissociative under methanol lower temperature is enhanced, and improves lower temperature
Lower methanol conversion；Construction enhances selectivity of light olefin by the special reaction path of shell phase of ZSM-5, inhibits by-product life
At；The hierarchical structure construction of micro--mesoporous system weakens the diffusion limitation of molecule, alleviates carbon distribution and is formed, extends catalyst life.I.e.
It is applied in CO with the obtained ZnO-ZrO2@ZSM-5 catalyst with core-casing structure of the present invention2Hydrogenation low-carbon alkene technique, compared with low temperature
Not only have compared with high reaction activity under degree, also has compared with high-low carbon olefine selective, while the catalyst reaction service life can also be extended.
Below by specific embodiment, the invention will be further described.
Specific implementation mode
Embodiment 1
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0 molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 40：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in ionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5
It is 1:8 by 200 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 170 DEG C of hydro-thermal reactions of homogeneous reactor
36h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 500 DEG C of roasting 3h, it is final to make
Obtain ZnO-ZrO2@ZSM-5 catalyst with core-casing structure.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1,
H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 62.35%, selectivity of light olefin 81.17%.
Embodiment 2
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0 molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 80：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in ionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5
It is 8:1 by 300 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 180 DEG C of hydro-thermal reactions of homogeneous reactor
48h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 550 DEG C roasting 3h, finally
ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1,
H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 61.70%, selectivity of light olefin 81.32%.
Embodiment 3
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O) = 200：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in deionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:
ZSM-5 is 1:3 by 400 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 190 DEG C of hydro-thermals of homogeneous reactor
React 48h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 600 DEG C roast 3h,
Finally obtained ZnO-ZrO2@ZSM-5 catalyst with core-casing structure.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0 MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1, H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 64.50%, selectivity of light olefin 81.70%.
Embodiment 4
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in ionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5
It is 3:1 by 200 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 180 DEG C of hydro-thermal reactions of homogeneous reactor
48h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 500 DEG C roasting 3h, finally
ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1, H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 62.38%, selectivity of light olefin 81.22%.
Embodiment 5
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in ionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5
It is 1:5 by 300 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 180 DEG C of hydro-thermal reactions of homogeneous reactor
48h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 500 DEG C roasting 3h, finally
ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1,
H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 55.17%, selectivity of light olefin 73.41%.
Embodiment 6
A kind of preparation method of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, ZnO- is made in washing, 110 DEG C of drying 4h, 500 DEG C of roasting 3h
ZrO2Powder.
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n
(NaAlO2)：n(TPAOH)：n(H2O)= 360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to
It in ionized water, persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5
It is 5:1 by 200 mesh ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 180 DEG C of hydro-thermal reactions of homogeneous reactor
48h, be cooled to room temperature, centrifuge, deionized water washing, absolute ethyl alcohol washing, 120 DEG C of dry 12h, 500 DEG C roasting 3h, finally
ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made.
Use example：ZnO-ZrO2@ZSM-5 catalyst with core-casing structure is made to apply in hydrogenation of carbon dioxide synthesizing low-carbon alkene
In technique（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：30 mL·min-1,
H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 57.22%, selectivity of light olefin 63.59%.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form, Ren Hewei
Be detached from technical solution of the present invention content, according to the technical essence of the invention to made by above example it is any it is simple modification, etc.
With variation and modification, in the range of still falling within technical solution of the present invention.
Claims (2)
1. a kind of ZnO-ZrO2The preparation method of@ZSM-5 catalyst with core-casing structure, includes the following steps：
（1）ZnO-ZrO2Preparation：NH is matched by feed molar4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:
1.0:0.2, under stirring, with the flow velocity of 3ml/min by 1.0 molL-1Sal volatile, which adds to be formed in zinc zirconium mixed solution, to sink
It forms sediment, persistently stirs aging 2h at 70 DEG C, be cooled to room temperature, filter, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h, levigate to be made
ZnO-ZrO2Powder；
（2）The preparation of ZnO-ZrO2@ZSM-5 catalyst with core-casing structure：By feed molar proportioning n (TEOS)：n(NaAlO2)：n
(TPAOH)：n(H2O)= 40-360：1：19：Under 4015 stirrings, successively by NaAlO2, TPAOH and TEOS be added to deionized water
In, it persistently stirs evenly, stirs aging 3h at room temperature and form sol system, by nucleocapsid mass ratio ZnO-ZrO2:ZSM-5 is 1:8-
8:1 by ZnO-ZrO2Powder is put into be continued to stir evenly into the system, in 170-190 DEG C of hydro-thermal reaction 36- of homogeneous reactor
48h is cooled to room temperature, centrifuges, deionized water is washed, absolute ethyl alcohol washs, 120 DEG C of dry 12h, 500-600 DEG C of roastings 3h, system
Obtain ZnO-ZrO2@ZSM-5 catalyst with core-casing structure.
2. a kind of ZnO-ZrO as described in claim 12The preparation method of@ZSM-5 catalyst with core-casing structure, wherein：The（1）Step
Middle ZnO-ZrO2The mesh number of powder is 200-400 mesh.
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