CN108246356A - A kind of preparation method of ZnO-ZrO2@Al2O3@SAPO-34 double-core shell catalysts - Google Patents
A kind of preparation method of ZnO-ZrO2@Al2O3@SAPO-34 double-core shell catalysts Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 89
- 229910001845 yogo sapphire Inorganic materials 0.000 title claims abstract description 89
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 12
- QMGSCCRUAVAONE-UHFFFAOYSA-N zinc zirconium Chemical compound [Zn].[Zn].[Zn].[Zr] QMGSCCRUAVAONE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000005406 washing Methods 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 28
- 150000001336 alkenes Chemical class 0.000 abstract description 18
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 230000007935 neutral effect Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 241000269350 Anura Species 0.000 abstract 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 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
- 239000002253 acid Substances 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
- 229960005181 morphine Drugs 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
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur 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
- 230000008859 change 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
- 239000012528 membrane Substances 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ZnO ZrO2@Al2O3The preparation method of 34 double-core shell catalysts of@SAPO, including：ZnO‑ZrO2@Al2O3The preparation of powder：Al is matched by feed molar2O3:P2O5:SiO2:MOR:H2O=1.0:0.8:0.6:2.5:80, under stirring, boehmite, ethyl orthosilicate and template morpholine are added in orthophosphoric acid solution successively, persistently stirred evenly, stirred aging at room temperature and form sol system for 24 hours, by nucleocapsid mass ratio ZnO ZrO2@Al2O3:SAPO 34 is 1:4‑4:1 by 200 400 mesh ZnO ZrO2@Al2O3Powder is put into the system, continues to be transferred in reaction kettle after stirring evenly, and 190 210 DEG C of 24 48 h of hydrothermal crystallizing, cooling, filtering, deionized water is washed to neutral, 105 DEG C of drying 6h, roasting 3h is made at 500 600 DEG C.Catalyst produced by the present invention is in CO2Add hydrogen through carbon dioxide conversion and selectivity of light olefin can be improved simultaneously in preparing light olefins from methanol two-step process.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of ZnO-ZrO2@Al2O3@SAPO-34 double-core shell catalysts
Preparation 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.SAPO-34 molecular sieves are by SiO4、AlO4And PO4Three
Kind tetrahedron element is staggered to the micropore silicoaluminophosphate system molecular sieve of three dimensional intersection pore passage structure, because it is with abundant adjustable
The features such as B Acidities, high specific surface area and unique microcellular products shape-selective function, it is widely used in methanol oxidation cracking low-carbon
Olefin process（MTO）.Accordingly, metal oxide and acidic molecular sieve are subjected to coupling and prepare difunctional nucleocapsid catalyst, and should
Use CO2Add hydrogen through in preparing light olefins from methanol technique, being CO2Hydrogenation low-carbon alkene technique new structure Catalyst Design is opened
Hair opens a new path.And existing composite catalyst active component is random distribution, and structure only provide it is open anti-
Answer environment, it is even more important that very poor as the anti-sintering stability of the distributed architecture of active component using Conventional nano copper particle, it is impossible to
Effectively solve CO2Add hydrogen through CO in preparing light olefins from methanol two-step process2Synthesizing methanol by hydrogenating technique and methanol oxidation conversion system
The differential responses of low-carbon alkene technological requirement generate and the contradictory problems of dissociation conversion environment condition, and existing composite catalyst is caused to urge
It is still bad to change effect.
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 olefin2@Al2O3The preparation side of@SAPO-34 double-core shell catalysts
Method.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of ZnO-ZrO of the present invention2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:2-1:9 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C
Dry 1 h, 600 DEG C of roastings 3h, levigate obtained 200-400 mesh ZnO-ZrO2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2:MOR:H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template
Coffee quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid quality
Compare ZnO-ZrO2@Al2O3:SAPO-34 is 1:4-4:1 by 200-400 mesh ZnO-ZrO2@Al2O3Powder is put into the system, after
Continue and be transferred in reaction kettle after stirring evenly, 190-210 DEG C of hydrothermal crystallizing 24-48 h, cooling, filtering, deionized water are washed into
Property, 105 DEG C drying 6h, 3h is roasted at 500-600 DEG C, be made ZnO-ZrO2@Al2O3@SAPO-34 double-core shell catalysts.
Compared with prior art, the present invention with 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 SAPO-34 is shell phase, and introduces intermediate layer γ-Al2O3New double-core shell structure
Catalyst, nuclear phase ZnO-ZrO2Construction zinc zirconium is promoted to form solid-solution structures, and then generate more Lacking oxygens and special surface L acid
Alkalinity improves CO2Conversion ratio；Intermediate layer γ-Al2O3Construction on the one hand formed with shell phase SAPO-34 and assisted suitable for L-B acid
Same catalytic center enhances the Dissociative under methanol lower temperature, improves methanol conversion under lower temperature, on the other hand promotes
SAPO-34 molecular screen membranes are in ZnO-ZrO2The growth on surface is conducive to nucleocapsid construction；Construction is using SAPO-34 as shell phase
Special reaction path enhances selectivity of light olefin, inhibits by-product generation；The hierarchical structure construction of micro--mesoporous system, which weakens, to be divided
The diffusion limitation of son, alleviates carbon distribution and is formed, extend catalyst life.I.e. with the obtained ZnO-ZrO of the present invention2@Al2O3@SAPO-34
Double-core shell catalyst is applied in CO2Hydrogenation low-carbon alkene technique not only has compared with high reaction activity, also has at a lower temperature
Have 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 embodiment
Embodiment 1
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:2 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying
ZnO-ZrO is made in 1h, 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2:MOR:H2O=1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template morphine
Quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid mass ratio
ZnO-ZrO2@Al2O3:SAPO-34 is 1:4 by 200 mesh ZnO-ZrO2@Al2O3Powder is put into the system, continues to stir evenly
After be transferred in reaction kettle, 190 DEG C of hydrothermal crystallizings for 24 hours, cooling, filtering, deionized water wash to neutral, 105 DEG C of drying 6h, in
3h is roasted at 500 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（Reaction pressure：3.0MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500h-1, nitrogen flow rate：30mL·
min-1, H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 67.33%, selectivity of light olefin 81.20%.
Embodiment 2
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:4 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying 1
H, ZnO-ZrO is made in 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2:MOR:H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template
Coffee quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid quality
Compare ZnO-ZrO2@Al2O3:SAPO-34 is 4:1 by 300 mesh ZnO-ZrO2@Al2O3Powder is put into the system, and it is equal to continue stirring
Be transferred in reaction kettle after even, 200 DEG C of hydrothermal crystallizing 36h, cooling, filtering, deionized water are washed to neutral, 105 DEG C of drying 6h, in
3h is roasted at 550 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（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 65.42%, selectivity of light olefin 77.31%.
Embodiment 3
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:6 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying 1
H, ZnO-ZrO is made in 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3: P2O5:
SiO2:MOR: H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template
Coffee quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid quality
Compare ZnO-ZrO2@Al2O3:SAPO-34 is 2:1 by 400 mesh ZnO-ZrO2@Al2O3Powder is put into the system, and it is equal to continue stirring
It is transferred in reaction kettle after even, 210 DEG C of 48 h of hydrothermal crystallizing, cooling, filtering, deionized water are washed to neutral, 105 DEG C of drying 6
H, 3 h are roasted at 600 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（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 63.92%, selectivity of light olefin 81.47%.
Embodiment 4
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:8 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying
ZnO-ZrO is made in 1 h, 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2 MOR:H2O=1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template morphine
Quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid mass ratio
ZnO-ZrO2@Al2O3:SAPO-34 is 1:2 by 200 mesh ZnO-ZrO2@Al2O3Powder is put into the system, continues to stir evenly
After be transferred in reaction kettle, 200 DEG C of hydrothermal crystallizing 48h, cooling, filtering, deionized water are washed to neutral, 105 DEG C of drying 6h, in
3h is roasted at 500 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（Reaction pressure：3.0 MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500h-1, nitrogen flow rate：30mL·
min-1, H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 62.13%, selectivity of light olefin 81.94%.
Embodiment 5
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:9 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying 1
H, ZnO-ZrO is made in 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2:MOR:H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template
Coffee quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid quality
Compare ZnO-ZrO2@Al2O3:SAPO-34 is 1:3 by 300 mesh ZnO-ZrO2@Al2O3Powder is put into the system, and it is equal to continue stirring
Be transferred in reaction kettle after even, 210 DEG C of 48 h of hydrothermal crystallizing, cooling, filtering, deionized water wash to neutral, 105 DEG C of drying 6h,
3h is roasted at 600 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（Reaction pressure：3.0 MPa, reaction temperature：325 DEG C, weight (hourly) space velocity (WHSV)：3500 h-1, nitrogen flow rate：
30mL·min-1, H2/CO2Molar ratio 3.0:1.0）, measure CO2Conversion ratio 51.38%, selectivity of light olefin 72.40%.
Embodiment 6
A kind of ZnO-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:3 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C of drying
ZnO-ZrO is made in 1h, 600 DEG C of roasting 3h2@Al2O3Powder.
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:
SiO2:MOR:H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template
Coffee quinoline is added in orthophosphoric acid solution, is persistently stirred evenly, and is stirred aging at room temperature and is formed sol system for 24 hours, by nucleocapsid quality
Compare ZnO-ZrO2@Al2O3:SAPO-34 is 3:1 by 200 mesh ZnO-ZrO2@Al2O3Powder is put into the system, and it is equal to continue stirring
Be transferred in reaction kettle after even, 200 DEG C of hydrothermal crystallizing 48h, cooling, filtering, deionized water wash to neutral, 105 DEG C of 6 h of drying,
3h is roasted at 500 DEG C, ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts.
Use example：ZnO-ZrO is made2@Al2O3@SAPO-34 double-core shell catalysts are applied low in hydrogenation of carbon dioxide synthesis
In olefins process（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 58.37%, selectivity of light olefin 61.22%.
The above described is only a preferred embodiment of the present invention, not make limitation in any form, Ren Hewei to the present invention
Technical solution of the present invention content is detached from, any simple modification that technical spirit according to the present invention makees above example, 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-ZrO2@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, includes the following steps：
（1）ZnO-ZrO2@Al2O3Preparation：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 adds to shape in zinc zirconium mixed solution
Into precipitation, aging 2h is persistently stirred at 70 DEG C, is cooled to room temperature, filtered, washing, 110 DEG C of drying 4h, 500 DEG C roast 3h and are made
ZnO-ZrO2Powder；By nucleocapsid mass ratio Al2O3:ZnO-ZrO2=1:2-1:9 by Al2O3It is sprayed on ZnO-ZrO2Surface, 105 DEG C
Dry 1 h, 600 DEG C of roastings 3h, levigate obtained ZnO-ZrO2@Al2O3Powder；
（2）ZnO-ZrO2@Al2O3The preparation of@SAPO-34 double-core shell catalysts：Al is matched by feed molar2O3:P2O5:SiO2:
MOR:H2O =1.0:0.8:0.6:2.5:80, under stirring, successively by boehmite, ethyl orthosilicate and template morpholine
It is added in orthophosphoric acid solution, persistently stirs evenly, stir aging at room temperature and form sol system for 24 hours, by nucleocapsid mass ratio
ZnO-ZrO2@Al2O3:SAPO-34 is 1:4-4:1 by 200-400 mesh ZnO-ZrO2@Al2O3Powder is put into the system, is continued
It is transferred in reaction kettle after stirring evenly, 190-210 DEG C of hydrothermal crystallizing 24-48 h, cooling, filtering, deionized water are washed into
Property, 105 DEG C drying 6h, 3h is roasted at 500-600 DEG C, be made ZnO-ZrO2@Al2O3@SAPO-34 double-core shell catalysts.
2. a kind of ZnO-ZrO as described in claim 12@Al2O3The preparation method of@SAPO-34 double-core shell catalysts, wherein：
The（1）ZnO-ZrO in step2@Al2O3The mesh number of powder is 200-400 mesh.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261199A (en) * | 2018-09-27 | 2019-01-25 | 太原理工大学 | A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications |
| CN109317192A (en) * | 2018-09-30 | 2019-02-12 | 宁夏大学 | A kind of CO2The nucleocapsid catalyst of hydrogenation coupled preparing low-carbon olefins and its preparation |
-
2018
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261199A (en) * | 2018-09-27 | 2019-01-25 | 太原理工大学 | A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications |
| CN109261199B (en) * | 2018-09-27 | 2021-03-19 | 太原理工大学 | Catalyst for directly preparing low-carbon olefin from high-stability synthesis gas, preparation method and application thereof |
| CN109317192A (en) * | 2018-09-30 | 2019-02-12 | 宁夏大学 | A kind of CO2The nucleocapsid catalyst of hydrogenation coupled preparing low-carbon olefins and its preparation |
| CN109317192B (en) * | 2018-09-30 | 2021-04-27 | 宁夏大学 | CO (carbon monoxide)2Core-shell catalyst for preparing low-carbon olefin by hydrogenation coupling and preparation thereof |
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