CN108855100B - Preparation method of multifunctional metal catalyst - Google Patents
Preparation method of multifunctional metal catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 16
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 16
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 9
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002028 Biomass Substances 0.000 description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 description 34
- 239000011269 tar Substances 0.000 description 33
- 239000000292 calcium oxide Substances 0.000 description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 17
- 238000005336 cracking Methods 0.000 description 16
- 238000000197 pyrolysis Methods 0.000 description 16
- 238000002309 gasification Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000007233 catalytic pyrolysis Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Industrial Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of the multifunctional metal catalyst is characterized in that the catalyst is prepared by the following steps: (a) preparation of hydrotalcite precursor to laminate containingHydrotalcite single precursor of Co, Fe, Ca and Al elements; (b) calcining and reducing: weighing a certain amount of the single hydrotalcite precursor obtained in the step (a), placing the single hydrotalcite precursor in a tubular atmosphere furnace, calcining for 2-10 h at the temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling to room temperature to obtain the multifunctional metal catalyst. The catalyst is made of Al2O3As a carrier, CoFe alloy is used as a main catalytic conversion active component, CaO is used as CO2The absorbent and the cocatalyst comprise the following components in percentage by mass: 25 to 52 percent of CoFe, 25 to 60 percent of CaO and Al2O310 to 25 percent.
Description
The application is a divisional application of Chinese patent application with the application date of 2016, 7, 18 and the application number of 2016105635397, namely a multifunctional metal catalyst and a preparation and application method.
Technical Field
The invention belongs to the field of energy and chemical industry, and particularly relates to Al for biomass catalytic pyrolysis2O3As a carrier, the main active component is CoFe alloy, CaO is added as CO2An absorbent and a multifunctional metal catalyst of a cocatalyst, and a preparation and application method thereof.
Background
The biomass pyrolysis gasification technology has the advantages of high efficiency, strong raw material adaptability, simple equipment and low investment, is an important aspect of biomass energy conversion technology, and is one of effective ways for cleanly and efficiently utilizing biomass energy. In the pyrolysis process of biomass, H is mainly produced2、CO、CO2、CH4And the like, and also part of organic (tar) and inorganic impurities and particles. The existence of tar not onlyResulting in a decrease in gas production rate and thermal efficiency, and also condensed into a liquid state at low temperature, and easily combined with water and dust to clog and corrode equipment. In addition, H in the gas obtained by pyrolysis and gasification of biomass2the/CO ratio is generally lower than 1, while the liquid fuel synthesis process generally requires H2the/CO ratio reaches a hydrogen-rich level of 2-3 or higher; at the same time, in order to reduce CO in the gasification gas2The influence of the efficiency and energy consumption of the subsequent synthesis gas conversion process needs to be influenced by CO2And carrying out in-situ absorption and removal. Therefore, the thermochemical conversion process of biomass needs to simultaneously solve the deep conversion of tar macromolecules and CO2Removal of H2And CO ratio adjustment.
The biomass pyrolysis steam is subjected to on-line catalytic cracking by adopting advanced catalytic materials to crack macromolecular tars to generate short-chain intermediate products and simultaneously generate more H2、CO、CO2The method has the advantages that the gasification efficiency is improved, the on-line adjustment of the components of the synthesis gas is realized, and the method is the most effective method for improving the utilization rate of the biomass and thoroughly reducing the secondary pollution. At present, the research on the catalytic pyrolysis of biomass at home and abroad mainly focuses on the selection of catalysts, and the used catalysts mainly comprise natural ore catalysts, alkali metal catalysts and transition metal-based catalysts. However, the method simply relies on a single catalyst to catalyze and crack organic macromolecules in the biomass pyrolysis process so as to simultaneously solve tar conversion and CO2Removal of H2The adjustment of the ratio of CO to CO is not ideal, and the preparation of the multifunctional catalyst with a plurality of active components superposed is imperative.
The patent "a catalyst and production method of biomass gasification furnace" (CN1686606A) discloses a catalyst and production method of biomass gasification furnace, the catalyst is composed of attapulgite clay, high alumina bauxite, ferric oxide, magnesium oxide, calcium oxide and anthracite, and the finished product is prepared by proportioning, stirring, grinding, granulating, drying, screening, detecting and packaging, and is used for thermal cracking decoking in various biomass gasification furnaces or gas furnaces, the decoking efficiency is 75%, however, the patent does not mention that the catalyst is used for CO gasification furnace and gas furnace2Absorption of (2) and H2The adjustment of the/CO ratio.
The patent 'biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof' (CNIO3394356A) discloses a biomass gasification multifunctional iron-based catalyst and a preparation method thereof, wherein the catalyst is prepared by adopting an impregnation method, consists of iron oxide, calcium oxide, cerium oxide and zirconium oxide, and is prepared by adding carbon monoxide (CO) into the mixture2Absorption, H2The catalyst has certain activity in the aspects of adjusting the/CO ratio and cracking tar. The method has the defects that the loading amount of the main active component iron oxide in the catalyst is low and is up to 15%, the catalyst shows high activity at 700 ℃, but is easy to gradually deactivate in the process of repeated use at high temperature (above 800 ℃), and the main reasons are that the interaction among the components of the catalyst prepared by an impregnation method is weak, and the high-content active component can migrate and grow under the high temperature condition to cause the sintering and activity reduction of the catalyst.
In the above patents, the catalytic materials all belong to a composite of iron oxide and calcium oxide, the main active components of which are mainly concentrated in a single metal (Ni or Fe). According to the research results reported by domestic and foreign documents, in tar catalytic cracking and steam reforming, metals have higher catalytic activity than oxides thereof, and particularly, alloy materials have higher catalytic activity and product selectivity than single metal catalysts. In addition, for the catalyst used in the circulating regenerated biomass moving bed gasification furnace or the fluidized bed gasification furnace, maintaining the high temperature activity stability of the catalyst is also a problem to be solved.
Hydrotalcite, also called Layered Double Hydroxide (LDHs), is an anionic Layered material with a supramolecular structure. Based on the fact that metal elements in a main body laminate can be dispersed in an atomic level according to a certain composition and proportion, the LDHs precursor method has great advantages and potentials in the aspect of preparing multifunctional catalytic materials with adjustable chemical compositions and uniform crystalline phase structures. However, at present, the application research of catalytic materials constructed based on LDHs precursors in the field of biomass pyrolysis catalytic conversion is few at home and abroad, and mainly single transition metal (Ni, Co) is used for the adjustment of tar cracking and synthesis gas composition, and no proposal is made on CO2An effective solution to the absorption problem.
Disclosure of Invention
Aiming at the problems, the invention overcomes the defects in the prior art and provides a CoFeCaAl-LDHs precursor-based catalyst which has the functions of tar cracking, synthesis gas component adjustment and CO2Multifunctional absorbing Al for biomass catalytic pyrolysis2O3And (3) loading the CoFe/CaO multifunctional metal catalyst.
The invention also provides a preparation method and an application method of the multifunctional metal catalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows: a multifunctional metal catalyst for catalytic pyrolysis of biomass is prepared from Al2O3As a carrier, CoFe alloy nano particles are used as a main catalytic conversion active component, CaO is used as CO2The absorbent and the cocatalyst comprise the following components in percentage by mass: 25 to 52 percent of CoFe, 25 to 60 percent of CaO and Al2O310 to 25 percent.
The invention is characterized in that the CoFe alloy nano particles as the main active component are highly dispersed in the carrier, and the particle size is controlled to be 10-17 nm.
The multifunctional metal catalyst is prepared by the following steps:
(a) preparation of hydrotalcite precursor: mixing Ca (NO)3)2∙6H2O、Co(NO3)2∙6H2O、Al(NO3)3∙9H2O、Fe(NO3)3∙9H2Dissolving O in deionized water to prepare a solution with a concentration of [ Co ]2+]+[Ca2+]+[Fe3+]+[Al3+]A mixed salt solution of = 1-1.6M; additionally preparing NaOH solution with the concentration of 0.5-2 mol/L as a precipitator; slowly and continuously dropwise adding the prepared mixed salt solution into an alkali solution under the condition of continuous strong stirring, controlling the pH value of the final solution to be 10-11.5, and forming a suspension after dropwise adding; crystallizing for 0.5-24 h at 60 ℃, centrifuging and washing the obtained precipitation solution until the pH of the supernatant is 7, drying for 12h at 100 ℃, and grinding to obtain the hydrotalcite single precursor with the laminate containing Co, Fe, Ca and Al elements.
(b) Calcining and reducing: weighing a certain amount of the single hydrotalcite precursor obtained in the step (a), placing the single hydrotalcite precursor in a tubular atmosphere furnace, calcining for 2-10 h at the temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling to room temperature to obtain the multifunctional metal catalyst.
A preparation method of a multifunctional metal catalyst comprises the following steps:
(a) preparation of hydrotalcite precursor: mixing Ca (NO)3)2∙6H2O、Co(NO3)2∙6H2O、Al(NO3)3∙9H2O、Fe(NO3)3∙9H2Dissolving O in deionized water to prepare a solution with a concentration of [ Co ]2+]+[Ca2+]+[Fe3+]+[Al3+]A mixed salt solution of = 1-1.6M; additionally preparing NaOH solution with the concentration of 0.5-2 mol/L as a precipitator; slowly and continuously dropwise adding the prepared mixed salt solution into an alkali solution under the condition of continuous strong stirring, controlling the pH value of the final solution to be 10-11.5, and forming a suspension after dropwise adding; crystallizing for 0.5-24 h at 60 ℃, centrifuging and washing the obtained precipitation solution until the pH of the supernatant is 7, drying for 12h at 100 ℃, and grinding to obtain the hydrotalcite single precursor with the laminate containing Co, Fe, Ca and Al elements.
(b) Calcining and reducing: weighing a certain amount of the single hydrotalcite precursor obtained in the step (a), placing the single hydrotalcite precursor in a tubular atmosphere furnace, calcining for 2-10 h at the temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling to room temperature to obtain the multifunctional metal catalyst.
According to a particular feature of the invention, the (Co) solution in the mixed salt solution of step (a) is2++Ca2+）/（Fe3++Al3+) The molar ratio is (1-3): 1, Co2+：Ca2+：Fe3+：Al3+The molar ratio is preferably 1: 1: 1: 1 or 1: 3: 1: 1 or 1: 5: 1: 1.
the reducing atmosphere in the step (b) is hydrogen or a mixed gas of hydrogen and nitrogen or argon, wherein H in the mixed gas2The volume percentage is preferably 10%.
An application method of the multifunctional metal catalyst in the biomass catalytic pyrolysis process comprises the following steps:
(a) tabletting, crushing and screening the prepared multifunctional metal catalyst to obtain catalyst powder with the granularity of 20-100 meshes;
(b) filling biomass material in a primary reactor of a fixed bed reaction device, filling the prepared catalyst powder with the particle size of 20-100 meshes in a secondary reactor, and introducing N2Discharging air in the reaction device, simultaneously heating the reactor to a set temperature, pyrolyzing the biomass material at the temperature of 700-2Carrying the catalyst at 600-900 ℃ for catalytic cracking on the surface of the catalyst.
The invention has the beneficial effects that:
1. the invention combines the higher catalytic activity and product selectivity of CoFe alloy material and the CO to CaO2Better absorption effect, and Al is added at the same time2O3The components realize the high dispersion of active centers so as to improve the high-temperature stability of the catalyst, and the LDHs precursor method is adopted to prepare the catalyst which has the functions of tar cracking, synthesis gas component adjustment and CO2An adsorbed multifunctional metal catalyst.
2. In the invention, the loading capacity (up to 52%) and the dispersity (the particle size is 10-17 nm) of the CoFe alloy nano particles serving as the main active component of the catalyst are obviously improved, the sintering resistance and the carbon deposition resistance of the catalyst under a high-temperature condition are improved, and the catalytic activity and the high-temperature stability of the catalyst are further improved.
3. The LDHs precursor method adopted by the invention can easily realize quantitative uniform doping and composition of the final product and regulation and control of the micro-nano structure, and the synthesis method is simple, stable in chemical property and low in price, and can be applied to industrial large-scale production.
4. The multifunctional metal catalyst prepared by the invention still maintains higher catalytic activity at the catalytic cracking temperature of 900 ℃, the tar conversion rate can reach 88.82 percent, and H2The ratio of/CO is 1.86, the activity of the catalyst is kept stable within 30h of reaction, and obvious sintering and inactivation phenomena are avoided.
Detailed Description
Example 1: a preparation method of a multifunctional metal catalyst comprises the following steps:
The multifunctional metal catalyst prepared by the method comprises the following components in percentage by mass: 51.86%, CaO: 25.06% of Al2O3: 23.08%, no other impurity phases were found, with the CoFe alloy nanoparticles having an average size of 10.3 nm.
An application method of the multifunctional metal catalyst in the biomass catalytic pyrolysis process comprises the following steps:
(a) tabletting, crushing and screening the prepared multifunctional metal catalyst to obtain catalyst powder with the granularity of 20-100 meshes;
(b) filling biomass material in a primary reactor of a fixed bed reaction device, filling the prepared catalyst powder with the particle size of 20-100 meshes in a secondary reactor, and introducing N2Discharging air in the reaction device, simultaneously heating the reactor to a set temperature, pyrolyzing the biomass material at 700 ℃, and generating pyrolysis steam with N of 50mL/min2Carrying the catalyst at 600-900 ℃ for catalytic cracking on the surface of the catalyst.
The typical components of the crude fuel gas produced by biomass pyrolysis gasification are (volume percentage): h2：15.06%、CO：44.28%、CO2：23.98%、CH4: 16.68% and the difference gives a tar content of 0.4429g/1g biomass.
The crude fuel gas and tar generated by the pyrolysis and gasification of the biomass with the components are subjected to online catalytic cracking, and the catalytic reaction temperature is 600 ℃. Experimental studies found that the gas components obtained after the reaction were (volume percent): h2：61.04%、CO：23.3%、CO2：8.43%、CH4: 7.23% and a tar content of 0.0201g/1g biomass. In contrast to pure pyrolysis, H2The ratio of/CO is obviously improved from 0.34 to 2.62, and the cracking rate of tar is 95.46%. The catalytic effect is higher than the performance of the catalyst reported in the literature at present. Within 30h of the reaction, the activity of the catalyst is maintained stable, the average size of CoFe alloy nano particles in the catalyst after the reaction is slightly increased to 13.3 nm, and the catalyst shows stronger high-temperature stability and anti-sintering performance.
Example 2:
the preparation method of the catalyst in this example is the same as that in example 1 and will not be described again except that the content of the active component is different, wherein Co is2+：Ca2+：Fe3+：Al3+The molar ratio is 1: 5: 1: 1. the prepared catalyst comprises the following components in percentage by mass: 25.56%, CaO: 59.86% of Al2O3: 14.58% and no other impurity phases were found, with the CoFe alloy nanoparticles having an average size of 13.7 nm。
The catalyst evaluation was carried out under the same experimental conditions as in example 1, and it was found that the gas composition obtained after the reaction was (volume percentage): h2：59.53%、CO：26.57%、CO2：3.71%、CH4：10.18%，H2The ratio of/CO was 2.24, the tar content was 0.0357g/1g biomass, and the tar cracking rate was 91.94%. The increased CaO content significantly enhanced the CO-tolerance compared to example 12The adsorption property of (2) to make CO in the synthesis gas2The content is reduced, however, the catalytic activity is reduced due to the reduction of the content of CoFe serving as a main active component, and H is caused2the/CO ratio and the tar cracking rate were slightly lowered. The average size of CoFe alloy nano particles in the catalyst after reaction is slightly increased to 17.3 nm, and the catalyst shows stronger high-temperature stability and anti-sintering performance.
Example 3:
the preparation method of the catalyst in this example is the same as that in example 1 and will not be described again, except that the preparation conditions and steps are different
The coprecipitation pH was 9.5. To the step of
XRD characterization of the obtained catalyst precursor shows that the product is prepared from LDHs and CaCO3Two phases are formed. The composition and mass percentage of the catalyst prepared by the precursor are close to those of the catalyst prepared in the embodiment 1, and the catalyst is CoFe: 50.46%, CaO: 26.16% of Al2O3: 23.38%, whereas the average CoFe alloy nanoparticle size increased significantly to 20.3 nm.
The catalyst evaluation was carried out under the same experimental conditions as in example 1, and it was found that the gas composition obtained after the reaction was (volume percentage): h2：46.67%、CO：27.14%、CO2：15.26%、CH4：10.93%，H2The ratio of/CO was 1.72, the tar content was 0.0494g/1g biomass, and the tar cracking rate was 88.84%. CaO vs. CO, in comparison with example 12The absorption performance is obviously reduced, and the water gas shift reaction is further reducedPromoting effect to result in H in synthetic gas2the/CO ratio is significantly reduced. In addition, CaO has weak interaction with other components in the catalyst, so that the activity of CaO in tar cracking reaction is reduced, and the tar cracking rate is slightly reduced.
Example 4:
the composition and mass percentage of the catalyst in the embodiment are consistent with those in embodiment 1, and the catalyst is CoFe: 51.86%, CaO: 25.06% of Al2O3: 23.08 percent. The preparation method is the same as that of example 1 and is not repeated herein, except that the preparation steps
The medium catalyst has different roasting conditions, and the roasting temperature is increased by 1000 ℃ from 600 ℃. Characterization found that the average size of the CoFe alloy nanoparticles in the prepared catalyst was 16.3 nm.
The catalyst evaluation was carried out under the same experimental conditions as in example 1, and it was found that the gas composition obtained after the reaction was (volume percentage): h2：57.48%、CO：24.87%、CO2：7.72%、CH4：9.93%，H2The ratio of/CO was 2.31, the tar content was 0.0265g/1g biomass, and the tar cracking rate was 94.01%. Compared with example 1, even when the roasting temperature is raised to 1000 ℃, the CoFe alloy particles of the main active component of the catalyst do not have sintering phenomenon and have obvious size increase, so that the high catalytic activity, H, is still maintained2the/CO ratio and the tar cracking rate were slightly lowered. After the reaction, the average size of the CoFe alloy nano particles in the catalyst is increased to 24.3 nm, and the catalyst shows stronger sintering resistance.
Example 5:
the composition and mass percentage of the catalyst in the embodiment are consistent with those in embodiment 1, and the catalyst is CoFe: 51.86%, CaO: 25.06% of Al2O3: 23.08%, no other impurity phases were found, with the CoFe alloy nanoparticles having an average size of 10.3 nm. The preparation method is the same as that of example 1, and the details are not repeated here.
The difference from the example 1 is that the pyrolysis temperature of the biomass is increased from 700 ℃ to 900 ℃, and the catalytic reaction temperature isAt 600 ℃, the gas components obtained after the reaction are found to be (volume content): h2：59.57%、CO：20.83%、CO2：7.72%、CH4：11.88%，H2The ratio of CO/tar was 2.86, the tar content was 0.0068g/1g biomass, and the tar cracking rate was 98.46%. Compared with the embodiment 1, when the pyrolysis temperature of the biomass is increased to 900 ℃, part of tar macromolecular organic compounds in the pyrolysis gas are decomposed under the high-temperature condition and are further subjected to catalytic cracking under the action of the catalyst, so that the quality of the synthesis gas and the cracking rate of the tar are further improved, however, the energy consumption of the system is increased when the pyrolysis temperature is increased, and the method is not beneficial to practical industrial application. The catalyst has no obvious change in structure after long-time reaction operation, and shows high heat stability and sintering resistance.
Example 6:
the composition and mass percentage of the catalyst in the embodiment are consistent with those in embodiment 1, and the catalyst is CoFe: 51.86%, CaO: 25.06% of Al2O3: 23.08%, no other impurity phases were found, with the CoFe alloy nanoparticles having an average size of 10.3 nm. The preparation method is the same as that of example 1, and the details are not repeated here.
The difference from example 1 is that the catalytic reaction temperature is raised from 600 ℃ to 900 ℃, and the biomass pyrolysis temperature is still 700 ℃. The gas components obtained after the reaction are found to be (volume percentage): h2：45.08%、CO：24.32%、CO2：18.72%、CH4：11.88%，H2The ratio of/CO was 1.86, the tar content was 0.0495g/1g biomass, and the tar cracking rate was 88.82%. When the catalytic temperature was increased to 900 ℃ the catalytic activity was reduced compared to example 1, whereas the resulting H2The ratio of CO to the oil and tar cracking rate is still higher than the results reported in most literatures. Within 30h of the reaction, the activity of the catalyst is maintained stable, the average size of the CoFe alloy nano particles in the catalyst after the reaction is increased to 21.8 nm, and the catalyst shows stronger sintering resistance.
Claims (5)
1. The preparation method of the multifunctional metal catalyst is characterized by comprising the following steps:
(a) preparation of hydrotalcite precursor: mixing Ca (NO)3)2∙6H2O、Co(NO3)2∙6H2O、Al(NO3)3∙9H2O、Fe(NO3)3∙9H2Dissolving O in deionized water to prepare a solution with a concentration of [ Co ]2+]+[Ca2+]+[Fe3+]+[Al3+]A mixed salt solution of = 1-1.6M; additionally preparing NaOH solution with the concentration of 0.5-2 mol/L as a precipitator; slowly and continuously dropwise adding the prepared mixed salt solution into an alkali solution under the condition of continuous strong stirring, controlling the pH value of the final solution to be 10-11.5, and forming a suspension after dropwise adding; crystallizing for 0.5-24 h at 60 ℃, centrifuging and washing the obtained precipitation solution until the pH of the supernatant is 7, drying for 12h at 100 ℃, and grinding to obtain a hydrotalcite single precursor with a laminate containing Co, Fe, Ca and Al elements;
(b) calcining and reducing: weighing a certain amount of the single hydrotalcite precursor obtained in the step (a), placing the single hydrotalcite precursor in a tubular atmosphere furnace, calcining for 2-10 h at the temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling to room temperature to obtain a multifunctional metal catalyst;
multifunctional metal catalyst with Al2O3As a carrier, CoFe alloy nano particles are used as a main catalytic conversion active component, CaO is used as CO2The absorbent and the cocatalyst comprise the following components in percentage by mass: 25 to 52 percent of CoFe, 25 to 60 percent of CaO and Al2O310 to 25 percent.
2. The method for preparing a multifunctional metal catalyst according to claim 1, wherein the (Co) mixed salt solution in the step (a) is2++Ca2+）/（Fe3++Al3+) The molar ratio is (1-3): 1, Co2+：Ca2+：Fe3+：Al3+The molar ratio is 1: 1: 1: 1 or 1: 3: 1: 1 or 1: 5: 1: 1.
3. the method of preparing a multifunctional metal catalyst according to claim 1, wherein the reducing atmosphere in the step (b) is hydrogen, or a mixture of hydrogen and nitrogen or argon.
4. The method of claim 1, wherein the volume percentage of hydrogen in the mixed gas is 10%.
5. The method for preparing a multifunctional metal catalyst according to claim 1, wherein the CoFe alloy nanoparticles as the main active component are highly dispersed in the carrier, and the particle diameter thereof is controlled to be 10-17 nm.
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