CN110227468A - Nickel calcium based composite catalysis agent preparation and application during catalytic pyrolysis of biomass - Google Patents
Nickel calcium based composite catalysis agent preparation and application during catalytic pyrolysis of biomass Download PDFInfo
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- CN110227468A CN110227468A CN201910637290.3A CN201910637290A CN110227468A CN 110227468 A CN110227468 A CN 110227468A CN 201910637290 A CN201910637290 A CN 201910637290A CN 110227468 A CN110227468 A CN 110227468A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title abstract description 9
- JEZHBSJTXKKFMV-UHFFFAOYSA-N calcium nickel Chemical compound [Ca].[Ni] JEZHBSJTXKKFMV-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 229910018107 Ni—Ca Inorganic materials 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000010792 warming Methods 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- -1 feature It is Substances 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 2
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 229960004025 sodium salicylate Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 24
- 239000007789 gas Substances 0.000 description 82
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- 229910052799 carbon Inorganic materials 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000001294 propane Substances 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000013067 intermediate product Substances 0.000 description 10
- 150000002576 ketones Chemical class 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000010903 husk Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
A kind of nickel calcium based composite catalysis agent preparation and application during catalytic pyrolysis of biomass, including the preparation of layered metal hydroxides precursor；Calcining reduction obtains forming Ni-Ca based composite catalyst by nano particle or nanometer sheet structural motif ordered fabrication.Its application during catalytic pyrolysis of biomass includes: that the Ni-Ca based composite catalyst of preparation is carried out tabletting, crushing, screening, obtains the catalyst fines that granularity is 20 ~ 80 mesh；Biomass material is loaded in fixed-bed reactor first-stage reactor, the catalyst of above-mentioned 20 ~ 80 mesh partial sizes prepared is loaded in second reactor, is passed through N2Air in reaction unit is discharged, while reactor is warming up to set temperature, the pyrolysis steam that biomass material pyrolysis generates is condensed in the cracking of Ni-Ca based composite catalyst surface, reformation, obtained cracking steam, is dried to obtain gas and product liquid.
Description
Technical field
The invention belongs to derived energy chemical fields, more particularly to one kind by nano particle or nanometer sheet structural motif
Application method of the Ni-Ca based composite catalyst of ordered fabrication during catalytic pyrolysis of biomass.
Background technique
Biomass-based liquid fuel is the research and development focus and future thrust in biomass resource conversion field.It is multiple from structure
Miscellaneous, miscellaneous lignocellulose-like biomass raw material is converted by pyrolysis into and forms simple, uniform synthesis gas, using
Controlled process be assembled into have ideal composition composition and the automobile-used of molecular structure, aviation provided with liquid fuel for biomass resource
One higher value application mode that is precisely controllable, being easily achieved.However, fuel synthesis process generally requires hydrogen carbon in synthesis gas
Than (H2/ CO) reach 2 ~ 3 or higher hydrogen-rich it is horizontal, the gaseous product directly obtained by biomass pyrolytic need to become through water-gas
The depth for changing process regulates and controls to obtain suitable H2/ CO ratio；Meanwhile CO in pyrolysis gas2Presence it is transformed to subsequent synthesis gas
Journey efficiency and energy consumption have certain influence, need to be to CO2Carry out situ absorption removing.In addition, in pyrolytic process, fiber in biomass
The macromolecule polyalcohols such as element, hemicellulose, lignin can not be converted thoroughly, so that often inevitable in pyrolysis gas product
The macromoleculars product such as appearance acid, aldehyde, ketone, phenyl ring and polycyclic compound.The presence of these macromoleculars is to flat based on synthesis gas
It is unfavorable for the preparation process of the liquid fuel of platform.Therefore, using synthesis gas as the biomass pyrolysis process of target product
In need emphasis solve H2The adjustment of/CO ratio, CO2The problems such as removing and macromolecular intermediate product orientation deep conversion.
Using catalyst material to H in pyrolysis gas2、CO、CO2、CH4、H2O micro-molecular gas reformed, CO2It is in situ to inhale
The reactions such as receipts, Water gas shift/WGS, which couple, can be achieved purified synthesis gas and adjustment of formula.In addition, pyrolysis gas of biomass is catalyzed online
Cracking can make cracked macromolecular intermediate product, deoxidation, dealkylation be converted to short chain intermediate product again, while generate more
Micro-molecular gas significantly improves synthesis gas yield.Therefore, the online catalyzed conversion of biomass is to improve synthesis gas quality and biomass
A kind of most efficient method of utilization rate.And the dispersibility of catalytic active center and the number of active sites of exposure are to influence material
The central factor of catalytic activity.Currently, domestic and foreign scholars mainly use the catalyst material pyrolysis fuel oil etc. of the unordered accumulation of particle
Macromolecular carrys out lift gas yield, and improves synthesis gas product by adding a large amount of vapor in pyrolytic process and being reformed
Matter, research emphasis are concentrated mainly on active component and carrier optimization aspect.However the unordered accumulation, aggregation in structure are often
It will lead to the covering in activated centre and duct blocking in reaction process, so that target product selectivity and catalytic activity are with reaction
It is reduced rapidly.In addition, with the development of nanotechnology, only by regulation chemical composition and the scale of control nanoparticle
Its limitation is gradually shown to improve catalyst performance.
Summary of the invention
In view of the above-mentioned problems, the present invention overcomes shortcoming in the prior art, a kind of multicomponent, Multi-scale model are provided
Application method of the novel Ni-Ca based composite catalyst of primitive ordered fabrication during catalytic pyrolysis of biomass.
The present invention solves technical problem and adopts the following technical scheme that a kind of Ni-Ca based composite catalyst, it is with following step
Suddenly prepare: (1) prepared by layered metal hydroxides (LDR) precursor: by Ni (NO3)2∙6H2O、Ca(NO3)2∙6H2O and Zn
(NO3)2∙6H2O or by Ni (NO3)2∙6H2O、Ca(NO3)2∙6H2O and Al (NO3)3∙9H2O, which is dissolved in deionized water, is made into salt-mixture
Solution；It is dissolved in wiring solution-forming in deionized water using organic acid as interlayer anion, separately with NaOH aqueous slkali as precipitating reagent；
The above-mentioned organic acid solution prepared and mixing salt solution are successively poured into reaction vessel, it under continual stirring conditions, will
NaOH solution, which is added dropwise in mixed solution, regulates and controls pH value in reaction, forms suspension after being added dropwise；24 ~ 72h of crystallization, gained is sunk
Solution centrifugation in shallow lake is washed to supernatant to be neutral, and grinding obtains Ni-Ca-Zn LDR precursor or Ni-Ca- after 80 DEG C of dry 12h
Al LDR precursor；
(2) calcining reduction: weighing Ni-Ca-Zn LDR precursor that a certain amount of step (1) obtains or Ni-Ca-Al LDR precursor is placed in
In tube-type atmosphere furnace, in air or inert atmosphere, 2h~4h is calcined under the conditions of temperature is 500 DEG C~800 DEG C, is naturally cooling to
Room temperature obtains forming Ni-Ca based composite catalyst by nano particle or nanometer sheet structural motif ordered fabrication.
Specific feature of the invention is in addition, the Ni-Ca based composite catalyst is deposited using Ni as the main active component of catalyzed conversion
It include W metal, NiO, NiAl in form2O4And Ni3ZnC0.7, CaO is as CO2Absorbent and cocatalyst component, wherein containing Ni
Object phase mass percentage is 48.2%-85.2%, and CaO mass percentage is 12.7%-15.8%.
Preparation step (1) organic acid is one of sodium salicylate and sodium benzoate.
Preparation step (1) solution final ph is controlled 8.0 ~ 8.5.
Preparation step (1) the Ni-Ca-Zn LDR precursor crystallization temperature is in room temperature ~ 100 DEG C；Preparation step (1) is described
Ni-Ca-Al LDR precursor crystallization temperature is at 120 DEG C ~ 160 DEG C.
The application also provide it is a kind of using the Ni-Ca based composite catalyst for preparing as described above in catalytic pyrolysis of biomass mistake
Application method in journey, it includes the following steps: that the Ni-Ca based composite catalyst of preparation is carried out tabletting, crushing, screening by (a),
Obtain the catalyst fines that granularity is 20 ~ 80 mesh；
(b) biomass material is loaded in fixed-bed reactor first-stage reactor, above-mentioned preparation is loaded in second reactor
The catalyst of 20 ~ 80 good mesh partial sizes, is passed through N2Air in reaction unit is discharged, while reactor is warming up to setting temperature
Degree, biomass material are pyrolyzed at a temperature of 600-900 DEG C, and generation is pyrolyzed steam in the N of 50mL/min2In 500- under carrying
800 DEG C are condensed in the cracking of Ni-Ca based composite catalyst surface, reformation, obtained cracking steam, are dried to obtain gas and liquid
Product.
Specific feature of the invention is in addition, biomass material described in step (b) is lignocellulose-like biomass.
The medicine have the advantages that the Ni-Ca base dual-function composite catalyst that the 1, present invention is prepared is by nano particle
Or nanometer sheet structural motif ordered fabrication forms, solving the unordered accumulation of traditional material structural motif causes activated centre covering to be asked
Topic, while the high load and high degree of dispersion of active component are realized, so that it is sufficiently exposed to catalyst surface, significantly increases and urge
Change the number of active sites that reactant can contact in reaction process.
2, the Ni-Ca based composite catalyst that the present invention is prepared shows higher anti-in biomass catalyzing conversion process
Answer activity.Ni-Ca-Zn catalyst can significantly improve synthesis gas H2/ CO ratio, the H under 600 DEG C of catalytic reaction temperatures2/ CO high
Up to 3.34.Ni-Ca-Al can significantly improve synthesis gas yield, show high heat stability under 800 DEG C of greater catalytic cracking temperatures
Property and high activity, gas production are up to 1015ml/g biomass；Meanwhile the Ni-Ca based composite catalyst energy that the present invention is prepared
It is enough that acid, aldehyde, ketone macromolecular intermediate product orientation deep conversion are accounted for into liquid for phenol and aromatic hydrocarbons high added value compound, content
90% or more body product.
3, the Ni-Ca based composite catalyst being prepared in the present invention possesses micropore-mesopore multi-stage artery structure, is conducive to
The diffusion mobility of reaction intermediate effectively inhibits carbon distribution in reaction process to be formed, so that catalyst is still protected after reacting 36h
Hold greater activity.
4, the step coprecipitation that the present invention uses is easy to operate, does not use without previously prepared template, reaction process
Organic reagent, product yield high, it is cheap, it can be applied to industrial scale production.
Specific embodiment
Embodiment 1: a kind of Ni-Ca based composite catalyst, it is prepared with following steps:
According to Ni2+: Ca2+: Zn2+The ratio that molar ratio is 1: 0.4: 0.6 weighs the Ni (NO of 21.81g3)2∙6H2O、7.09g
Ca(NO3)2∙6H2O and 13.39g Zn (NO3)2∙6H2O is added deionized water and is configured to 300 ml mixed solutions, weighs 36.64g
C6H5300 ml deionized water wiring solution-formings are added in COONa, separately weigh 8g NaOH deionized water is added and be configured to 400mL concentration and be
The aqueous slkali of 0.5M.By mixing salt solution and C6H5COONa solution pours into four-hole boiling flask, under mechanical stirring by NaOH solution
It is added drop-wise in above-mentioned mixed solution, so that final solution pH is 8.0, by gained slurries crystallization 48 hours under the conditions of 90 DEG C, uses
Deionized water washing, centrifugation to supernatant are in neutrality, 12 hours dry at 80 DEG C, and grinding obtains Ni-Ca-Zn LDR forerunner
Body.
10g Ni-Ca-Zn LDR presoma is weighed, uniformly divides and is placed in tube-type atmosphere furnace in Ci Zhou, in nitrogen
Under atmosphere, 600 DEG C are warming up to 10 DEG C/min, 2 hours is kept the temperature, is down to room temperature naturally to temperature and obtains Ni-Ca-Zn catalyst.
The Ni-Ca-Zn catalyst of above method preparation is in one-dimensional rod-like pattern, and length is about 2-3 μm, and diameter is about
53nm, nanoparticle are its structural motif, and average-size is about 11nm, and high uniformity is scattered in nanorod surfaces, does not occur
Agglomeration.Catalyst composition and mass percentage are Ni:15.4%, Ni3ZnC0.7: 40.6%, ZnO:30.4%, CaO:
13.6%, other impurities object phase is not found.
Using application method of the Ni-Ca based composite catalyst prepared as described above during catalytic pyrolysis of biomass,
It includes the following steps: that the Ni-Ca based composite catalyst of preparation is carried out tabletting, crushing, screening by (a), and obtaining granularity is 20 ~ 80
Purpose catalyst fines；
(b) load rice husk in fixed-bed reactor first-stage reactor, loaded in second reactor above-mentioned 20 prepared ~
The catalyst of 80 mesh partial sizes, is passed through N2Air in reaction unit is discharged, while reactor is warming up to set temperature, biomass
Material is pyrolyzed at a temperature of 600 DEG C, and generation is pyrolyzed steam in the N of 50mL/min2It is compound in Ni-Ca base in 600 DEG C under carrying
Catalyst surface cracking is reformed, and obtained cracking steam is condensed, is dried to obtain gas and product liquid.
The gas flow that rice husk thermal decomposition generates is 387mL/g, and the typical component of thick combustion gas is (volumn concentration): H2:
15.06%, CO:44.28%, CO2: 23.98%, CH4: 11.44%, C2-C3(ethylene, ethane, propane): 5.24%, H2/ CO ratio is
0.34。
The one-dimensional rod-like Ni-Ca-Zn catalyst prepared in aforementioned manners to rice husk carry out catalytic cracking, biomass pyrolytic,
Catalytic temperature is 600 DEG C.Experimental studies have found that the gas flow that catalytic pyrolysis generates is 725mL/g, gas component is (volume hundred
Divide content): H2: 59.13%, CO:17.70%, CO2: 10.32%, CH4: 8.06%, C2-C3(ethylene, ethane, propane): 4.79%,
Middle synthesis gas active principle content is 76.83vol%.Compared with pure pyrolysis, H2/ CO ratio improves significantly to 3.34 by 0.34, produces gas
Amount dramatically increases, CO2Content reduces by 57%.In addition, GC/MS analysis the result shows that, in pyrolysis gas in the macromoleculars such as acid, aldehyde, ketone
Between product be directed and be converted into the high added values compound such as phenol and aromatic hydrocarbons, content accounts for 71% He of product liquid respectively
22.1%.In the 36h of reaction, catalyst activity maintains to stablize, and post catalyst reaction carbon deposition rate is 2.36%, shows stronger anti-
Carbon distribution performance.
Embodiment 2: this embodiment place same as Example 1 repeats no more, the difference is that catalyst preparation process
In do not add Ca (NO3)2∙6H2O, according to Ni2+: Zn2+The ratio that molar ratio is 1: 1 weighs the Ni (NO of 21.81g3)2∙6H2O and
22.31g Zn(NO3)2∙6H2O.The Ni-Zn catalyst being prepared still keeps one-dimensional rod-like pattern, and length is about 1.8 μm, directly
Diameter is about 130nm, and nanoparticle is its structural motif, and average-size is about 22nm, is dispersed in nanorod surfaces.Catalyst
Composition and mass percentage are Ni:10.7%, Ni3ZnC0.7: 45.3%, ZnO:44% do not have found other impurities object phase.
Evaluating catalyst is carried out under experiment condition same as Example 1, research finds that the gas flow obtained after reaction is
456 mL/g, gas component are (volumn concentration): H2: 37.17%, CO:18.87%, CO2: 34.61%, CH4: 5.1%, C2-C3
(ethylene, ethane, propane): 4.25%, wherein synthesis gas active principle content is 56.04vol%, H2/ CO ratio is 1.97.With implementation
Example 1 is compared, when not adding CaO in catalyst as CO2When absorbent, CO in gained gaseous product2Content significantly increases, and produces gas
Amount and H2/ CO is declined, and catalytic activity reduces.Mainly since CaO can promote with CO2For product pyrolysis gas cracking and
The progress of the reactions such as Water gas shift/WGS, and then gas yield is improved, and promote the generation of hydrogen-rich gas.Service life is carried out to catalyst
And the discovery of anti-carbon performance study, in the 36h of reaction, gas production declines about 15%, and post catalyst reaction carbon deposition rate is
12.03%, it mainly can be further improved the dispersibility and catalyst alkalinity of active component, enhancing catalysis as carrier due to CaO
Agent anti-carbon performance.
Embodiment 3: this embodiment place same as Example 1 repeats no more, the difference is that catalyst calcination atmosphere
For air.The Ni-Ca-Zn catalyst being prepared still keeps one-dimensional rod-like pattern, and length is about 3 μm, and diameter is about 86nm, is received
Rice corpuscles is its structural motif, and average-size is about 18nm, and high uniformity is scattered in nanorod surfaces, does not occur reuniting existing
As.Catalyst composition and mass percentage are NiO:51.95%, ZnO:35.25%, CaO:12.8%, do not find other impurities object
Phase.
Evaluating catalyst is carried out under experiment condition same as Example 1, research finds the gas yield obtained after reaction
For 599mL/g, wherein group is divided into (volumn concentration): H2: 51.83%, CO:19.34%, CO2: 15.03%, CH4: 8.24%,
C2-C3(ethylene, ethane, propane): 5.56%, synthesis gas active principle accounting is 71.17 vol%, H2/ CO ratio is 2.68.With reality
Example 1 is applied to compare, when calcination atmosphere is air, gained Ni-Ca-Zn catalyst activity decreases, however compared with pure pyrolysis,
The catalyst still shows greater activity, to H2, the active principles such as CO show more highly selective, H2/ CO is also significantly greater than pure heat
Solution value, CO2Content reduces by 37.3%, effectively improves synthesis gas quality-improving.In addition, GC/MS analysis the result shows that, pyrolysis gas
The macromoleculars intermediate product such as acid, aldehyde, ketone, which is directed, in body is converted into the high added values compound such as phenol and aromatic hydrocarbons, content difference
Account for the 40.7% and 55.3% of product liquid.Service life and the discovery of anti-carbon performance study are carried out to catalyst, in the 36h of reaction,
Catalyst activity kept stable, post catalyst reaction carbon deposition rate are 4.03%.
Embodiment 4: this embodiment place same as Example 1 repeats no more, the difference is that catalyst maturing temperature
It is 800 DEG C.The Ni-Ca-Zn catalyst being prepared is in one-dimensional rod-like pattern, and length is about 2.2 μm, and diameter is about 67nm, is received
Rice corpuscles is its structural motif, and average-size is about 15nm, and high uniformity is scattered in nanorod surfaces, does not occur reuniting existing
As.Catalyst composition and mass percentage are Ni3ZnC0.7: 85.2%, CaO:15.8% do not have found other impurities object phase.
Evaluating catalyst is carried out under experiment condition same as Example 1, research finds the gas yield obtained after reaction
For 626mL/g, wherein group is divided into (volumn concentration): H2: 56.08%, CO:18.39%, CO2: 13.59%, CH4: 7.34%,
C2-C3(ethylene, ethane, propane): 4.60%, synthesis gas active principle accounting is 74.47 vol%, H2/ CO ratio is 3.05.With reality
It applies example 1 to compare, even if maturing temperature is increased to 800 DEG C, catalyst still keeps greater activity, to H2Show it is more highly selective,
H2/ CO ratio is up to 3.2, CO2Content reduces by 43.3%, significantly improves synthesis gas quality.In addition, GC/MS analysis the result shows that, pyrolysis
The macromoleculars intermediate product such as acid, aldehyde, ketone, which is directed, in gas is converted into the high added values compound such as phenol and aromatic hydrocarbons, content point
The 75.5% and 15.3% of product liquid is not accounted for.Service life and the discovery of anti-carbon performance study are carried out to catalyst, in the 36h of reaction
It is interior, catalyst activity be decreased slightly as it is low, post catalyst reaction carbon deposition rate be 5.82%.
Embodiment 5:
The preparation method of catalyst is same as Example 1 in this embodiment, and details are not described herein again, used catalyst structure and morphology with
Embodiment 1 is consistent, and Ni-Ca-Zn catalyst is in one-dimensional rod-like pattern, and length is about 2-3 μm, and diameter is about 53nm, nanoparticle
For its structural motif, average-size is about 11nm, and high uniformity is scattered in nanorod surfaces, agglomeration do not occur.Catalysis
Agent composition and mass percentage are Ni:15.4%, Ni3ZnC0.7: 40.6%, ZnO:30.4%, CaO:13.6% do not have found other
Impurity thing phase.
Difference from Example 1 is that 600 DEG C of biomass pyrolytic temperature holding is constant, and catalytic reaction temperature is by 600 DEG C
800 DEG C are increased to, the study found that the gas yield obtained after reaction is increased to 876mL/g, wherein gas component is (volume hundred
Divide content): H2: 51.97%, CO:18.36%, CO2: 15.83%, CH4: 8.15%, C2-C3(ethylene, ethane, propane): 5.69%,
H2/ CO ratio is 2.83, CO2Content reduces by 34%, and synthesis gas active principle volume accounting is 70.33%.Compared with Example 1, with
Reaction temperature increases, and catalyst still keeps greater activity, can be obviously improved gas yield.H2/ CO is than being also significantly greater than pure heat
Solution value.In addition, GC/MS analysis the result shows that, the macromoleculars intermediate product such as acid, aldehyde, ketone, which is directed, in pyrolysis gas is converted into benzene
The high added values compound such as phenol and aromatic hydrocarbons, content account for the 26.6% and 70.1% of product liquid respectively.Service life is carried out to catalyst
And the discovery of anti-carbon performance study, in the 36h of reaction, catalyst activity is decreased slightly as low, and post catalyst reaction carbon deposition rate is
6.81%。
Embodiment 6: a kind of Ni-Ca based composite catalyst, it is prepared with following steps:
According to Ni2+: Ca2+: Al3+The ratio that molar ratio is 1.5: 0.5: 1 weighs the Ni (NO of 21.81g3)2∙6H2O、5.904g
Ca(NO3)2∙6H2O and 18.757g Al (NO3)3∙9H2O is added deionized water and is configured to 200 ml mixed solutions, weighs 48.03g
NaC7H5O3200 ml deionized waters are added and are configured to solution, separately weighs 10g NaOH addition deionized water and is configured to 500mL concentration
For the aqueous slkali of 0.5M.By mixing salt solution and NaC7H5O3Solution pours into four-hole boiling flask, under mechanical stirring by NaOH solution
It is added drop-wise in above-mentioned mixed solution, so that final solution pH is 8.2, gained slurries is transferred to hydrothermal reaction kettle, in 120 DEG C of items
Crystallization 48 hours under part are washed with deionized, are centrifuged to supernatant and are in neutrality, and 12 hours dry at 80 DEG C, grinding obtains
NiCaAl-LDR presoma.
10g NiCaAl-LDR presoma is weighed, uniformly divides and is placed in tube-type atmosphere furnace in Ci Zhou, in nitrogen gas
Under atmosphere, 600 DEG C are warming up to 10 DEG C/min, 2 hours is kept the temperature, is down to room temperature naturally to temperature and obtains Ni-Ca-Al catalyst.
The Ni-Ca-Al catalyst of above method preparation is in three-dimensional flower-shaped pattern, and diameter is about 1.5 μm, and nanometer sheet is structure
Primitive, average-size be 100 nm, with a thickness of 20nm, nanometer sheet surface it is evenly dispersed Ni nano particle, average-size 6
There is not agglomeration in nm.Catalyst composition and mass percentage are Ni:50.8%, Al2O3: 34.4%, CaO:14.7%,
Other impurities object phase is not found.
Using application method of the Ni-Ca based composite catalyst prepared as described above during catalytic pyrolysis of biomass,
It includes the following steps: that the Ni-Ca based composite catalyst of preparation is carried out tabletting, crushing, screening by (a), and obtaining granularity is 20 ~ 80
Purpose catalyst fines；
(b) load rice husk in fixed-bed reactor first-stage reactor, loaded in second reactor above-mentioned 20 prepared ~
The three-dimensional flower-shaped Ni-Ca-Al catalyst of 80 mesh partial sizes, is passed through N2Air in reaction unit is discharged, while reactor being heated up
To set temperature, biomass material is pyrolyzed at a temperature of 600 DEG C, and generation is pyrolyzed steam in the N of 50mL/min2Under carrying in
600 DEG C are condensed in the cracking of Ni-Ca based composite catalyst surface, reformation, obtained cracking steam, are dried to obtain gas and liquid
Product.
Experimental studies have found that the gas flow that catalytic pyrolysis generates is 897mL/g, wherein gas component is that (volume basis contains
Amount): H2: 53.26%, CO:19.09%, CO2: 16.62%, CH4: 6.42%, C2-C3(ethylene, ethane, propane): 4.60%, synthesis gas
Active principle volume accounting is 72.35%.Compared with pure pyrolysis, H2/ CO ratio improves significantly to 2.79, CO by 0.342Content reduces
30.7%, synthesis gas quality is obviously optimized.In addition, GC/MS analysis the result shows that, in pyrolysis gas acid, aldehyde, ketone etc. greatly divides
Sub- intermediate product, which is directed, is converted into the high added values compound such as phenol and aromatic hydrocarbons, and content accounts for the 82.2% of product liquid respectively
With 9.9%.In the 36h of reaction, catalyst activity maintains to stablize, and post catalyst reaction carbon deposition rate is 3.19%, shows stronger
Anti-carbon performance.
Embodiment 7: this embodiment place same as Example 6 repeats no more, the difference is that catalyst preparation stepMiddle adjusting pH value of solution is 7.5.The Ni-Ca-Al catalyst of above method preparation still keeps three-dimensional flower-shaped pattern, and diameter is about
2.1 μm, nanometer sheet is structural motif, and average-size is 600 nm, with a thickness of 52nm, nanometer sheet surface it is evenly dispersed Ni nanometers
Particle, average-size are 25 nm, agglomeration do not occur.Catalyst composition and mass percentage are Ni:58.2%,
Al2O3: 39.5%, CaO:2.3% do not have found other impurities object phase.
Evaluating catalyst is carried out under experiment condition same as Example 6, research finds that the gas flow obtained after reaction is
532 mL/g, gas component are (volumn concentration): H2: 36.25%, CO:19.28%, CO2: 29.05%, CH4: 8.63%, C2-
C3(ethylene, ethane, propane): 6.79%, wherein synthesis gas active principle content is 55.53vol%, H2/ CO ratio is 1.88.With reality
It applies example 6 to compare, when reducing coprecipitation reaction pH value, micro CaO component only occurs in catalyst structure, so that in gaseous product
CO2Content increases, gas production, synthesis gas active principle content and H2/ CO is declined, mainly due to Ca2+It need to be higher
Ability and Ni under pH value condition2+、Al3+Coprecipitation reaction occurs, the CaO for roasting generation can promote with CO2For the pyrolysis gas of product
The progress of the reactions such as cracking and Water gas shift/WGS, and then gas yield is improved, and promote the generation of hydrogen-rich gas.To catalyst into
Row service life and the discovery of anti-carbon performance study, in the 36h of reaction, gas production declines about 18%, and post catalyst reaction carbon deposition rate is
14.86%, it mainly can be further improved the dispersibility and catalyst alkalinity of active component, enhancing catalysis as carrier due to CaO
Agent anti-carbon performance.
Embodiment 8: this embodiment place same as Example 6 repeats no more, the difference is that catalyst maturing temperature
It is 800 DEG C.The Ni-Ca-Al catalyst being prepared still keeps three-dimensional flower-shaped pattern, and diameter is about 1.8 μm, and structural motif is to receive
Rice piece, there is the metallic particles that a large amount of average-size is 12nm in nanometer sheet surface, and high uniformity disperses, and does not roll into a ball
Poly- phenomenon.Catalyst composition and mass percentage are Ni:52.2%, Al2O3: 35.1%, CaO:12.7% do not have found other impurities
Object phase.
Evaluating catalyst is carried out under experiment condition same as Example 6, research finds the gas yield obtained after reaction
For 758mL/g, wherein group is divided into (volumn concentration): H2: 51.44%, CO:18.98%, CO2: 19.05%, CH4: 5.43%,
C2-C3(ethylene, ethane, propane): 5.10%, synthesis gas active principle volume content is 70.42%, H2/ CO ratio is 2.71.With it is pure
Pyrolysis is compared, even if maturing temperature is increased to 800 DEG C, catalyst still keeps greater activity, and gas production and synthesis gas quality are obvious
Better than experimental result under this condition.In addition, GC/MS analysis the result shows that, production among the macromoleculars such as acid, aldehyde, ketone in pyrolysis gas
Object, which is directed, is converted into the high added values compound such as phenol and aromatic hydrocarbons, and content accounts for the 87.2% and 9.5% of product liquid respectively.It is right
Catalyst carries out service life and the discovery of anti-carbon performance study, and in the 36h of reaction, catalyst activity is decreased slightly as low, is catalyzed after reaction
Agent carbon deposition rate is 6.29%.
Embodiment 9: this embodiment place same as Example 6 repeats no more, the difference is that catalyst calcination atmosphere
For air.The Ni-Ca-Al catalyst being prepared still keeps three-dimensional flower-shaped pattern, and diameter is about 1.4 μm, and nanometer sheet is structure
Primitive, surface are dispersed by the nano particle high uniformity that a large amount of average-size is 18 nm, agglomeration do not occur.It urges
Agent composition and mass percentage are NiO:48.2%, NiAl2O4: 21.9%, Al2O3: 15.2%, CaO:14.7% do not have found it
His impurity thing phase.
Evaluating catalyst is carried out under experiment condition same as Example 6, research finds the gas yield obtained after reaction
For 793mL/g, wherein group is divided into (volumn concentration): H2: 52.95%, CO:19.83%, CO2: 16.13%, CH4: 6.14%,
C2-C3(ethylene, ethane, propane): 4.95%, synthesis gas active principle volume content is 72.78%, H2/ CO ratio is 2.67.With reality
It applies example 6 to compare, in air under roasting gained Ni-Ca-Al catalyst action, biomass pyrolytic gas production and synthesis gas quality are equal
It is decreased obviously, but still better than experimental results under pure pyrolytical condition.In addition, GC/MS analysis the result shows that, in pyrolysis gas
The macromoleculars intermediate product such as acid, aldehyde, ketone, which is directed, is converted into the high added values compound such as phenol and aromatic hydrocarbons, and content accounts for liquid respectively
The 84.4% of body product and 9.6%.Service life and the discovery of anti-carbon performance study, in the 36h of reaction, catalyst are carried out to catalyst
Activity be decreased slightly as it is low, post catalyst reaction carbon deposition rate be 8.24%.
Embodiment 10: the preparation method of catalyst is same as Example 6 in this embodiment, and details are not described herein again, used to urge
Agent structure and morphology and embodiment 6 are consistent, and Ni-Ca-Al catalyst is in three-dimensional flower-shaped pattern, and diameter is about 1.5 μm, and nanometer sheet is
Structural motif, average-size be 100 nm, with a thickness of 20nm, nanometer sheet surface it is evenly dispersed Ni nano particle, average-size
For 6 nm, there is not agglomeration.Catalyst composition and mass percentage are Ni:50.8%, Al2O3: 34.4%, CaO:
14.7%, other impurities object phase is not found.
Difference from Example 6 is that 600 DEG C of biomass pyrolytic temperature holding is constant, and catalytic reaction temperature is by 600 DEG C
800 DEG C are increased to, the study found that obtained gas yield increases rapidly as 1015mL/g after reaction, wherein gas component is (body
Product percentage composition): H2: 55.47%, CO:21.92%, CO2: 11.11%, CH4: 7.21%, C2-C3(ethylene, ethane, propane):
4.29%, H2/ CO ratio is 2.53, and synthesis gas active principle volume accounting is 77.39%.Compared with Example 6, it is urged in Ni-Ca-Al
Under agent effect, reaction temperature raising is obviously improved gas yield.Meanwhile the CO compared with pure pyrolysis2Content reduces by 53.7%.This
Outside, GC/MS analysis the result shows that, the macromoleculars intermediate product such as acid, aldehyde, ketone, which is directed, in pyrolysis gas is converted into phenol and aromatic hydrocarbons
Etc. high added values compound, content account for the 76.2% and 14.6% of product liquid respectively.Service life and anti-carbon are carried out to catalyst
Performance study discovery, in the 36h of reaction, catalyst activity kept stable, post catalyst reaction carbon deposition rate is 8.16%.
Claims (7)
1. a kind of preparation of Ni-Ca based composite catalyst, it is prepared with following steps:
(1) prepared by layered metal hydroxides precursor: by Ni (NO3)2∙6H2O、Ca(NO3)2∙6H2O and Zn (NO3)2∙6H2O will
Ni(NO3)2∙6H2O、Ca(NO3)2∙6H2O and Al (NO3)3∙9H2O, which is dissolved in deionized water, is made into mixing salt solution；By organic acid
Root is dissolved in wiring solution-forming in deionized water as interlayer anion, separately with NaOH aqueous slkali as precipitating reagent；It is prepared above-mentioned
Organic acid solution and mixing salt solution successively pour into reaction vessel, and under continual stirring conditions, NaOH solution is added dropwise to
Regulate and control pH value in reaction in mixed solution, forms suspension after being added dropwise；24 ~ 72h of crystallization by the centrifugation of gained precipitation solution, is washed
Washing to supernatant is neutrality, and grinding obtains Ni-Ca-Zn LDR precursor or Ni-Ca-Al LDR precursor after 80 DEG C of dry 12h；
(2) calcining reduction: weighing Ni-Ca-Zn LDR precursor that a certain amount of step (1) obtains or Ni-Ca-Al LDR precursor is placed in
In tube-type atmosphere furnace, in air or inert atmosphere, 2h~4h is calcined under the conditions of temperature is 500 DEG C~800 DEG C, is naturally cooling to
Room temperature obtains forming Ni-Ca based composite catalyst by nano particle or nanometer sheet structural motif ordered fabrication.
2. the preparation of Ni-Ca based composite catalyst according to claim 1, which is characterized in that the Ni-Ca base is compound to urge
For agent using Ni as the main active component of catalyzed conversion, existence form includes W metal, NiO, NiAl2O4And Ni3ZnC0.7, CaO conduct
CO2Absorbent and cocatalyst component, wherein the phase mass percentage of object containing Ni is 48.2%-85.2%, CaO mass percentage
For 12.7%-15.8%.
3. the preparation of Ni-Ca based composite catalyst according to claim 1, which is characterized in that preparation step (1) is described to be had
Machine acid group is one of sodium salicylate and sodium benzoate.
4. the preparation of Ni-Ca based composite catalyst according to claim 1, which is characterized in that the preparation step (1) is molten
Liquid final ph is controlled 8.0 ~ 8.5.
5. the preparation of Ni-Ca based composite catalyst according to claim 1, which is characterized in that preparation step (1) is described
Ni-Ca-Zn LDR precursor crystallization temperature is in room temperature ~ 100 DEG C；Preparation step (1) the Ni-Ca-Al LDR precursor crystallization temperature
At 120 DEG C ~ 160 DEG C.
6. a kind of application of Ni-Ca based composite catalyst prepared using claim 1 during catalytic pyrolysis of biomass,
It is characterized in that it includes the following steps:
(a) the Ni-Ca based composite catalyst of preparation is subjected to tabletting, crushing, screening, obtains the catalyst that granularity is 20 ~ 80 mesh
Powder；
(b) biomass material is loaded in fixed-bed reactor first-stage reactor, above-mentioned preparation is loaded in second reactor
The catalyst of 20 ~ 80 good mesh partial sizes, is passed through N2Air in reaction unit is discharged, while reactor is warming up to setting temperature
Degree, biomass material are pyrolyzed at a temperature of 600-900 DEG C, and generation is pyrolyzed steam in the N of 50mL/min2In 500- under carrying
800 DEG C are condensed in the cracking of Ni-Ca based composite catalyst surface, reformation, obtained cracking steam, are dried to obtain gas and liquid
Product.
7. application of the Ni-Ca based composite catalyst according to claim 6 during catalytic pyrolysis of biomass, feature
It is, biomass material described in step (b) is lignocellulose-like biomass.
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| CN114308093A (en) * | 2021-12-29 | 2022-04-12 | 太原理工大学 | High-load nickel-based carbide catalyst and preparation method and application thereof |
| CN114733527A (en) * | 2022-04-08 | 2022-07-12 | 同济大学 | Preparation method of Ca-Ni ash-based catalyst and hydrogen-rich synthesis gas |
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| CN112221507A (en) * | 2020-10-28 | 2021-01-15 | 华南理工大学 | Organic acid intercalated Ni-CaO-Al2O3Bifunctional catalyst, preparation method and application thereof |
| CN114308093A (en) * | 2021-12-29 | 2022-04-12 | 太原理工大学 | High-load nickel-based carbide catalyst and preparation method and application thereof |
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| CN115041173A (en) * | 2022-07-09 | 2022-09-13 | 山东省科学院能源研究所 | Ferronickel bimetallic flower-like cluster catalyst and preparation and application methods thereof |
| CN115041173B (en) * | 2022-07-09 | 2024-02-02 | 山东省科学院能源研究所 | Ferronickel bimetallic flower-like cluster catalyst and preparation and application methods thereof |
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