CN114950441A - Nickel-based catalyst for hydrogen production by biological oil steam reforming and preparation method and application thereof - Google Patents
Nickel-based catalyst for hydrogen production by biological oil steam reforming and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 238000000629 steam reforming Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 229910015999 BaAl Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000002195 synergetic effect Effects 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002407 reforming Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- DDEHZCWFAUZBEH-UHFFFAOYSA-O azanium;ethanol;nitrate Chemical compound [NH4+].CCO.[O-][N+]([O-])=O DDEHZCWFAUZBEH-UHFFFAOYSA-O 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008021 deposition Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
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- 230000000052 comparative effect Effects 0.000 description 19
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000012075 bio-oil Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910000943 NiAl Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
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- 241000282326 Felis catus Species 0.000 description 1
- 206010017577 Gait disturbance Diseases 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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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
-
- 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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- B01J35/393—
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- B01J35/40—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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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
Abstract
The invention discloses a biological oil steam reforming hydrogen production nickel-based catalyst which comprises a carrier, an active component and a synergistic component, wherein the active component is nickel, the synergistic component is barium, and the carrier is aluminum oxide. The nickel-based catalyst for hydrogen production by biological oil steam reforming has the advantages of simple components, low price, good carbon deposition resistance and reaction activity and long service life. The invention also provides a preparation method of the nickel-based catalyst for hydrogen production by biological oil steam reforming, which comprises the following steps: (1) preparation of Al 2 O 3 A precursor; (2) preparation of BaAl 2 O 3 A precursor; (3) preparation of NiBaAl 2 O 3 A precursor; (4) and (4) reducing. The preparation method of the nickel-based catalyst for hydrogen production by biological oil steam reforming has simple process steps and lower requirements on process conditions, and can improve the dispersibility of nickel.
Description
Technical Field
The invention relates to a catalyst for hydrogen production by reforming biological oil vapor, in particular to a nickel-based catalyst for hydrogen production by reforming biological oil vapor as well as a preparation method and application thereof.
Background
Hydrogen has wide application as a clean energy source in the aspects of ammonia synthesis, hydrogenation reaction and hydrogen fuel cells. Currently, about 80% of industrial hydrogen production relies primarily on steam reforming of natural gas, however, the global warming is becoming increasingly significant due to the excessive use of fossil fuels. Therefore, it is particularly urgent to find a sustainable hydrogen production process that can replace fossil fuels.
Biomass with huge reserves and easy regeneration is a direction for developing new energy in the future, biomass can be liquefied into bio-oil through rapid thermal cracking, and the bio-oil can be converted into hydrogen through a steam reforming technology. The first step (rapid thermal cracking) in the process is mature and industrialized; in the second step (steam reforming), because the bio-oil has complex components and contains a large amount of oxygen-containing compounds and macromolecular aromatic compounds, the catalyst is often inactivated due to high-temperature sintering, carbon deposition and the like in the using process, and the bio-oil becomes stumbling stone for realizing industrialization of the scheme.
The catalysts used for steam reforming are mainly classified into two major types, i.e., transition metals (Ni, Co, etc.) and noble metals (Pt, Ru, etc.). The noble metal catalyst is expensive and high in use cost, so that the noble metal catalyst is not suitable for being popularized and used in the biological oil steam reforming hydrogen production, and the Ni-based catalyst which is low in price and high in activity is generally used in industry. The most serious problem of the existing Ni-based catalyst in the biological oil steam reforming reaction is the precipitation of carbon deposit on the surface of the catalyst, and the precipitated carbon deposit not only covers active sites to deactivate the catalyst, but also easily leads the catalyst to be powdered and lost, thereby causing the service life of the catalyst to be short.
Although the existing reports that the carbon deposition resistance of Ni-based catalysts is improved by loading other elements exist, the problems of complex components, poor dispersibility of active components in the catalysts on the surface of a carrier and the like generally exist.
For example, Chinese patent application publication No. CN110639527A discloses a biological organismThe integral catalyst for hydrogen production by oil-water vapor reforming is composed of an active component and a carrier, wherein the active component is NiOX-NiTiO 3 Nanoparticles in which the active component NiOX-NiTiO 3 In-situ growth on mesoporous carbon material to form composite catalyst NiOX-NiTiO 3 and/C, the carrier is integral charcoal WC. The carrier in the catalyst is integral charcoal WC, the mechanical strength is low, the stability is poor, the falling of active ingredients is easy to cause, high-temperature pyrolysis, etching and the like are required in the preparation process, the requirements on process conditions are strict, the process is complex, and the mechanical strength of the carrier can be further reduced by etching.
Disclosure of Invention
The invention aims to solve the problems of the integral catalyst for hydrogen production by reforming the biological oil steam in the prior art, and provides the nickel-based catalyst for hydrogen production by reforming the biological oil steam, which has the advantages of simple components, low price, good carbon deposition resistance and reaction activity and long service life.
The invention also provides a preparation method of the nickel-based catalyst for hydrogen production by reforming the biological oil steam, which has the advantages of simple process steps, strong operability and lower requirements on process conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the biological oil steam reforming hydrogen production nickel-based catalyst comprises a carrier, an active component and a synergistic component, wherein the active component is nickel, the synergistic component is barium, and the carrier is aluminum oxide. The inventor finds that loading barium (Ba) in the catalyst can relieve the precipitation of carbon deposit in the catalyst and improve the carbon deposit resistance of the catalyst, which may be caused by that Ba changes the molecular adsorption on the surface of the catalyst, improves the acid sites on the surface of a carrier (the carbon deposit rate is mainly related to the acid sites on the surface of the catalyst), or catalyzes reactant molecules in cooperation with active components; in addition, the nickel-based catalyst for hydrogen production by biological oil steam reforming has simple components and low price.
Preferably, the mass percentage of the active component is 15-20%, the mass percentage of the synergistic component is 1-20%, and the balance is a carrier, based on the total mass of the nickel-based catalyst.
Preferably, the nickel-based catalyst for hydrogen production by biological oil steam reforming is granular, and the particle size is 420-850 mu m.
A preparation method of a nickel-based catalyst for hydrogen production by biological oil steam reforming comprises the following steps:
(1) preparation of Al 2 O 3 Precursor: dissolving aluminum isopropoxide in a proper amount of absolute ethyl alcohol, adding a proper amount of hexadecyl trimethyl ammonium bromide, stirring at normal temperature, and performing ultrasonic treatment to obtain a mixed solution; slowly dripping deionized water into the mixed solution under the stirring state, and stirring under the sealing condition until no precipitate is generated; filtering, and cleaning the filtrate with ammonium nitrate ethanol solution to obtain Al 2 O 3 And (3) precursor. In the invention, hexadecyl trimethyl ammonium bromide is used as a template agent, deionized water is used as a precipitating agent, and the Al with the microporous structure is prepared 2 O 3 The precursor can provide enough specific surface area, provide good dispersity for metallic nickel, increase effective active sites on the surface of the catalyst, and improve the activity and stability of the catalyst in the steam reforming reaction.
(2) Preparation of BaAl 2 O 3 Precursor: adding a proper amount of deionized water into barium acetate, and mixing with Al 2 O 3 Mixing the precursors, drying by distillation after ultrasonic treatment, calcining the obtained solid to obtain BaAl 2 O 3 And (3) precursor. In the invention, the surface of the carrier is loaded with the synergistic component Ba by adding barium acetate.
(3) Preparation of NiBaAl 2 O 3 Precursor: dissolving nickel nitrate and urea in deionized water, adding BaAl 2 O 3 Performing ultrasonic treatment on the precursor, reacting under the conditions of stirring and 90 +/-3 ℃, centrifuging and drying after reaction, performing compression molding on the dried powder, crushing and screening to obtain NiBaAl 2 O 3 Powder, namely the nickel-based catalyst for hydrogen production by biological oil steam reforming. The invention is used for preparing NiBaAl 2 O 3 Urea is creatively added and heatedSlowly decompose to release OH - The pH value of the solution is slowly changed to enable Ni to be precipitated homogeneously, so that Ni agglomeration is avoided, the dispersity of Ni on a carrier is improved, and the overall efficiency of the catalyst in steam reforming is improved.
(4) Reduction: mixing NiBaAl 2 O 3 And (3) reducing the precursor by using hydrogen and treating the precursor by using water vapor to obtain the biological oil vapor reforming hydrogen production nickel-based catalyst. Reducing hydrogen at 600 ℃ for 3h, and treating with water vapor at 750 ℃ for 1 h; the NiO is reduced to Ni by hydrogen, and the adsorption capacity of the catalyst to water is improved by steam treatment, so that the activity is improved.
Preferably, in the step (1), the mass ratio of the hexadecyl trimethyl ammonium bromide to the aluminum isopropoxide is (3-4): 1, the mass ratio of deionized water to aluminum isopropoxide is (5-6): 1; the mass concentration of ammonium nitrate in the ammonium nitrate ethanol solution is 5-6 g/L.
Preferably, in step (2), barium acetate is mixed with Al 2 O 3 The molar ratio of the precursor is (0.025-0.17): 1; evaporating to dryness and adopting 110 ℃ sand bath; the calcination temperature is 800 ℃, and the calcination time is 4-6 h.
Preferably, in the step (3), the mass ratio of the nickel nitrate to the urea is (3-4): 1; nickel nitrate and BaAl 2 O 3 The mass ratio of the precursor is (0.45-0.5): 1. the urea addition is too little to provide enough OH for the reaction system - If the amount is too low, a large amount of by-products may be produced.
Preferably, in the step (4), the particle size of the nickel-based catalyst for hydrogen production by biological oil steam reforming is 420-850 μm.
Therefore, the invention has the following beneficial effects:
(1) the nickel-based catalyst for hydrogen production by reforming the biological oil steam has the advantages of simple components, low price, good carbon deposition resistance and reaction activity and long service life;
(2) the preparation method of the nickel-based catalyst for hydrogen production by biological oil steam reforming is provided, the process steps are simple, the requirements on process conditions are low, and the nickel dispersibility can be improved.
Drawings
FIG. 1 is a TEM image of the bio-oil steam reforming hydrogen production nickel-based catalyst obtained in example 1.
Fig. 2 is a TEM image of the bio-oil steam reforming hydrogen production nickel-based catalyst obtained in comparative example 1.
FIG. 3 is a TEM image of the nickel-based catalyst for hydrogen production by steam reforming of a bio-oil obtained in comparative example 2.
FIG. 4 is a superimposed graph of pore structure curves of the catalysts in example 1 and comparative examples 1 to 2.
FIG. 5 is a graph comparing hydrogen yields.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
(1) Preparation of Al 2 O 3 Precursor: dissolving aluminum isopropoxide in absolute ethyl alcohol, adding a proper amount of hexadecyl trimethyl ammonium bromide, stirring at normal temperature, and performing ultrasonic treatment to obtain a mixed solution; slowly dripping deionized water into the mixed solution under the stirring state, and stirring under the sealing condition until no precipitate is generated; filtering, washing the filtrate with ammonium nitrate ethanol solution to obtain Al 2 O 3 The precursor, wherein the mass ratio of hexadecyl trimethyl ammonium bromide to aluminum isopropoxide is 4: 1, the mass ratio of the deionized water to the aluminum isopropoxide is 6: 1; the mass concentration of ammonium nitrate in the ammonium nitrate ethanol solution is 6 g/L;
(2) preparation of BaAl 2 O 3 Precursor: adding a proper amount of deionized water into barium acetate, and mixing with Al 2 O 3 Mixing the precursors, barium acetate and Al 2 O 3 The molar ratio of the precursors is 0.17: 1, evaporating to dryness by adopting a 110 ℃ sand bath after ultrasonic treatment, and calcining the obtained solid at 800 ℃ for 6 hours to obtain BaAl 2 O 3 ；
(3) Preparation of NiBaAl 2 O 3 Precursor: dissolving nickel nitrate and urea in deionized water, wherein the mass ratio of the nickel nitrate to the urea is 4: 1, adding BaAl 2 O 3 Precursor, nickel nitrate and BaAl 2 O 3 The mass ratio of the precursor is 0.45: 1, carrying out reaction under the conditions of stirring and 90 +/-3 ℃ after ultrasonic treatment, and centrifuging after reactionDrying, pressing the dried powder to form, crushing and screening to obtain NiBaAl 2 O 3 And (3) precursor.
(4) Reduction: mixing NiBaAl 2 O 3 The precursor is reduced by hydrogen at 600 ℃ for 3h and treated by water vapor at 750 ℃ for 1h to obtain the biological oil vapor reforming hydrogen production nickel-based catalyst with the particle size of 450 mu m.
The TEM image of the obtained nickel-based catalyst for hydrogen production by steam reforming of biological oil is shown in FIG. 1. As can be seen from FIG. 1, BaAl was produced 2 O 3 Has a porous structure and forms Ni metal phase with particle size after reduction<10nm, and has good dispersibility.
The pore structure curve of the obtained nickel-based catalyst for hydrogen production by biological oil steam reforming is shown in fig. 4.
Comparative example 1
(1) Preparation of Al 2 O 3 Precursor: dissolving aluminum isopropoxide in absolute ethyl alcohol, adding a proper amount of hexadecyl trimethyl ammonium bromide, stirring at normal temperature, and performing ultrasonic treatment to obtain a mixed solution; slowly dripping deionized water into the mixed solution under the stirring state, and stirring under the sealing condition until no precipitate is generated; filtering, and cleaning the filtrate with ammonium nitrate ethanol solution to obtain Al 2 O 3 The precursor, wherein the mass ratio of hexadecyl trimethyl ammonium bromide to aluminum isopropoxide is 4: 1, the mass ratio of the deionized water to the aluminum isopropoxide is 6: 1; the mass concentration of ammonium nitrate in the ammonium nitrate ethanol solution is 6 g/L;
(2) preparation of NiAl 2 O 3 Precursor: dissolving nickel nitrate and urea in deionized water, wherein the mass ratio of the nickel nitrate to the urea is 4: 1, adding Al 2 O 3 Precursor, nickel nitrate and Al 2 O 3 The mass ratio of the precursor is 0.45: 1, carrying out ultrasonic treatment, stirring, reacting at 90 +/-3 ℃, centrifuging and drying after reaction, pressing and molding dried powder, crushing and screening to obtain NiAl 2 O 3 And (3) precursor.
(3) Reduction: mixing NiAl 2 O 3 The precursor is reduced by hydrogen at 600 ℃ for 3h and treated by water vapor at 750 ℃ for 1h to obtain the biological oil with the particle size of 450 mu m, and the hydrogen is prepared by reforming the water vaporA nickel-based catalyst.
The TEM image of the obtained biological oil steam reforming hydrogen production nickel-based catalyst is shown in FIG. 2. As can be seen from fig. 2, the prepared catalyst has a porous structure, and the morphology of the Ni metal phase formed after reduction is similar to that of example 1.
The pore structure curve of the obtained nickel-based catalyst for hydrogen production by biological oil steam reforming is shown in fig. 4.
Comparative example 2
Comparative example 2 differs from example 1 in that: in the step (3), no urea is added, and Ni is introduced into Ba Al by adopting an immersion method 2 O 3 The precursor and the impregnation method specifically comprise the following steps: mixing BaAl 2 O 3 Dispersing the precursor in nickel nitrate water solution, and slowly evaporating the water in a sand bath at 110 ℃; the rest is the same as in example 1.
The TEM image of the obtained bio-oil steam reforming hydrogen production nickel-based catalyst is shown in fig. 3. As can be seen from FIG. 3, the metal particle size of Ni in the catalyst was 20nm, and the dispersibility of Ni was poor.
The pore structure curve of the obtained nickel-based catalyst for hydrogen production by biological oil steam reforming is shown in fig. 4.
As can be seen from fig. 4, the catalyst prepared in comparative example 2 had the largest number of micropores, indicating that the introduction of Ba blocked some of the channels.
NO adsorption amount and ammonia adsorption amount test
The specific method for testing the NO adsorption amount comprises the following steps: 1.5g of the catalyst reduced at 600 ℃ is placed in an adsorption measuring chamber, the temperature is increased to 100 ℃ at the speed of 10 ℃/min, degassing is carried out for 1h, then the temperature of a sample is maintained at 25 ℃, NO adsorption is carried out, and the adsorption quantity of NO is measured as the first step; degassing the sample at 25 ℃ for 60min after adsorption is finished, and measuring the adsorption quantity (physical adsorption quantity) of the removed NO to be ②; and (3) calculating the amount of NO chemically adsorbed on the surface of the sample by using the first step and the second step.
The specific method for the ammonia adsorption capacity test comprises the following steps: 1.5g of the catalyst reduced at 600 ℃ is placed in an adsorption measuring chamber, the temperature is increased to 150 ℃ at the first speed of 10 ℃/min, degassing is carried out for 1h, then the temperature of a sample is maintained at 100 ℃, and NH is carried out 3 Adsorption, measurement of NH 3 The adsorption amount of (a) is (i); after adsorption the sample was degassed at 100 ℃ 90min, measuring the removed NH 3 Adsorption amount (physical adsorption amount); calculating NH chemically adsorbed on the surface of the sample by using the formula I-II 3 Amount of the compound (A).
The test results are shown in table 1.
TABLE 1 test results of NO and Ammonia adsorption amounts
As can be seen from table 1, the catalyst of example 1 has a higher NO adsorption amount than comparative example 2, indicating that this method achieves a high Ni dispersion; the ammonia adsorption amount of the catalyst in example 1 is lower than that of comparative example 1, which shows that the number of acid sites on the surface of the catalyst prepared by the method is obviously reduced.
Evaluation of catalyst Activity
Respectively filling the catalyst particles obtained in the example 1, the comparative example 1 and the comparative example 2 into a fixed bed reactor, wherein the reactor is made of 316L stainless steel; the pipe diameter is phi 10 multiplied by 1mm, and the pipe length is 35 cm; the amount of the catalyst is 0.5 g; the method takes a model compound (acetic acid) of bio-oil and water vapor as raw materials, and comprises the following reaction process parameters: (700 ℃, 1MPa, space velocity WHSV of 21.4h -1 The water-carbon ratio S/C is 3.49); running for 10 h; the gas and liquid phase products were separately chromatographically quantified.
The evaluation results are shown in table 2.
TABLE 2 evaluation results of catalyst Activity
| Catalyst and process for preparing same | Conversion (%) | Hydrogen yield (%) |
| Example 1 | 100 | 83 |
| Comparative example 1 | 100 | 71 |
| Comparative example 2 | 95 | 67 |
As can be seen from table 2, since the catalyst obtained in example 1 has the highest hydrogen conversion rate and yield in the steam reforming reaction, it is shown that the catalyst Ni has good dispersibility and better catalytic performance.
Carbon deposit amount test
The catalyst particles obtained in example 1, comparative example 1 and comparative example 2 were subjected to a carbon deposition amount test, and the specific method of the carbon deposition amount test was as follows: 20mg of the sample which is used for 10 hours under the conditions (the same as the catalyst evaluation test conditions) is placed in a thermogravimetric analyzer, the temperature is raised to 900 ℃ at the speed of 10 ℃/min, and the carbon deposition amount is the percentage of the weight loss of the sample to the total mass of the sample.
The results of the carbon deposit amount test are shown in table 3.
TABLE 3 catalyst carbon deposition test results
| Catalyst and process for preparing same | Carbon deposition amount (g/g cat) |
| Example 1 | 2.3 |
| Comparative example 1 | 5.6 |
| Comparative example 2 | 6.7 |
As can be seen from table 3, example 1 had the least amount of carbon deposition, indicating that carbon deposition from the catalyst can be mitigated by the present invention.
Evaluation of catalyst stability
Respectively filling the catalyst particles obtained in the example 1, the comparative example 1 and the comparative example 2 into a fixed bed reactor, wherein the reactor is made of 316L stainless steel; the pipe diameter is phi 10 multiplied by 1mm, and the pipe length is 35 cm; the amount of the catalyst is 0.5 g; the method takes a model compound (acetic acid) of biological oil and water vapor as raw materials, and the reaction process parameters are as follows: (700 ℃, 1MPa, space velocity WHSV of 21.4h -1 Water-carbon ratio S/C3.49), the catalyst was subjected to continuous stability testing, sampling was performed at intervals, the hydrogen content was measured by gas chromatography, the hydrogen yield was calculated, and the comparison of the hydrogen yields is shown in fig. 5.
As can be seen from fig. 5, the catalyst of example 1 showed no significant decrease in hydrogen yield, indicating a high stability.
The above-described embodiment is a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The nickel-based catalyst for hydrogen production by biological oil steam reforming is characterized by comprising a carrier, an active component and a synergistic component, wherein the active component is nickel, the synergistic component is barium, and the carrier is aluminum oxide.
2. The nickel-based catalyst for hydrogen production by steam reforming of biological oil as claimed in claim 1, wherein the mass percentage of the active component is 15-20%, the mass percentage of the synergistic component is 1-20%, and the balance is a carrier, based on the total mass of the nickel-based catalyst.
3. The nickel-based catalyst for hydrogen production by biological oil steam reforming as claimed in claim 1, wherein the nickel-based catalyst for hydrogen production by biological oil steam reforming is granular and has a particle size of 420-850 μm.
4. The preparation method of the nickel-based catalyst for hydrogen production by steam reforming of the biological oil as claimed in claim 1, characterized by comprising the following steps:
(1) preparation of Al 2 O 3 Precursor: dissolving aluminum isopropoxide in a proper amount of absolute ethyl alcohol, adding a proper amount of hexadecyl trimethyl ammonium bromide, stirring at normal temperature, and performing ultrasonic treatment to obtain a mixed solution; slowly dripping deionized water into the mixed solution under the stirring state, and stirring under the sealing condition until no precipitate is generated; filtering, washing the filtrate with ammonium nitrate ethanol solution to obtain Al 2 O 3 A precursor;
(2) preparation of BaAl 2 O 3 Precursor: adding a proper amount of deionized water into barium acetate, and mixing with Al 2 O 3 Mixing the precursors, drying by distillation after ultrasonic treatment, calcining the obtained solid to obtain BaAl 2 O 3 A precursor;
(3) preparation of NiBaAl 2 O 3 Precursor: dissolving nickel nitrate and urea in deionized water, adding BaAl 2 O 3 Performing ultrasonic treatment on the precursor, reacting under the conditions of stirring and 90 +/-3 ℃, centrifuging and drying after reaction, performing compression molding on the dried powder, crushing and screening to obtain the NiBaAl powder 2 O 3 A precursor;
(4) reduction: mixing NiBaAl 2 O 3 And (3) reducing the precursor by using hydrogen and treating the precursor by using water vapor to obtain the biological oil vapor reforming hydrogen production nickel-based catalyst.
5. The preparation method of the nickel-based catalyst for hydrogen production by steam reforming of biological oil according to claim 4, wherein in the step (1), the mass ratio of cetyl trimethyl ammonium bromide to aluminum isopropoxide is (3-4): 1, the mass ratio of deionized water to aluminum isopropoxide is (5-6): 1; the mass concentration of ammonium nitrate in the ammonium nitrate ethanol solution is 5-6 g/L.
6. The method for preparing the nickel-based catalyst for hydrogen production by steam reforming of biological oil as claimed in claim 4, wherein in the step (2), barium acetate and Al are added 2 O 3 The molar ratio of the precursor is (0.025-0.17): 1; evaporating to dryness by adopting a 110 ℃ sand bath; the calcining temperature is 800 ℃, and the calcining time is 4-6 h.
7. The preparation method of the nickel-based catalyst for hydrogen production by biological oil steam reforming as claimed in claim 4, wherein in the step (3), the mass ratio of nickel nitrate to urea is (3-4): 1; nickel nitrate and BaAl 2 O 3 The mass ratio of the precursor is (0.45-0.5): 1.
8. the preparation method of the nickel-based catalyst for hydrogen production by biological oil steam reforming as claimed in claim 4 or 7, wherein in the step (4), the particle size of the nickel-based catalyst for hydrogen production by biological oil steam reforming is 420-850 μm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988661A (en) * | 1988-09-09 | 1991-01-29 | Catalysts And Chemicals Inc., Far East | Steam reforming catalyst for hydrocarbons and method of producing the catalyst |
| CN1473074A (en) * | 2000-11-08 | 2004-02-04 | ������������ʽ���� | Catalyst for reforming hydrocarbon and method for reforming hydrocarbon using the same |
| CN101444740A (en) * | 2008-12-16 | 2009-06-03 | 中国科学院广州能源研究所 | Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof |
-
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- 2022-05-06 CN CN202210484452.6A patent/CN114950441A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4988661A (en) * | 1988-09-09 | 1991-01-29 | Catalysts And Chemicals Inc., Far East | Steam reforming catalyst for hydrocarbons and method of producing the catalyst |
| CN1473074A (en) * | 2000-11-08 | 2004-02-04 | ������������ʽ���� | Catalyst for reforming hydrocarbon and method for reforming hydrocarbon using the same |
| CN101444740A (en) * | 2008-12-16 | 2009-06-03 | 中国科学院广州能源研究所 | Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JIANGLONG PU ET AL.: ""Highly active Nd-promoted Ni@Al2O3 core-shell catalyst for steam reforming of acetic acid: Insights of the remarkable coke resistance"", vol. 46, pages 39108 - 39121, XP086848560, DOI: 10.1016/j.ijhydene.2021.08.238 * |
| ZHANMING ZHANG ET AL.: ""Steam reforming of acetic acid over Ni–Ba/Al2O3 catalysts: Impacts of barium addition on coking behaviors and formation of reaction intermediates"", vol. 43, pages 208 - 210 * |
| 邹卫兵等: ""制备方法对二甲醚水蒸气重整制氢催化剂Cu-Ni/γ-Al2O3性能的影响"", vol. 35, no. 5, pages 11 - 14 * |
| 马正先等: "《纳米氧化锌制备原理与技术》", 31 August 2014, 中国矿业大学出版社, pages: 170 - 171 * |
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