CN114471580A - Synthesis and application method of supported nickel-gallium catalyst - Google Patents
Synthesis and application method of supported nickel-gallium catalyst Download PDFInfo
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- CN114471580A CN114471580A CN202210106982.7A CN202210106982A CN114471580A CN 114471580 A CN114471580 A CN 114471580A CN 202210106982 A CN202210106982 A CN 202210106982A CN 114471580 A CN114471580 A CN 114471580A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000006229 carbon black Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000001294 propane Substances 0.000 claims abstract description 38
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims abstract description 33
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 29
- 238000000629 steam reforming Methods 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229940044658 gallium nitrate Drugs 0.000 claims description 10
- 229910052759 nickel 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 150000002258 gallium Chemical class 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 239000007789 gas Substances 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
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 4
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-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
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a synthesis method and an application method of a supported nickel-gallium catalyst, wherein the catalyst is a supported nickel-gallium intermetallic compound catalyst which is composed of NiGa and a carbon black carrier, the mass fractions of the components are 5-95% of NiGa and 80-95% of C, the synthesis method comprises the steps of 1, treatment of the carbon black carrier, 2, preparation of gallium hydroxide, 3, preparation of nickel-gallium hydroxide, 4, reduction treatment and 5, annealing treatment, the supported nickel-gallium intermetallic compound catalyst is prepared and is applied to propane steam reforming hydrogen production, and the problems of low catalytic activity and poor stability of the existing nickel-gallium catalyst in the propane steam reforming hydrogen production reaction are effectively solved.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a preparation method of a supported nickel-gallium catalyst and application of the supported nickel-gallium catalyst in propane steam reforming reaction.
Background
The development and design of efficient, cheap and green catalysts promote the high-quality development of petrochemical and chemical industries, and are one of effective ways for solving the problems of global energy shortage and environmental pollution, and the traditional single-metal catalyst often causes the problems of excessive hydrogenation, bond breaking, carbon deposition on the surface of the catalyst and the like due to the overhigh activity of the surface pair C, H, O, so that the selectivity and the stability of a target product are reduced. In addition, the activity regulation range of the single metal material is limited, and the activity degree of C, H, O and N can not be regulated according to the catalytic reaction requirement, so that a plurality of challenging reactions such as green hydrogen production, selective hydrogenation, biomass catalytic conversion, ammonia gas preparation by nitrogen reduction and the like still exist in the petrochemical industryCO2Transformation and the like restrict transformation and upgrading of related industries.
Intermetallic compounds composed of metal elements and p-region elements and having highly ordered atomic arrangement have a specific crystal structure and a unique electronic structure, and exhibit physicochemical properties different from those of other single metals and disordered alloys, and thus such materials have been widely used in many fields. In particular, in recent years, researchers have found that the catalytic activity, selectivity and stability of intermetallic compounds are all significantly improved compared with that of single metal components of the intermetallic compounds, so that the intermetallic compounds are used as novel catalytic materials with development potential. In addition, tens of thousands of elemental combinations provide more room for catalyst selection for different reactions. However, the problem faced in the current study of intermetallic compounds is the controlled synthesis of intermetallic compounds, including crystal composition, particle size and dispersibility of particles on the support, which are necessary conditions for systematic study of the catalytic performance of intermetallic compounds. However, obtaining phase-pure ordered intermetallic compounds, especially supported nanoparticles, often requires harsh synthesis conditions, and control of particle dispersion and size is particularly difficult.
The existing synthesis method of nickel-gallium Intermetallic Compound applied to preparation of hydrogen by propane steam Reforming comprises a Wet impregnation method (Controlling selection and stabilization in the Hydrocarbon Well-Reforming Reaction Using Well-Defined Ni + Ga Intermetallic Compounds, ACS Catal.2020,10, 8968-8980). They used a wet impregnation method, which used silica as a carrier, and dipped it in mixed solutions of nickel nitrate and gallium nitrate of different concentrations, and then subjected to reduction treatment at 700 ℃ for 2h in a hydrogen atmosphere, thereby obtaining nickel-gallium catalysts of different compositions. Through a series of characterization and catalytic performance tests, the annealed Ni is found3Ga/SiO2The hydrogen selectivity in the reaction of preparing hydrogen by reforming propane steam can reach 73%, but the once-through conversion rate of propane is as low as 15-20%, and the initial deactivation rate of the catalyst is high. These problems are caused by the non-uniform size distribution of nickel gallium intermetallic compound nanoparticles and the poor dispersibility on silica supports.
The existing research shows that the nickel metal catalyst has two active sites in the application of propane steam reforming hydrogen production. One is a high-activity site such as an edge, a corner, a step and the like at a contact interface with a carrier, the high-activity site shows the problems of low selectivity to hydrogen, high methane content, easy carbon deposition inactivation, short service life of a catalyst and the like caused by the overhigh surface activity to carbon elements and unbalanced surface chemical properties, and the high-activity site is dominant; the other is a cascade active site, generally with weaker surface activity, which mainly determines the selectivity of the by-products carbon monoxide and carbon dioxide. In addition, the nickel metal catalyst may also suffer from agglomeration or sintering problems during the catalytic reaction, thereby further reducing its dispersibility and stability.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a synthesis method and an application method of a supported nickel-gallium catalyst, wherein the addition of gallium can form a stable nickel-gallium intermetallic compound with nickel element so as to improve the stability of the nickel-gallium intermetallic compound in reaction. Meanwhile, the unique electronic structure of the nickel-gallium intermetallic compound enables the nickel-gallium intermetallic compound to show unique surface chemical properties, improves the selectivity to hydrogen and reduces the degree of carbon deposition. The invention relates to a preparation method of a supported nickel-gallium catalyst with uniform nano-particle size distribution and good dispersibility, and the preparation method is applied to propane steam reforming reaction.
The technical scheme is as follows: in the synthesis method of the supported nickel-gallium catalyst, the catalyst is a supported nickel-gallium intermetallic compound catalyst and consists of 5-20% of NiGa and 80-95% of C in mass fraction, and the synthesis method of the supported nickel-gallium intermetallic compound catalyst comprises the following steps:
and 4, reduction treatment: drying the nickel-gallium hydroxide obtained in the step (3) in a vacuum drying oven for 2-36 hours, and then reducing at 400-800 ℃ in a mixed gas atmosphere of hydrogen and argon to obtain a pure-phase ordered supported nickel-gallium intermetallic compound catalyst;
step 5, annealing treatment: and (4) annealing the supported nickel-gallium intermetallic compound catalyst obtained in the step (4) at 300-800 ℃ for 2-12 h in an argon atmosphere.
Wherein,
the nickel salt in the step 3 is nickel dichloride, nickel nitrate hexahydrate or nickel acetate.
The gallium salt in the step 2 is gallium trichloride, hydrated gallium nitrate or gallium acetate.
And 4, in the mixed gas atmosphere of hydrogen and argon, the hydrogen concentration accounts for 2-100% of the volume fraction in the argon, and the reduction time is 30 min-12 h.
The application of the supported nickel-gallium catalyst synthesized by the method of the invention is as follows: the application of the supported nickel-gallium intermetallic compound catalyst in a propane steam reforming reaction hydrogen production system has the reaction temperature of 300-600 ℃, the molar ratio of water to propane of 3-9 and the reaction mass space velocity of 0.5-3.0 h-1The reaction time is 20 h.
Has the advantages that: compared with the prior art, the invention has the following beneficial effects:
1. the NiGa intermetallic compound nano-particles loaded by the carbon black have uniform size distribution, good dispersity, high crystallinity and few crystal defects.
2. The carrier type catalyst is applied to a propane steam reforming hydrogen production system, the conversion per pass is 40-60%, the selectivity of hydrogen is up to 75%, the content of a byproduct carbon monoxide is lower than 3%, and the stability is good.
Drawings
Figure 1 is an XRD diffractogram of the catalyst of example 1 of the present invention,
FIG. 2 is a TEM image of the catalyst of example 1 of the present invention.
Detailed Description
The preparation method of the supported nickel-gallium catalyst provided by the invention comprises the following steps: firstly, pretreating a carbon black carrier, uniformly mixing nickel salt and gallium salt according to the body composition of the catalyst, preparing nickel-gallium hydroxide loaded on the carbon black carrier by adopting a deposition-precipitation method, filtering, drying in a vacuum drying oven, and reducing in a reducing atmosphere to obtain the catalyst. In the invention, the carrier is pretreated carbon black; the nickel salt is nickel dichloride, nickel nitrate hexahydrate and nickel acetate; the gallium salt is gallium trichloride, hydrated gallium nitrate and gallium acetate.
The catalyst is applied to the hydrogen production by reforming propane steam, reduction and annealing pretreatment are carried out on the catalyst before use, the reaction temperature is 300-600 ℃, the molar ratio of water to propane is 9-3, 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. 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 supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 5 percent of active component and 95 percent of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
1055mg of carbon black is weighed and added into a 20% nitric acid solution, heated to 70 ℃, stirred for 6h, filtered, cleaned and dried in a vacuum drying oven for 12 h. 160.5mg of hydrated gallium nitrate was weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 5, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. Then weighing 125.1mg of nickel nitrate hexahydrate, adding 2M sodium hydroxide to adjust the pH value to 9, reacting for 1h to obtain nickel-gallium hydroxide deposited on a carbon black carrier, drying for 12h in a vacuum drying oven, reducing for 2h at 700 ℃ in hydrogen, and finally introducing argon to anneal for 12h at 800 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 2: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 10 percent of active component and 90 percent of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
1000mg of carbon black is weighed and added into 10 percent nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered, cleaned and dried in a vacuum drying oven for 12 hours. 320.9mg of gallium acetate were weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 7, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. Then 250.2mg of nickel acetate is weighed, 2M sodium hydroxide is added to adjust the pH value to 9, reaction is carried out for 1h, nickel gallium hydroxide deposited on a carbon black carrier is obtained, drying is carried out for 12h in a vacuum drying oven, and then reduction is carried out for 2h in hydrogen at 700 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 3: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 15% of active component and 85% of carbon black carrier, wherein the preparation method is a deposition-precipitation method, and the preparation method comprises the following specific steps:
944mg of carbon black is weighed and added into a 20% nitric acid solution, heated to 70 ℃, stirred for 6h, filtered, cleaned and dried in a vacuum drying oven for 12 h. 481.3mg of hydrated gallium nitrate was weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 4, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. Then weighing 375.3mg of nickel nitrate hexahydrate, adding 2M sodium hydroxide to adjust the pH value to 8, reacting for 1h to obtain nickel gallium hydroxide deposited on a carbon black carrier, drying for 12h in a vacuum drying oven, then reducing for 2h at 400 ℃ in 5% hydrogen, and finally introducing argon to carry out annealing treatment for 12h at 800 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 4: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 20% of active component and 80% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
889mg of carbon black is weighed and added into a 20% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered, cleaned and dried in a vacuum drying oven for 12 hours. 641.8mg of hydrated gallium nitrate was weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 7, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. 500.4mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH value to 9, reaction is carried out for 1h, nickel-gallium hydroxide deposited on a carbon black carrier is obtained, the nickel-gallium hydroxide is dried for 12h in a vacuum drying oven, then reduction is carried out for 2h in hydrogen at 500 ℃, and finally, argon is introduced to carry out annealing treatment for 12h at 300 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 5: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 7 percent of active component and 93 percent of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
1033mg of carbon black is weighed and added into 20 percent nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered, cleaned and dried in a vacuum drying oven for 12 hours. 224.6mg of gallium trichloride was weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 2, then adding the treated carbon black carrier and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. Then 175.1mg of nickel dichloride was weighed, added with 2M sodium hydroxide to adjust the pH to 7 and reacted for 1h to obtain nickel gallium hydroxide deposited on a carbon black support, dried in a vacuum oven for 12h and then reduced in hydrogen at 700 ℃ for 2 h.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 6: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 13 percent of active component and 87 percent of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
967mg of carbon black is weighed and added into a 10% nitric acid solution, the temperature is heated to 70 ℃, the stirring treatment is carried out for 6 hours, and the carbon black is dried for 12 hours in a vacuum drying oven after being filtered and cleaned. 417.2mg of hydrated gallium nitrate was weighed and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH value to 5, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. 325.3mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH value to 9, the mixture reacts for 1 hour to obtain nickel-gallium hydroxide deposited on a carbon black carrier, the nickel-gallium hydroxide is dried for 12 hours in a vacuum drying oven, then the nickel-gallium hydroxide is reduced for 2 hours at 700 ℃ in hydrogen, and finally argon is introduced to perform annealing treatment for 12 hours at 300 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Example 7: the supported nickel-gallium catalyst described in this example contains the following components in mass fraction: 17 percent of active component and 83 percent of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following steps:
922mg of carbon black is weighed and added into a 20% nitric acid solution, the mixture is heated to 70 ℃, stirred for 6 hours, filtered, cleaned and dried in a vacuum drying oven for 12 hours. 545.5mg of hydrated gallium nitrate was weighed out and dissolved in a small amount of deionized water. Heating the mixture to 80 ℃, adding 2M sodium hydroxide to adjust the pH to 5, then adding the treated carbon black carrier, and reacting for 1h to prepare the gallium hydroxide deposited on the carbon black carrier. 425.3mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH value to 9, reaction is carried out for 1h, nickel-gallium hydroxide deposited on a carbon black carrier is obtained, the nickel-gallium hydroxide is dried for 12h in a vacuum drying oven, then reduction is carried out for 2h in hydrogen at 700 ℃, and finally, argon is introduced to carry out annealing treatment for 12h at 800 ℃.
The catalyst is used in a propane-alkane steam reforming hydrogen production system, the reaction temperature is 500 ℃, the molar ratio of water to propane is 3:1, and the reaction mass space velocity is 0.5h-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 carbon black.
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: 1000mg of carbon black is weighed and added into 10 percent nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered, cleaned and dried in a vacuum drying oven for 12 hours. 547.3mg of nickel nitrate hexahydrate was 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 8, washed with deionized water and filtered three times to prepare the nickel hydroxide deposited on the carbon black 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.
The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 400 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
Comparative example 2:
a nickel-gallium 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 Ni3Ga, the carrier is silica.
The preparation method of the nickel-gallium catalyst for producing hydrogen from propane, which is described in the comparative example, is a wet impregnation method, and specifically comprises the following steps: 392.1mg of nickel nitrate hexahydrate and 167.7mg of gallium nitrate hydrate were weighed and dissolved in a small amount of deionized water to obtain a mixture solution of nickel salt and gallium salt. And (2) soaking the silicon dioxide carrier in the nickel salt and gallium salt mixture solution, drying the silicon dioxide carrier in a vacuum drying oven at 80 ℃ for 12h, reducing the silicon dioxide carrier in a hydrogen atmosphere at 700 ℃ for 2h, and annealing the silicon dioxide carrier in an argon atmosphere at 700 ℃ for 12h to obtain the silicon dioxide-loaded nickel-gallium intermetallic compound catalyst.
The catalyst is used in a propane steam reforming hydrogen production system, the reaction temperature is 400 ℃, the molar ratio of water to propane is 9:1, and the reaction mass space velocity is 0.5h-1。
The catalysts for the hydrogen production by propane steam reforming are prepared according to the methods described in examples 1 to 7 and comparative examples 1 to 2, 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 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 carbon black-supported nickel-gallium catalyst provided by the invention is applied to the propane steam reforming hydrogen production, the conversion rate of propane is remarkably improved, and the high selectivity and purity of hydrogen are maintained.
The above detailed description of the preferred embodiments of the present invention is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A method for synthesizing a supported nickel-gallium catalyst is characterized in that the catalyst is a supported nickel-gallium intermetallic compound catalyst and consists of 5-20% of NiGa and 80-95% of carbon black as a carrier, and the method for synthesizing the supported nickel-gallium intermetallic compound catalyst comprises the following steps:
step 1, processing a carbon black carrier: adding carbon black into 1-16M nitric acid aqueous solution, heating to 20-95 ℃, stirring for 0.5-10 h, filtering, cleaning, and drying in a vacuum drying oven for 2-36 h;
step 2, preparation of gallium hydroxide: dissolving gallium salt in deionized water, heating to 20-95 ℃, adding 0.1-4M sodium hydroxide to adjust the pH to 2-9, putting the carbon black carrier treated in the step (1), and reacting for 30 min-1 h to obtain gallium hydroxide;
step 3, preparing nickel gallium hydroxide: dissolving nickel salt in deionized water, putting the solution into the gallium hydroxide solution obtained in the step 2, adding 0.1-4M sodium hydroxide to adjust the pH value to 2-9, and reacting for 30 min-1 h to obtain nickel-gallium hydroxide;
and 4, reduction treatment: drying the nickel-gallium hydroxide obtained in the step (3) in a vacuum drying oven for 2-36 hours, and then reducing at 400-800 ℃ in a mixed gas atmosphere of hydrogen and argon to obtain a pure-phase ordered supported nickel-gallium intermetallic compound catalyst;
step 5, annealing treatment: and (4) annealing the supported nickel-gallium intermetallic compound catalyst obtained in the step (4) at 300-800 ℃ for 2-12 h in an argon atmosphere.
2. The method for synthesizing the supported nickel-gallium catalyst according to claim 1, wherein the nickel salt in step 3 is nickel dichloride, nickel nitrate hexahydrate or nickel acetate.
3. The method for synthesizing the supported nickel-gallium catalyst according to claim 1, wherein the gallium salt in step 2 is gallium trichloride, gallium nitrate hydrate or gallium acetate.
4. The method for synthesizing the supported nickel-gallium catalyst according to claim 1, wherein the hydrogen concentration in the mixed gas atmosphere of hydrogen and argon in step 4 is 2-100% by volume fraction in argon, and the reduction time is 30 min-12 h.
5. The application of the supported nickel-gallium catalyst synthesized by the method according to claim 1, wherein the supported nickel-gallium intermetallic compound catalyst is applied to a propane steam reforming reaction hydrogen production system, the reaction temperature is 300-600 ℃, the molar ratio of water to propane is 3-9, and the reaction mass space velocity is 0.5-3.0 h-1The reaction time is 20 h.
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