CN110227468B - Preparation of nickel-calcium based composite catalyst and application of nickel-calcium based composite catalyst in biomass catalytic pyrolysis process - Google Patents
Preparation of nickel-calcium based composite catalyst and application of nickel-calcium based composite catalyst in biomass catalytic pyrolysis process Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000002028 Biomass Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 12
- JEZHBSJTXKKFMV-UHFFFAOYSA-N calcium nickel Chemical compound [Ca].[Ni] JEZHBSJTXKKFMV-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000000197 pyrolysis Methods 0.000 claims abstract description 39
- 229910018107 Ni—Ca Inorganic materials 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000012263 liquid product Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000002407 reforming Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 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 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 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
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 15
- 239000007789 gas Substances 0.000 description 83
- 229910052799 carbon Inorganic materials 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 description 23
- 230000008021 deposition Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 239000013067 intermediate product Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 12
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- 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
- 239000001294 propane Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012535 impurity 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
- 238000005054 agglomeration Methods 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 239000011575 calcium Substances 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 229910018605 Ni—Zn Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 229920002488 Hemicellulose Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 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
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- 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
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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
- 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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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- 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
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- 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
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- 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
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- 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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- 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
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Abstract
Preparation of a nickel-calcium based composite catalyst and application of the nickel-calcium based composite catalyst in a biomass catalytic pyrolysis process, wherein the preparation comprises preparation of a layered metal hydroxide precursor; calcining and reducing to obtain the Ni-Ca-based composite catalyst which is formed by orderly assembling nano-particles or nano-sheet structural elements. The application of the catalyst in the biomass catalytic pyrolysis process comprises the following steps: tabletting, crushing and screening the prepared Ni-Ca-based composite catalyst to obtain catalyst powder with the granularity of 20 to 80 meshes; filling biomass materials in a primary reactor of a fixed bed reaction device, filling the prepared catalyst with the particle size of 20-80 meshes in a secondary reactor, and introducing N 2 And discharging air in the reaction device, simultaneously heating the reactor to a set temperature, cracking and reforming pyrolysis steam generated by pyrolysis of the biomass material on the surface of the Ni-Ca-based composite catalyst, and condensing and drying the obtained pyrolysis steam to obtain gas and liquid products.
Description
Technical Field
The invention belongs to the field of energy and chemical engineering, and particularly relates to an application method of a Ni-Ca-based composite catalyst orderly assembled by nano-particles or nano-sheet structural elements in a biomass catalytic pyrolysis process.
Background
The biomass-based liquid fuel is a research and development hotspot and a future development direction in the field of biomass resource conversion. The lignocellulose biomass raw materials with complex structures and various varieties are converted into synthesis gas with simple and uniform composition through pyrolysis, and then the synthesis gas is assembled into the liquid fuel for vehicles and aviation with ideal component composition and molecular structures through a controllable process, so that a high-valued utilization mode which is accurate, controllable and easy to realize is provided for biomass resources. However, fuel synthesis processes typically require the hydrogen to carbon ratio (H) of the syngas 2 /CO) to reach 2~3 or higher hydrogen-rich level, the gas product directly obtained from biomass pyrolysis needs to be deeply regulated and controlled by water gas shift process to obtain proper H 2 The ratio of/CO; at the same time, CO is in the pyrolysis gas 2 The existence of the catalyst has certain influence on the efficiency and energy consumption of the subsequent synthesis gas conversion process, and needs to be on CO 2 And carrying out in-situ absorption and removal. In addition, in the pyrolysis process, macromolecular polymers such as cellulose, hemicellulose, lignin and the like in the biomass cannot be completely converted, so that macromolecular products such as acid, aldehyde, ketone, benzene ring, polycyclic compounds and the like are inevitably generated in the pyrolysis gas product. The presence of these macromolecules is detrimental to the production of liquid fuels based on syngas platforms. Therefore, the H needs to be solved in the biomass pyrolysis process taking the synthesis gas as the target product 2 Adjustment of the/CO ratio, CO 2 Removal, directional deep conversion of macromolecular intermediate products and the like.
Use of catalyst material to remove H from pyrolysis gas 2 、CO、CO 2 、CH 4 、H 2 Reforming O micromolecular gas and CO 2 The synthesis gas purification and component adjustment can be realized by reaction coupling of in-situ absorption, water gas shift and the like. In addition, the biomass pyrolysis gas can convert macromolecule intermediate products into short-chain intermediate products through cracking, deoxidation and dealkylation through on-line catalytic cracking, and simultaneously generate more micromolecule gases, thereby obviously improving the yield of the synthesis gas. Therefore, the biomass on-line catalytic conversion is one of improving the quality of the synthesis gas and the utilization rate of the biomassThe most efficient method. The dispersity of the catalytic active center and the number of exposed active sites are the core factors affecting the catalytic activity of the material. At present, scholars at home and abroad mainly adopt large molecules such as catalyst material cracking tar and the like which are randomly stacked by particles to improve the gas yield, and a large amount of steam is added in the pyrolysis process to reform so as to improve the quality of the synthesis gas, and the research is mainly focused on the optimization of the types of active components and carriers. However, disordered accumulation and aggregation of the structure often cause coverage of active centers and blockage of channels in the reaction process, so that the selectivity and catalytic activity of target products are rapidly reduced along with the reaction. In addition, with the development of nanotechnology, the improvement of catalyst performance by merely controlling the chemical composition and the size of nanoparticles has gradually shown its limitations.
Disclosure of Invention
Aiming at the problems, the invention overcomes the defects in the prior art and provides an application method of a novel Ni-Ca-based composite catalyst with orderly assembled multi-component and multi-scale structural elements in the catalytic pyrolysis process of biomass.
The technical scheme adopted by the invention for solving the technical problems is as follows: a Ni-Ca based composite catalyst is prepared by the following steps: (1) layered metal hydroxide (LDR) precursor preparation: mixing Ni (NO) 3 ) 2 ∙6H 2 O、Ca(NO 3 ) 2 ∙6H 2 O and Zn (NO) 3 ) 2 ∙6H 2 O or Ni (NO) 3 ) 2 ∙6H 2 O、Ca(NO 3 ) 2 ∙6H 2 O and Al (NO) 3 ) 3 ∙9H 2 Dissolving O in deionized water to prepare a mixed salt solution; dissolving organic acid radical as interlayer anion in deionized water to prepare solution, and additionally preparing NaOH aqueous alkali as a precipitator; pouring the prepared organic acid radical solution and the mixed salt solution into a reaction container in sequence, dropwise adding a NaOH solution into the mixed solution under the condition of continuous stirring to regulate and control the pH value of the reaction, and forming a suspension after dropwise adding; crystallizing for 24 to 72h, centrifuging and washing the obtained precipitate solution until the supernatant is neutral, drying at 80 ℃ for 12h, and grinding to obtain a precursor Ni-Ca-Zn LDR or a precursor Ni-Ca-Al LDRA body;
(2) Calcining and reducing: weighing a certain amount of the Ni-Ca-Zn LDR precursor or the Ni-Ca-Al LDR precursor obtained in the step (1), placing the precursor or the Ni-Ca-Al LDR precursor into a tubular atmosphere furnace, calcining for 2 to 4 hours in the air or inert atmosphere at the temperature of 500 to 800 ℃, and naturally cooling to room temperature to obtain the Ni-Ca-based composite catalyst which is formed by orderly assembling nano-particles or nano-sheet structure elements.
The specific characteristics of the invention are that the Ni-Ca based composite catalyst takes Ni as a main catalytic conversion active component, and the existing form of the Ni-Ca based composite catalyst comprises metal Ni, niO and NiAl 2 O 4 And Ni 3 ZnC 0.7 CaO as CO 2 The absorbent and the cocatalyst components comprise 48.2-85.2 mass percent of Ni phase and 12.7-15.8 mass percent of CaO.
The organic acid radical in the preparation step (1) is one of sodium salicylate and sodium benzoate.
The final pH value of the solution in the preparation step (1) is controlled to be 8.0-8.5.
The crystallization temperature of the Ni-Ca-Zn LDR precursor in the preparation step (1) is between room temperature and 100 ℃; the crystallization temperature of the Ni-Ca-Al LDR precursor in the preparation step (1) is 120-160 ℃.
The application also provides an application method of the Ni-Ca-based composite catalyst prepared by the method in the biomass catalytic pyrolysis process, which comprises the following steps: (a) Tabletting, crushing and screening the prepared Ni-Ca-based composite catalyst to obtain catalyst powder with the granularity of 20 to 80 meshes;
(b) Filling biomass materials in a primary reactor of a fixed bed reaction device, filling the prepared catalyst with the particle size of 20-80 meshes in a secondary reactor, and introducing N 2 Discharging air in the reaction device, simultaneously heating the reactor to a set temperature, pyrolyzing the biomass material at 600-900 ℃, and generating pyrolysis steam with N of 50mL/min 2 Carrying the catalyst on the surface of the Ni-Ca-based composite catalyst at 500-800 ℃, cracking and reforming, condensing and drying the obtained cracking steam to obtain gas and liquid products.
The invention is also characterized in that the biomass material in the step (b) is lignocellulose biomass.
The invention has the beneficial effects that: 1. the Ni-Ca-based bifunctional composite catalyst prepared by the invention is formed by orderly assembling nano-particles or nano-sheet structural elements, solves the problem of active center coverage caused by disordered accumulation of the structural elements of the traditional material, simultaneously realizes high load and high dispersion of active components, fully exposes the active components on the surface of the catalyst, and obviously increases the number of active sites which can be contacted by reactants in the catalytic reaction process.
2. The Ni-Ca-based composite catalyst prepared by the invention shows higher reaction activity in the process of biomass catalytic conversion. The Ni-Ca-Zn catalyst can obviously improve the synthesis gas H 2 Ratio of/CO, catalytic reaction temperature of 600 ℃ H 2 the/CO is up to 3.34. The Ni-Ca-Al can obviously improve the yield of the synthesis gas, and shows high thermal stability and high activity at a high catalytic cracking temperature of 800 ℃, and the gas yield is up to 1015ml/g of biomass; meanwhile, the Ni-Ca-based composite catalyst prepared by the invention can directionally and deeply convert macromolecular intermediate products of acid, aldehyde and ketone into high value-added compounds of phenol and aromatic hydrocarbon, and the content of the high value-added compounds accounts for more than 90% of that of the liquid product.
3. The Ni-Ca-based composite catalyst prepared by the invention has a micropore-mesopore multi-level pore channel structure, is beneficial to the migration and diffusion of reaction intermediate products, effectively inhibits the formation of carbon deposition in the reaction process, and enables the catalyst to still keep higher activity after reacting for 36 hours.
4. The one-step coprecipitation method adopted by the invention is simple to operate, does not need to prepare a template agent in advance, does not use an organic reagent in the reaction process, has high product yield and low cost, and can be applied to industrial large-scale production.
Detailed Description
Example 1: a Ni-Ca based composite catalyst is prepared by the following steps:
The Ni-Ca-Zn catalyst prepared by the method is in a one-dimensional rod-like shape, the length is about 2-3 mu m, the diameter is about 53nm, the nano particles are structural elements of the Ni-Ca-Zn catalyst, the average size is about 11nm, the Ni-Ca-Zn catalyst is highly and uniformly dispersed on the surface of the nano rods, and the agglomeration phenomenon does not occur. The catalyst comprises the following components in percentage by mass: 15.4% of Ni 3 ZnC 0.7 :40.6%, znO:30.4%, caO:13.6%, no other impurity phases were found.
The application method of the Ni-Ca-based composite catalyst prepared as described above in the biomass catalytic pyrolysis process comprises the following steps: (a) Tabletting, crushing and screening the prepared Ni-Ca-based composite catalyst to obtain catalyst powder with the granularity of 20-80 meshes;
(b) Rice hulls are filled in a primary reactor of a fixed bed reaction device, the prepared catalyst with the particle size of 20-80 meshes is filled in a secondary reactor, and N is introduced 2 Exhausting air in the reaction device, and simultaneously heating the reactor to a set temperatureThe biomass material is pyrolyzed at the temperature of 600 ℃, and the generated pyrolysis steam is N of 50mL/min 2 Carrying the catalyst on the surface of the Ni-Ca-based composite catalyst at 600 ℃, cracking and reforming the catalyst, condensing and drying the obtained cracking steam to obtain gas and liquid products.
The gas generated by rice hull pyrolysis is 387mL/g, and the typical components of the crude fuel gas are as follows (volume percentage): h 2 ：15.06%、CO：44.28%、CO 2 ：23.98%、CH 4 ：11.44%，C 2 -C 3 (ethylene, ethane, propane): 5.24%, H 2 the/CO ratio was 0.34.
The rice hull is catalytically cracked by the one-dimensional rod-shaped Ni-Ca-Zn catalyst prepared by the method, and the biomass pyrolysis and catalysis temperatures are 600 ℃. Experimental study shows that the gas quantity generated by catalytic pyrolysis is 725mL/g, and the gas components are as follows (volume percentage): h 2 ：59.13%、CO：17.70%、CO 2 ：10.32%、CH 4 ：8.06%，C 2 -C 3 (ethylene, ethane, propane): 4.79 percent, wherein the content of the effective components of the synthesis gas is 76.83vol percent. In contrast to pure pyrolysis, H 2 the/CO ratio is remarkably improved from 0.34 to 3.34, the gas production is remarkably increased, and CO is remarkably reduced 2 The content is reduced by 57 percent. In addition, the GC/MS analysis result shows that macromolecular intermediate products such as acid, aldehyde, ketone and the like in the pyrolysis gas are directionally converted into high-value-added compounds such as phenol, aromatic hydrocarbon and the like, and the content of the macromolecular intermediate products respectively accounts for 71 percent and 22.1 percent of the liquid product. Within 36h of reaction, the activity of the catalyst is maintained stable, the carbon deposition rate of the catalyst after the reaction is 2.36%, and the catalyst shows stronger carbon deposition resistance.
Example 2: this example is the same as example 1 and will not be repeated except that Ca (NO) is not added during the preparation of the catalyst 3 ) 2 ∙6H 2 O, according to Ni 2+ ：Zn 2+ 21.81g of Ni (NO) were weighed out in a molar ratio of 1: 1 3 ) 2 ∙6H 2 O and 22.31g Zn (NO) 3 ) 2 ∙6H 2 And O. The prepared Ni-Zn catalyst still maintains the one-dimensional rod-like morphology, the length is about 1.8 mu m, the diameter is about 130nm, the nano particles are structural elements of the Ni-Zn catalyst, the average size is about 22nm, and the Ni-Zn catalyst is uniformly dispersed on the surface of the nano rods. The catalyst comprises the following components in percentage by mass: 10.7% of Ni 3 ZnC 0.7 :45.3%, znO:44%, no other impurity phases were found.
The catalyst evaluation was carried out under the same experimental conditions as in example 1, and it was found that the amount of gas obtained after the reaction was 456 mL/g, and the gas components (volume percentage): h 2 ：37.17%、CO：18.87%、CO 2 ：34.61%、CH 4 ：5.1%，C 2 -C 3 (ethylene, ethane, propane): 4.25 percent, wherein the content of the effective components of the synthesis gas is 56.04vol percent, H 2 The ratio/CO was 1.97. In comparison with example 1, no CaO was added to the catalyst as CO 2 When absorbing agent, CO in obtained gas product 2 The content is obviously increased, and the gas production and H are 2 the/CO is reduced and the catalytic activity is reduced. Mainly because CaO can promote CO 2 The pyrolysis gas cracking and water gas shift of the product are carried out, so that the gas yield is improved, and the generation of hydrogen-rich gas is promoted. Research on the service life and the anti-carbon deposition performance of the catalyst shows that the gas yield is reduced by about 15% within 36h of the reaction, the carbon deposition rate of the catalyst after the reaction is 12.03%, and the CaO serving as a carrier can further improve the dispersibility of the active component and the alkalinity of the catalyst and enhance the anti-carbon deposition performance of the catalyst.
Example 3: this example is the same as example 1 and will not be described again except that the catalyst calcination atmosphere is air. The prepared Ni-Ca-Zn catalyst still maintains a one-dimensional rod-like shape, the length is about 3 mu m, the diameter is about 86nm, the nano particles are structural elements of the catalyst, the average size is about 18nm, the catalyst is highly and uniformly dispersed on the surface of the nano rod, and the agglomeration phenomenon does not occur. The catalyst comprises the following components in percentage by mass: 51.95%, znO:35.25%, caO:12.8%, no other impurity phases were found.
The catalyst evaluation was carried out under the same experimental conditions as in example 1, and it was found that the gas yield obtained after the reaction was 599mL/g, in which the components (volume percentage): h 2 ：51.83%、CO：19.34%、CO 2 ：15.03%、CH 4 ：8.24%，C 2 -C 3 (ethylene, ethane, propane): 5.56 percent of the total weight of the steel,the effective component of the synthetic gas accounts for 71.17 vol%, H 2 the/CO ratio was 2.68. The obtained Ni-Ca-Zn catalyst was reduced in activity when the calcination atmosphere was air as compared with example 1, but the catalyst still showed higher activity against H than that of pure pyrolysis 2 The effective components such as CO and the like show higher selectivity, H 2 CO is also significantly higher than the pure pyrolysis value, CO 2 The content is reduced by 37.3 percent, and the quality improvement of the synthesis gas is effectively improved. In addition, GC/MS analysis results show that macromolecular intermediate products such as acid, aldehyde and ketone in the pyrolysis gas are directionally converted into high value-added compounds such as phenol and aromatic hydrocarbon, and the content of the macromolecular intermediate products respectively accounts for 40.7% and 55.3% of the liquid product. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is basically kept stable within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 4.03%.
Example 4: this example is the same as example 1 and will not be described again except that the catalyst calcination temperature is 800 ℃. The prepared Ni-Ca-Zn catalyst is in a one-dimensional rod-like shape, the length is about 2.2 mu m, the diameter is about 67nm, the nano particles are structural elements of the catalyst, the average size is about 15nm, the catalyst is highly and uniformly dispersed on the surface of the nano rods, and the agglomeration phenomenon does not occur. The catalyst comprises Ni 3 ZnC 0.7 :85.2%, caO:15.8%, no other impurity phases were found.
The catalyst evaluation was carried out under the same experimental conditions as in example 1 and it was found that the gas yield obtained after the reaction was 626mL/g, wherein the components (volume percent): h 2 ：56.08%、CO：18.39%、CO 2 ：13.59%、CH 4 ：7.34%，C 2 -C 3 (ethylene, ethane, propane): 4.60 percent, the effective component of the synthetic gas accounts for 74.47 vol percent, and H 2 the/CO ratio was 3.05. The catalyst remained highly active against H even when the calcination temperature was raised to 800 ℃ as compared with example 1 2 Exhibits a high selectivity, H 2 The ratio of CO/CO is as high as 3.2 2 The content is reduced by 43.3 percent, and the quality of the synthesis gas is obviously improved. In addition, GC/MS analysis results show that macromolecular intermediate products such as acid, aldehyde, ketone and the like in pyrolysis gas are directionally converted into high-adsorption products such as phenol, aromatic hydrocarbon and the likeThe value-added compounds were present in amounts of 75.5% and 15.3% of the liquid product, respectively. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is slightly reduced within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 5.82%.
Example 5:
the preparation method of the catalyst in the embodiment is the same as that in the embodiment 1, and is not repeated here, the structural morphology of the used catalyst is consistent with that in the embodiment 1, the Ni-Ca-Zn catalyst is in a one-dimensional rod shape, the length is about 2-3 mu m, the diameter is about 53nm, the nano particles are structural elements of the Ni-Ca-Zn catalyst, the average size is about 11nm, the Ni-Ca-Zn catalyst is highly uniformly dispersed on the surface of the nano rods, and the agglomeration phenomenon does not occur. The catalyst comprises the following components in percentage by mass: 15.4% of Ni 3 ZnC 0.7 :40.6%, znO:30.4%, caO:13.6%, no other impurity phases were found.
The difference from the example 1 is that the pyrolysis temperature of the biomass is kept unchanged at 600 ℃, the catalytic reaction temperature is increased from 600 ℃ to 800 ℃, and the research shows that the yield of the gas obtained after the reaction is increased to 876mL/g, wherein the gas components are (volume percentage): h 2 ：51.97%、CO：18.36%、CO 2 ：15.83%、CH 4 ：8.15%，C 2 -C 3 (ethylene, ethane, propane): 5.69%, H 2 The ratio of/CO was 2.83, 2 the content is reduced by 34 percent, and the volume ratio of the effective components of the synthesis gas is 70.33 percent. Compared with example 1, the catalyst still maintains higher activity with the increase of the reaction temperature, and the gas yield can be obviously improved. H 2 the/CO ratio is also significantly higher than the pure pyrolysis value. In addition, the GC/MS analysis result shows that macromolecular intermediate products such as acid, aldehyde, ketone and the like in the pyrolysis gas are directionally converted into high-value-added compounds such as phenol, aromatic hydrocarbon and the like, and the content of the macromolecular intermediate products respectively accounts for 26.6% and 70.1% of the liquid product. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is slightly reduced within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 6.81 percent.
Example 6: a Ni-Ca based composite catalyst is prepared by the following steps:
The Ni-Ca-Al catalyst prepared by the method is in a three-dimensional flower-like shape, the diameter is about 1.5 mu m, the nanosheets are structural elements, the average size is 100 nm, the thickness is 20nm, ni nanoparticles are uniformly dispersed on the surface of the nanosheets, the average size is 6nm, and the agglomeration phenomenon does not occur. The catalyst comprises the following components in percentage by mass: 50.8% of Al 2 O 3 :34.4%, caO:14.7%, no other impurity phases were found.
The application method of the Ni-Ca-based composite catalyst prepared as described above in the biomass catalytic pyrolysis process comprises the following steps: (a) Tabletting, crushing and screening the prepared Ni-Ca-based composite catalyst to obtain catalyst powder with the granularity of 20-80 meshes;
（b）rice hulls are filled in a primary reactor of a fixed bed reaction device, the prepared three-dimensional flower-shaped Ni-Ca-Al catalyst with the grain diameter of 20-80 meshes is filled in a secondary reactor, and N is introduced 2 Discharging air in the reaction device, simultaneously heating the reactor to a set temperature, pyrolyzing the biomass material at 600 ℃, and generating pyrolysis steam with N of 50mL/min 2 Carrying the catalyst on the surface of the Ni-Ca-based composite catalyst at 600 ℃, cracking and reforming the catalyst, condensing and drying the obtained cracking steam to obtain gas and liquid products.
Experimental study shows that the amount of gas generated by catalytic pyrolysis is 897mL/g, wherein the gas components are as follows (volume percentage): h 2 ：53.26%、CO：19.09%、CO 2 ：16.62%、CH 4 ：6.42%，C 2 -C 3 (ethylene, ethane, propane): 4.60 percent and the volume ratio of the effective components of the synthesis gas is 72.35 percent. In contrast to pure pyrolysis, H 2 The ratio of the/CO is obviously improved to 2.79 from 0.34 2 The content is reduced by 30.7 percent, and the quality of the synthesis gas is obviously optimized. In addition, GC/MS analysis results show that macromolecular intermediate products such as acid, aldehyde and ketone in the pyrolysis gas are directionally converted into high value-added compounds such as phenol and aromatic hydrocarbon, and the content of the macromolecular intermediate products respectively accounts for 82.2% and 9.9% of the liquid product. Within 36h of reaction, the activity of the catalyst is maintained stable, the carbon deposition rate of the catalyst after the reaction is 3.19%, and the catalyst shows stronger carbon deposition resistance.
Example 7: this example is the same as example 6 and will not be repeated except that the catalyst preparation step
The pH of the solution was adjusted to 7.5. The Ni-Ca-Al catalyst prepared by the method still maintains the three-dimensional flower-like morphology, the diameter is about 2.1 mu m, the nanosheets are structural elements, the average size is 600 nm, the thickness is 52nm, ni nanoparticles are uniformly dispersed on the surface of the nanosheets, the average size is 25 nm, and the agglomeration phenomenon does not occur. The catalyst comprises the following components in percentage by mass: 58.2% of Al 2 O 3 :39.5%, caO:2.3%, no other impurity phases were found.
Catalysis was carried out under the same experimental conditions as in example 6Agent evaluation, and research shows that the gas quantity obtained after the reaction is 532 mL/g, and the gas components are (volume percentage): h 2 ：36.25%、CO：19.28%、CO 2 ：29.05%、CH 4 ：8.63%，C 2 -C 3 (ethylene, ethane, propane): 6.79 percent, wherein the content of effective components of the synthesis gas is 55.53vol percent, and H 2 the/CO ratio was 1.88. In comparison with example 6, when the pH value of the coprecipitation reaction was lowered, only a trace amount of CaO component was present in the catalyst structure, so that CO in the gaseous product 2 Increased content, gas production, content of effective components of synthesis gas and H 2 all/CO were reduced mainly due to Ca 2+ Need to react with Ni under the condition of higher pH value 2+ 、Al 3+ The coprecipitation reaction occurs, and CaO generated by roasting can be promoted by CO 2 The pyrolysis gas cracking and water gas shift of the product are carried out, so that the gas yield is improved, and the generation of hydrogen-rich gas is promoted. Research on the service life and the anti-carbon deposition performance of the catalyst shows that the gas yield is reduced by about 18% within 36h of the reaction, the carbon deposition rate of the catalyst after the reaction is 14.86%, and the CaO serving as a carrier can further improve the dispersibility of the active component and the alkalinity of the catalyst and enhance the anti-carbon deposition performance of the catalyst.
Example 8: this example is the same as example 6 and will not be repeated except that the catalyst calcination temperature is 800 ℃. The prepared Ni-Ca-Al catalyst still maintains three-dimensional flower-like morphology, the diameter is about 1.8 mu m, structural elements are nanosheets, a large number of metal particles with the average size of 12nm appear on the surfaces of the nanosheets, and the nanosheets are highly uniformly dispersed without agglomeration. The catalyst comprises the following components in percentage by mass: 52.2% of Al 2 O 3 :35.1%, caO:12.7%, no other impurity phases were found.
The evaluation of the catalyst was carried out under the same experimental conditions as in example 6, and it was found that the gas yield obtained after the reaction was 758mL/g, wherein the components (volume percentage): h 2 ：51.44%、CO：18.98%、CO 2 ：19.05%、CH 4 ：5.43%，C 2 -C 3 (ethylene, ethane, propane): 5.10 percent, the volume content of the effective components of the synthetic gas is 70.42 percent, and H 2 The ratio/CO was 2.71. Compared with pure pyrolysis, the catalyst still keeps higher activity even if the roasting temperature is raised to 800 ℃, and the gas yield and the quality of the synthesis gas are obviously superior to the experimental results under the condition. In addition, GC/MS analysis results show that macromolecular intermediate products such as acid, aldehyde and ketone in the pyrolysis gas are directionally converted into high value-added compounds such as phenol and aromatic hydrocarbon, and the content of the macromolecular intermediate products respectively accounts for 87.2% and 9.5% of the liquid product. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is slightly reduced within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 6.29 percent.
Example 9: this example is the same as example 6 and will not be described again except that the catalyst calcination atmosphere is air. The prepared Ni-Ca-Al catalyst still keeps a three-dimensional flower-like shape, the diameter is about 1.4 mu m, the nanosheets are structural elements, the surfaces of the nanosheets are highly and uniformly dispersed by a large number of nanoparticles with the average size of 18nm, and the agglomeration phenomenon is avoided. The catalyst comprises the following components in percentage by mass: 48.2% of NiAl 2 O 4 ：21.9%，Al 2 O 3 :15.2%, caO:14.7%, no other impurity phases were found.
Evaluation of the catalyst was carried out under the same experimental conditions as in example 6, and it was found that the gas yield obtained after the reaction was 793mL/g, in which the components (volume percentage): h 2 ：52.95%、CO：19.83%、CO 2 ：16.13%、CH 4 ：6.14%，C 2 -C 3 (ethylene, ethane, propane): 4.95 percent, the volume content of the effective component of the synthetic gas is 72.78 percent, and H 2 the/CO ratio was 2.67. Compared with example 6, the biomass pyrolysis gas yield and the synthesis gas quality are both obviously reduced under the action of the Ni-Ca-Al catalyst obtained by roasting in the air, but still better than the experimental results obtained under the pure pyrolysis condition. In addition, the GC/MS analysis result shows that macromolecular intermediate products such as acid, aldehyde, ketone and the like in the pyrolysis gas are directionally converted into high-value-added compounds such as phenol, aromatic hydrocarbon and the like, and the content of the macromolecular intermediate products respectively accounts for 84.4% and 9.6% of the liquid product. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is slightly reduced within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 8.24%.
Example 10: the preparation method of the catalyst in the embodiment is the same as that in the embodiment 6, and is not repeated here, the structural morphology of the used catalyst is consistent with that in the embodiment 6, the Ni-Ca-Al catalyst is in a three-dimensional flower-like morphology, the diameter is about 1.5 mu m, the nanosheets are structural elements, the average size is 100 nm, the thickness is 20nm, ni nanoparticles are uniformly dispersed on the surface of the nanosheets, the average size is 6nm, and no agglomeration phenomenon occurs. The catalyst comprises the following components in percentage by mass: 50.8% of Al 2 O 3 :34.4%, caO:14.7%, no other impurity phases were found.
The difference from example 6 is that the pyrolysis temperature of biomass is kept constant at 600 ℃, the catalytic reaction temperature is increased from 600 ℃ to 800 ℃, and the research shows that the gas yield obtained after the reaction is rapidly increased to 1015mL/g, wherein the gas components are as follows (volume percentage): h 2 ：55.47%、CO：21.92%、CO 2 ：11.11%、CH 4 ：7.21%，C 2 -C 3 (ethylene, ethane, propane): 4.29%, H 2 The ratio of/CO is 2.53, and the volume ratio of the effective components of the synthesis gas is 77.39 percent. The increase in reaction temperature significantly increased the gas yield compared to example 6 with the Ni-Ca-Al catalyst. At the same time, CO is present in comparison with pure pyrolysis 2 The content is reduced by 53.7%. In addition, GC/MS analysis results show that macromolecular intermediate products such as acid, aldehyde and ketone in the pyrolysis gas are directionally converted into high value-added compounds such as phenol and aromatic hydrocarbon, and the content of the macromolecular intermediate products respectively accounts for 76.2% and 14.6% of the liquid product. The research on the service life and the carbon deposition resistance of the catalyst shows that the activity of the catalyst is basically kept stable within 36 hours of the reaction, and the carbon deposition rate of the catalyst after the reaction is 8.16%.
Claims (3)
1. A preparation method of Ni-Ca based composite catalyst is characterized in that the catalyst is prepared by the following steps: (1) preparation of layered metal hydroxide precursor: mixing Ni (NO) 3 ) 2 ∙6H 2 O、Ca(NO 3 ) 2 ∙6H 2 O and Zn (NO) 3 ) 2 ∙6H 2 Dissolving O in deionized water to prepare a mixed salt solution; dissolving organic acid radical as interlayer anion in deionized water to obtain solution, and adding NaOH to obtain alkali solutionThe liquid is used as a precipitating agent; pouring the prepared organic acid radical solution and the mixed salt solution into a reaction container in sequence, dropwise adding a NaOH solution into the mixed solution under the condition of continuous stirring to regulate the reaction pH value to be 8.0-8.5, and forming a suspension after dropwise adding; crystallizing at room temperature to 100 ℃ for 24 to 72h, centrifuging and washing the obtained precipitation solution until the supernatant is neutral, drying at 80 ℃ for 12h, and grinding to obtain a Ni-Ca-Zn LDR precursor; (2) calcination reduction: weighing a certain amount of the Ni-Ca-Zn LDR precursor obtained in the step (1), placing the precursor in a tubular atmosphere furnace, calcining for 2-4 h at the temperature of 500-800 ℃ in an inert atmosphere, and naturally cooling to room temperature to obtain a Ni-Ca-based composite catalyst formed by orderly assembling nano-particle structural elements; the Ni-Ca-based composite catalyst takes Ni as a main catalytic conversion active component, and the existing form of the Ni-Ca-based composite catalyst comprises metal Ni and Ni 3 ZnC 0.7 CaO as CO 2 The absorbent and the cocatalyst components comprise 48.2 to 85.2 mass percent of Ni phase and 12.7 to 15.8 mass percent of CaO; the organic acid radical in the preparation step (1) is one of sodium salicylate and sodium benzoate; the Ni-Ca-Zn catalyst prepared by the method is in a one-dimensional rod shape.
2. The use of the Ni-Ca-based composite catalyst obtained by the preparation method of claim 1 in the process of catalytic pyrolysis of biomass is characterized by comprising the following steps: (a) Tabletting, crushing and screening the prepared Ni-Ca-based composite catalyst to obtain catalyst powder with the granularity of 20-80 meshes;
(b) Filling biomass materials in a primary reactor of a fixed bed reaction device, filling the prepared catalyst with the particle size of 20-80 meshes in a secondary reactor, and introducing N 2 Discharging air in the reaction device, simultaneously heating the reactor to a set temperature, pyrolyzing the biomass material at 600-900 ℃, and generating pyrolysis steam with N of 50mL/min 2 Carrying the catalyst on the surface of the Ni-Ca-based composite catalyst at 500-800 ℃, cracking and reforming, condensing and drying the obtained cracking steam to obtain gas and liquid products.
3. The use of the Ni-Ca-based composite catalyst according to claim 2, wherein the biomass material in the step (b) is lignocellulosic biomass.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211790A (en) * | 2011-03-04 | 2011-10-12 | 北京化工大学 | Salicylate intercalation layered metal hydroxide nano rod and preparation method thereof |
| CN103121665A (en) * | 2013-03-12 | 2013-05-29 | 北京化工大学 | Three-dimensional flower-like salicylic acid radical intercalation layered hydroxide nano material and preparation method thereof |
| CN106238061A (en) * | 2016-07-18 | 2016-12-21 | 山东省科学院能源研究所 | Multi-function metal catalyst and methods for making and using same |
| CN107233888A (en) * | 2017-07-06 | 2017-10-10 | 山东省科学院能源研究所 | Biomass prepares gas combustion multifunction catalyst and preparation method |
-
2019
- 2019-07-15 CN CN201910637290.3A patent/CN110227468B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211790A (en) * | 2011-03-04 | 2011-10-12 | 北京化工大学 | Salicylate intercalation layered metal hydroxide nano rod and preparation method thereof |
| CN103121665A (en) * | 2013-03-12 | 2013-05-29 | 北京化工大学 | Three-dimensional flower-like salicylic acid radical intercalation layered hydroxide nano material and preparation method thereof |
| CN106238061A (en) * | 2016-07-18 | 2016-12-21 | 山东省科学院能源研究所 | Multi-function metal catalyst and methods for making and using same |
| CN108686664A (en) * | 2016-07-18 | 2018-10-23 | 山东省科学院能源研究所 | Application process of multi-function metal catalyst during catalytic pyrolysis of biomass |
| CN108855100A (en) * | 2016-07-18 | 2018-11-23 | 山东省科学院能源研究所 | The preparation method of multi-function metal catalyst |
| CN107233888A (en) * | 2017-07-06 | 2017-10-10 | 山东省科学院能源研究所 | Biomass prepares gas combustion multifunction catalyst and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Gas production by catalytic pyrolysis of herb residues using Ni/CaO catalysts;Anzhuang Xu等;《Journal of Analytical and Applied Pyrolysis》;20180110;第130卷;全文 * |
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