CN114534732A - Synthesis method of catalyst for preparing hydrogen by reforming propane steam - Google Patents
Synthesis method of catalyst for preparing hydrogen by reforming propane steam Download PDFInfo
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- CN114534732A CN114534732A CN202210106998.8A CN202210106998A CN114534732A CN 114534732 A CN114534732 A CN 114534732A CN 202210106998 A CN202210106998 A CN 202210106998A CN 114534732 A CN114534732 A CN 114534732A
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- indium
- propane
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 75
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000001294 propane Substances 0.000 title claims abstract description 50
- 238000002407 reforming Methods 0.000 title claims abstract description 9
- 238000001308 synthesis method Methods 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000629 steam reforming Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- YLZGECKKLOSBPL-UHFFFAOYSA-N indium nickel Chemical compound [Ni].[In] YLZGECKKLOSBPL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 13
- 229910015335 Ni2In Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- -1 nickel indium hydroxide Chemical compound 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 150000002471 indium Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/70—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
- B01J23/825—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 gallium, indium or thallium
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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
- B01J23/83—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 rare earths or actinides
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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
- 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
- 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
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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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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
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Abstract
The invention belongs to the technical field of hydrogen preparation, and discloses a method for preparing a hydrogen catalyst by reforming propane steam. The catalyst comprises the following components in percentage by mass: 5-20% of active component and 95-80% of oxide carrier; the active component comprises NixIny with different Ni/In ratios; the carrier is an oxide. The non-toxic nickel indium intermetallic compound exhibits excellent selectivity and stability in the production of hydrogen by propane steam reforming due to a unique electronic structure. Wherein the hydrogen selectivity is Ni2In/SiO2Up to 72 percent, has the potential of replacing the industrialized nickel-based catalyst and has wide application prospect.
Description
Technical Field
The invention relates to the field of hydrogen preparation, in particular to a preparation method of a novel supported nickel-indium catalyst and application of the supported nickel-indium catalyst in propane steam reforming reaction.
Background
In order to solve the problems of global energy and environmental pollution, new green energy is sought by all countries in the world. Compared with the traditional energy, the hydrogen has the advantages of high combustion value, high comprehensive heat efficiency, zero carbon emission and the like, and is the new energy with the most potential in the future. Meanwhile, the hydrogen fuel cell has ultra-strong cruising ability and extremely short inflation time, so that the hydrogen energy automobile gradually occupies the market of the fuel automobile. However, the current problem limiting the development of the hydrogen energy industry is the excessive cost of hydrogen production.
At present, six types of hydrogen production modes are mainly used in China: natural gas hydrogen production, coal gasification hydrogen production, industrial byproduct hydrogen production, water electrolysis hydrogen production, water photolysis hydrogen production, biomass and other hydrogen production modes. Although the hydrogen production methods are various, the methods are superior and inferior. The hydrogen production by natural gas has wide application range, but has low utilization rate of raw materials, complex process and high operation difficulty, and the environmental protection is reduced by greenhouse gases such as carbon dioxide in the product. The coal gasification hydrogen production is not only limited by the supply of raw materials, and the construction site needs to depend on coal enterprises, but also discharges a large amount of greenhouse gases. The industrial byproduct hydrogen production utilizes the industrial product byproduct, and the cost is lower. The hydrogen production product by electrolyzing water has high purity and no pollution, but the popularization is limited due to high cost. The hydrogen production technology by photolysis of water and biomass is not mature, and certain time is needed for commercialization. In addition, the electrodes of hydrogen fuel cells are made of special porous materials, which not only provide a large contact surface for gas and electrolyte, but also catalyze the chemical reaction of the cell, and because compounds containing C and S have irreversible poisoning effects on the electrodes, the requirements on the impurity concentration in hydrogen are high.
The natural gas hydrogen production is still the main method for industrial hydrogen production by comprehensively considering the economy, environmental protection and quality. The natural gas steam reforming technology in China is mature, and comprises (1) desulfurization pretreatment of raw materials; (2) steam conversion; (3) carrying out a shift reaction; (4) the method has the advantages of purification, reliable operation of the device, strong economy and suitability for large-scale production, but because the main component of the natural gas is methane, the technology has the problems of complex process flow, high reaction temperature (800 ℃), low utilization rate of raw materials, low CO conversion rate (less than 45%) in the shift reaction, easy carbon deposition and inactivation of the traditional Ni catalyst and the like.
The existing research shows that the nickel catalyst has low selectivity to hydrogen due to the overhigh surface activity to carbon element and unbalanced surface chemical property in the application of propane steam reforming hydrogen production, and has the problems of high contents of byproducts such as carbon monoxide, carbon dioxide and methane, easy carbon deposition inactivation, short service life of the catalyst and the like.
Disclosure of Invention
The technical problem is as follows: aiming at the defects of the prior art, the invention aims to provide a synthesis method of a catalyst for preparing hydrogen by propane steam reforming, compared with the preparation of hydrogen by natural gas steam reforming, the method has the advantages of high propane raw material utilization rate, high hydrogen yield, low impurity content in crude hydrogen, low reaction temperature, low energy consumption and simple process flow.
The technical scheme is as follows: in the synthesis method of the catalyst for preparing hydrogen by reforming propane steam, the catalyst is a supported nickel-indium intermetallic compound catalyst, and Ni is used2In or Ni2In3And an oxide carrier, wherein the mass fraction of each component is as follows: 5 to 20% of Ni2In or Ni2In380-95% of an oxide carrier; the preparation method of the supported nickel-indium intermetallic compound catalyst comprises the following steps:
step 3, deposition-precipitation: heating the precursor mixture obtained in the step 2 to 30-90 ℃, putting the precursor mixture into the oxide carrier treated in the step 1, adding 0.4-4M sodium hydroxide to adjust the pH value to 4-9, washing with deionized water, and filtering to obtain a composite with nickel indium hydroxide deposited in the oxide carrier;
and 4, reduction treatment: drying the compound obtained in the step 3) in a vacuum drying oven for 2-24 hours, and then reducing the compound at 400-800 ℃ in the atmosphere of hydrogen or the mixed gas of carbon monoxide and argon, thereby obtaining Ni2In or Ni2In3And an oxide support.
Wherein the content of the first and second substances,
the oxide carrier in the step 1) is as follows: silicon dioxide, titanium dioxide or cerium dioxide.
The nickel salt in the step 2) is nickel dichloride, nickel nitrate hexahydrate or nickel acetate; the indium salt is indium trichloride, hydrated indium nitrate or indium acetate.
The concentration of the hydrogen or the carbon monoxide in the step 4 is 2 to 100 percent of the volume fraction in the argon, and the reduction time is 30min to 12 h.
The application of the catalyst synthesized by the method in preparation of hydrogen by reforming propane steam is that the reaction temperature is 400-700 ℃, the molar ratio of water to propane is 9-3, and the reaction mass space velocity is 0.5-3.0 h-1And the reaction time is 20 h.
Has the advantages that: compared with the prior art, the invention has the following beneficial effects:
1. the oxide obtained by the invention carries Ni2In and Ni2In3The intermetallic compound has ordered pure phase, no toxicity, low cost, good synthesis repeatability, simple synthesis steps, no three-waste discharge and large-scale production.
2. The supported catalyst is applied to a propane steam reforming hydrogen production system, the selectivity of hydrogen is up to 72%, the content of by-products, namely carbon monoxide and methane is lower than 3%, and the stability is high.
Drawings
Figure 1 is an XRD diffractogram of the catalysts of example 1 and example 6 of the present invention.
Detailed Description
During research, the inventors of the present invention found that by adding p-block elements, such as indium, the surface chemical properties of nickel, including surface adsorption and activation to C, H, O, can be adjusted, thereby increasing hydrogen selectivity. In addition, the proportion of nickel and indium in the catalyst is changed, so that the catalyst can show different catalytic performances in the propane steam reforming reaction. Meanwhile, due to the formation of covalent bonds in the nickel-indium intermetallic compound, the nickel-indium intermetallic compound has better thermal stability and anti-carbon deposition performance than pure metal nickel under reaction conditions. The invention therefore provides a catalyst for the steam reforming of propane to produce hydrogen, comprising a nickel-indium intermetallic compound supported on an oxide support.
The preparation method of the supported nickel-indium catalyst provided by the invention comprises the following steps: the preparation method comprises the steps of pretreating an oxide carrier, uniformly mixing nickel salt and indium salt according to the body composition of the catalyst, preparing nickel-indium hydroxide loaded on the oxide by a deposition-precipitation method, filtering, cleaning, drying in a vacuum drying oven, and reducing in a reducing atmosphere to obtain the catalyst. The carrier is pretreated oxide such as silicon dioxide, titanium dioxide and cerium dioxide; the nickel salt is nickel dichloride, nickel nitrate hexahydrate and nickel acetate; the indium salt is indium trichloride, indium nitrate hydrate, and indium acetate.
The catalyst is applied to the hydrogen production by reforming propane steam, carbon monoxide or hydrogen reduction pretreatment needs to be carried out on the catalyst before use, the reaction temperature is 400-700 ℃, the molar ratio of water to propane is 3-9, and the reaction mass space velocity is 0.5-3.0 h-1。
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. The specific experimental conditions and methods not indicated in the following examples are generally conventional means well known to those skilled in the art.
Example 1:
the catalyst for preparing hydrogen by reforming propane steam comprises the following components, by mass, 5% of active components and 95% of silica carriers; the active component is a nickel-indium intermetallic compound with the molar ratio of Ni/In of 2.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 950mg of silica are weighed into a preconditioner and calcined at 400 ℃ for 6h with air. 123 mg of nickel nitrate hexahydrate and 87mg of indium nitrate hydrate were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated silicon dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 6-8, washing and filtering with deionized water for three times, and preparing the nickel indium hydroxide deposited on the silicon dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12 hours and then reduced by introducing carbon monoxide at 800 ℃ for 4 hours.
(2) The catalyst of the embodiment is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, and the reaction temperature of water and propaneThe molar ratio of (A) to (B) is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 2:
a novel supported catalyst comprises the following components, by mass, 10% of active components and 90% of a titanium dioxide carrier; the active component is a nickel-indium intermetallic compound with the molar ratio of Ni/In of 2.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 900mg of titanium dioxide are weighed out and calcined in a preconditioner at 200 ℃ for 6 hours by passing air through the preconditioner. 247 mg of nickel nitrate hexahydrate and 174mg were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated titanium dioxide carrier, then adding 2M sodium hydroxide to adjust the pH to 9, washing with deionized water and filtering for three times to prepare the nickel-indium hydroxide deposited on the titanium dioxide carrier. The obtained nickel indium hydroxide was dried in a vacuum oven for 12 hours and then reduced with carbon in a carbon monoxide atmosphere at 400 ℃ for 4 hours.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 3:
a novel supported catalyst comprises the following components, by mass, 15% of active components and 85% of a silica carrier; the active component is a nickel-indium intermetallic compound with the molar ratio of Ni/In of 2.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 850mg of silica are weighed out and calcined in a preconditioner at 400 ℃ for 6h with air. 168 mg of nickel dichloride and 171mg of indium trichloride were weighed out and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated silicon dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 6-8, washing and filtering with deionized water for three times, and preparing the nickel indium hydroxide deposited on the silicon dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12 hours and then reduced by introducing carbon monoxide at 800 ℃ for 4 hours.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 2h-1。
Example 4:
a novel supported catalyst comprises the following active components, by mass, 20% and a cerium oxide carrier 80%; the active component is a nickel-indium intermetallic compound with the molar ratio of Ni/In of 2.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 800mg of cerium oxide are weighed out and calcined in a preconditioner at 500 ℃ for 6h by passing air through the preconditioner. 494 mg of nickel nitrate hexahydrate and 348mg of indium nitrate hydrate were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated cerium dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 6-8, washing with deionized water, and filtering for three times to prepare the nickel indium hydroxide deposited on the cerium dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12 hours and then reduced for 4 hours at 700 ℃ by introducing hydrogen.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 5:
a novel supported catalyst comprises the following active components, namely 13% by mass of a cerium dioxide carrier; the active component is a nickel-indium intermetallic compound with the molar ratio of Ni/In of 2.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 870mg of cerium oxide were weighed out and calcined in a preconditioner at 500 ℃ for 6h with air. 321 mg of nickel acetate and 226mg of indium acetate were weighed out and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated cerium dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 6-8, washing with deionized water, and filtering for three times to prepare the nickel indium hydroxide deposited on the cerium dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12 hours and then reduced by introducing carbon monoxide at 800 ℃ for 4 hours.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, the molar ratio of water to propane is 3:1, and the reaction mass space velocity is 3h-1。
Example 6:
a novel supported catalyst comprises the following components, by mass, 17% of an active component and 83% of a silica carrier; the active component Ni/In mol ratio is 2/3.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 830mg of silica were weighed into a preconditioner and calcined at 400 ℃ for 6h with air. 211 mg of nickel nitrate hexahydrate and 447mg of indium nitrate hydrate were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated silicon dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 4-7, washing with deionized water and filtering for three times to prepare the nickel indium hydroxide deposited on the silicon dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12h, and then reduced by introducing carbon monoxide at 700 ℃ for 4 h.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 650 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 2h-1。
Example 7:
a novel supported catalyst comprises the following components, by mass, 7% of active components and 93% of a silica carrier; the active component Ni/In mol ratio is 2/3.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 930mg of silica was weighed out and calcined in a preconditioner at 400 ℃ for 6h with air. 87mg of nickel nitrate hexahydrate and 184mg of indium nitrate hydrate were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated silicon dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 4-7, washing with deionized water and filtering for three times to prepare the nickel indium hydroxide deposited on the silicon dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12 hours and then reduced for 4 hours at 700 ℃ by introducing hydrogen.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 650 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 2h-1。
Example 8:
a novel supported catalyst comprises the following components, by mass, 10% of an active component and 90% of a cerium oxide carrier; the active component Ni/In mol ratio is 2/3.
The preparation method of the novel supported catalyst described in this example is a deposition-precipitation method, which specifically includes the following steps:
(1) 900mg of cerium oxide are weighed out and calcined in a preconditioner at 500 ℃ for 6h by passing air through the preconditioner. 165 mg of nickel nitrate hexahydrate and 233mg of indium nitrate hydrate were weighed and dissolved in a small amount of deionized water. And heating the mixture to 80 ℃, simultaneously adding the treated cerium dioxide carrier, then adding 2M sodium hydroxide to adjust the pH value to 7-9, washing with deionized water, and filtering for three times to prepare the nickel indium hydroxide deposited on the cerium dioxide carrier. The obtained nickel indium hydroxide is dried in a vacuum drying oven for 12h, and then reduced by introducing carbon monoxide at 700 ℃ for 4 h.
(2) The catalyst of the embodiment is used in a propane steam reforming hydrogen production system, the reaction temperature is 700 ℃, and the molar ratio of water to propaneThe ratio is 9:1, and the reaction mass space velocity is 2h-1。
Comparative example 1:
a nickel catalyst for propane steam reforming hydrogen production contains the following components, by mass, 10% of active components and 90% of a carrier; the active component nickel and the carrier are silicon dioxide.
The preparation method of the nickel catalyst for producing hydrogen from propane, which is described in the comparative example, is a deposition-precipitation method, which specifically comprises the following steps:
(1) 900mg of silica are weighed out and calcined in a preconditioner at 400 ℃ for 6h with air. 493 mg of nickel nitrate hexahydrate were weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, then 2M sodium hydroxide was added to adjust the pH to 7, washed with deionized water and filtered three times to prepare nickel hydroxide deposited on a silica support. The obtained nickel hydroxide was dried in a vacuum oven for 12 hours and then reduced in a hydrogen atmosphere at 400 ℃ for 2 hours.
(2) The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 550 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
The reaction conditions for the catalyst described in this comparative example for the production of hydrogen by steam reforming of propane were identical to those for the catalyst used in example 1.
The catalysts for the hydrogen production by propane steam reforming are prepared according to the methods described in examples 1 to 8 and comparative example 1, the catalytic performance of the catalysts is tested in a gas-phase fixed bed reactor according to the corresponding reaction conditions of the hydrogen production by propane steam reforming, the products of hydrogen, carbon dioxide, carbon monoxide and methane are quantitatively analyzed by a gas chromatograph, the conversion rate of propane and the content of the products are calculated according to a conventional method, and the specific results are shown in table 1.
Table 1 propane conversion and hydrogen, carbon dioxide, carbon monoxide and methane content in the product of a propane steam reforming hydrogen production process using a catalyst.
As can be seen from the results of the propane steam reforming reaction in Table 1 and the examples and comparative examples, the novel catalyst for preparing hydrogen by propane steam reforming provided by the invention has the advantages of remarkably improving the selectivity and purity of hydrogen and still maintaining high propane conversion rate.
The above detailed description is of the preferred embodiments of the present invention, and should not be taken as limiting the invention, but rather the appended claims are intended to cover all such modifications, equivalents, and improvements as fall within the true spirit and scope of the invention.
Claims (5)
1. A process for synthesizing the catalyst used to prepare hydrogen by reforming propane vapour features that said catalyst is a carried intermetallic Ni-in compound catalyst2In or Ni2In3And an oxide carrier, wherein the mass fraction of each component is as follows: 5 to 20% of Ni2In or Ni2In380-95% of an oxide carrier; the preparation method of the supported nickel-indium intermetallic compound catalyst comprises the following steps:
step 1, treating an oxide carrier: heating the oxide carrier in an air atmosphere to 200-600 ℃ and calcining for 2-8 h;
step 2, mixing of precursors: weighing nickel salt and indium salt with the molar ratio of 0.667-2, and dissolving in a small amount of deionized water;
step 3, deposition-precipitation: heating the precursor mixture obtained in the step 2 to 30-90 ℃, putting the precursor mixture into the oxide carrier treated in the step 1, adding 0.4-4M sodium hydroxide to adjust the pH value to 4-9, washing with deionized water, and filtering to obtain a composite with nickel indium hydroxide deposited in the oxide carrier;
and 4, reduction treatment: drying the compound obtained in the step 3) in a vacuum drying oven2-24 h, and then reducing at 400-800 ℃ in the atmosphere of hydrogen or the mixed gas of carbon monoxide and argon, thereby obtaining Ni2In or Ni2In3And an oxide support.
2. The method of synthesizing a catalyst for hydrogen gas production by propane steam reforming as set forth in claim 1, wherein the oxide support in step 1) is: silicon dioxide, titanium dioxide or cerium dioxide.
3. The method for synthesizing a catalyst for producing hydrogen by reforming propane steam as set forth in claim 1, wherein the nickel salt in the step 2) is nickel dichloride, nickel nitrate hexahydrate, or nickel acetate; the indium salt is indium trichloride, hydrated indium nitrate or indium acetate.
4. A method for synthesizing a catalyst for hydrogen production by propane steam reforming as set forth in claim 1, wherein the concentration of hydrogen or carbon monoxide in step 4 is 2 to 100% by volume in argon gas, and the reduction time is 30min to 12 hours.
5. The application of the catalyst synthesized by the method of claim 1 in preparation of hydrogen by propane steam reforming is characterized in that the reaction temperature is 400-700 ℃, the molar ratio of water to propane is 9-3, and the reaction mass space velocity is 0.5-3.0 h-1And the reaction time is 20 h.
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| CN107649157A (en) * | 2017-10-15 | 2018-02-02 | 华东师范大学 | A kind of support type carbonization nickel indium alloy catalyst and its preparation method and application |
| CN109675569A (en) * | 2019-01-28 | 2019-04-26 | 华东师范大学 | A kind of load-type nickel based alloy catalyst and its preparation method and application |
| CN109876808A (en) * | 2019-02-27 | 2019-06-14 | 中国石油大学(北京) | A kind of catalyst of preparing propylene by dehydrogenating propane and its preparation and application |
| US20200238259A1 (en) * | 2017-08-01 | 2020-07-30 | Purdue Research Foundation | Nickel alloy catalysts for light alkane dehydrogenation |
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| US20200238259A1 (en) * | 2017-08-01 | 2020-07-30 | Purdue Research Foundation | Nickel alloy catalysts for light alkane dehydrogenation |
| CN107649157A (en) * | 2017-10-15 | 2018-02-02 | 华东师范大学 | A kind of support type carbonization nickel indium alloy catalyst and its preparation method and application |
| CN109675569A (en) * | 2019-01-28 | 2019-04-26 | 华东师范大学 | A kind of load-type nickel based alloy catalyst and its preparation method and application |
| CN109876808A (en) * | 2019-02-27 | 2019-06-14 | 中国石油大学(北京) | A kind of catalyst of preparing propylene by dehydrogenating propane and its preparation and application |
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