CN114471580B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000006229 carbon black Substances 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 239000001294 propane Substances 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims abstract description 35
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims abstract description 34
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 28
- 238000000629 steam reforming Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 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
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 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
- 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
- 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 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
- 238000001914 filtration Methods 0.000 claims description 4
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 4
- 238000010438 heat treatment Methods 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 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
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 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
- 239000011833 salt mixture Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 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
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a supported nickel-gallium catalyst and an application method thereof, wherein the catalyst is a supported nickel-gallium intermetallic compound catalyst, and consists of 5-95% of NiGa and 80-95% of C by mass percent, the synthesis method comprises the steps of 1. Treating the carbon black carrier, 2. Preparing gallium hydroxide, 3. Preparing nickel-gallium hydroxide, 4. Reducing, 5. Annealing, preparing the supported nickel-gallium intermetallic compound catalyst, and being applied to propane steam reforming hydrogen production, thereby effectively solving the problems of low catalytic activity and poor stability of the existing nickel-gallium catalyst in the propane steam reforming hydrogen production reaction.
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 catalyst in a propane steam reforming reaction.
Background
The development and design of efficient, cheap and green catalysts are one of effective ways for promoting the high-quality development of petrochemical and chemical industries and solving the problems of global energy shortage and environmental pollution, and the traditional single-metal catalysts often cause the problems of excessive hydrogenation, bond breakage, carbon deposition on the surface of the catalysts and the like due to the excessive activity of the surface pair C, H, O, so that the selectivity and stability of target products are reduced. In addition, the activity regulation and control range of the monometal 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 still exist in the petrochemical industry, such as green hydrogen production, selective hydrogenation, biomass catalytic conversion, nitrogen reduction for preparing ammonia and CO 2 Transformation, etc., restricts transformation and upgrading of related industries.
Intermetallic compounds composed of a metal element and a p-region element, which are highly ordered in atomic arrangement, have specific crystal structures and unique electronic structures, and exhibit physicochemical properties different from those of other single metals and disordered alloys, and thus such materials are widely used in many fields. In particular, in recent years, researchers find that the catalytic activity, selectivity and stability of intermetallic compounds are remarkably improved compared with the single metal component of the intermetallic compounds, so that the intermetallic compounds are used as novel catalytic materials with development potential. In addition, tens of thousands of combinations of double elements provide more room for catalyst selection for different reactions. However, the current research of intermetallic compounds faces problems of controlled synthesis of intermetallic compounds, including crystal composition, particle size and dispersibility of particles on a carrier, which are necessary conditions for systematically studying the catalytic properties of intermetallic compounds. However, obtaining pure phase ordered intermetallic compounds, especially supported nanoparticles, often requires harsh synthesis conditions, particularly difficult to control the particle dispersion and size.
Existing synthetic methods of nickel gallium intermetallic compounds for the steam reforming of propane to hydrogen include wet impregnation (Controlling Selectivity and Stability in the Hydrocarbon Wet-Reforming Reaction Using Well-Defined ni+ Ga Intermetallic Compound Catalysts, ACS catalyst.2020, 10, 8968-8980). They used a wet impregnation method, using silica as a carrier, impregnating it in a mixed solution of nickel nitrate and gallium nitrate of different concentrations, and then performing a reduction treatment at 700 ℃ for 2 hours in a hydrogen atmosphere, thereby obtaining nickel-gallium catalysts of different compositions. Through a series of characterization and catalytic performance tests, it was found that annealed Ni 3 Ga/SiO 2 The hydrogen selectivity in the reaction for preparing hydrogen by steam reforming of propane can reach 73 percent, but the single pass conversion rate of propane is as low as 15 to 20 percent, and the initial deactivation rate of the catalyst is high. These problems are caused by the non-uniform size distribution of nickel gallium intermetallic nanoparticles and poor dispersibility on silica supports.
Existing studies indicate that nickel metal catalysts include two types of nickel active sites in propane steam reforming hydrogen production applications. One is the high activity site such as side, corner, step, etc. at the interface with carrier contact, this activity site shows the surface activity too high to carbon element and unbalanced surface chemical property causes the selectivity to hydrogen gas low, methane content is high, easy carbon deposition is deactivated, the catalyst life-span is short, etc., and this activity site is dominant; the other is the active site of the step, which is generally weak in surface activity and mainly determines the selectivity of by-product carbon monoxide and carbon dioxide. In addition, during the catalytic reaction, the nickel metal catalyst may undergo agglomeration or sintering problems, thereby further reducing its dispersibility and stability.
Disclosure of Invention
Technical problems: the invention aims to provide a synthesis and application method of a supported nickel-gallium catalyst, wherein the addition of gallium element can form stable nickel-gallium intermetallic compound with nickel element so as to improve the stability of the nickel-gallium intermetallic compound in the reaction. Meanwhile, the unique electronic structure of the nickel-gallium intermetallic compound enables the nickel-gallium intermetallic compound to show unique surface chemical property, improves the selectivity to hydrogen and reduces the carbon deposition degree. The invention relates to a preparation method of a supported nickel-gallium catalyst with uniform nanoparticle size distribution and good dispersibility, and the preparation method is applied to a propane steam reforming reaction.
The technical scheme is as follows: the invention relates to a method for synthesizing a supported nickel-gallium catalyst, which is a supported nickel-gallium intermetallic compound catalyst and consists of 5-20% of NiGa and 80-95% of C by mass percent of a carbon black carrier, wherein the method for synthesizing the supported nickel-gallium intermetallic compound catalyst comprises the following steps:
step 1, carbon black carrier treatment: 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, preparing gallium hydroxide: dissolving gallium salt in deionized water, heating to 20-95 ℃, then adding 0.1-4M sodium hydroxide to adjust the pH to 2-9, adding 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 deionized water into the gallium hydroxide solution obtained in the step 2, then adding 0.1-4M sodium hydroxide to adjust the pH to 2-9, and reacting for 30 min-1 h to obtain nickel gallium hydroxide;
step 4, reduction treatment: drying the nickel gallium hydroxide obtained in the step 3 in a vacuum drying oven for 2-36 h, and then reducing the nickel gallium hydroxide in a mixed gas atmosphere of hydrogen and argon at 400-800 ℃ to obtain a pure-phase ordered supported nickel gallium intermetallic compound catalyst;
step 5, annealing treatment: and (3) annealing the supported nickel-gallium intermetallic compound catalyst obtained in the step (4) for 2-12 hours at 300-800 ℃ 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, gallium nitrate hydrate or gallium acetate.
And (3) the concentration of hydrogen in the mixed gas atmosphere of the hydrogen and the argon in the step (4) is 2-100% of the volume fraction of the hydrogen in the argon, and the reduction time is 30 min-12 h.
The application of the supported nickel-gallium catalyst synthesized by the method disclosed by 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 airspeed of 0.5-3.0 h -1 The reaction time was 20h.
The beneficial effects are that: compared with the prior art, the invention has the following beneficial effects:
1. the obtained carbon black loaded NiGa intermetallic compound nano particles have the advantages of uniform size distribution, good dispersity, high crystallinity and few crystal defects.
2. The carrier catalyst of the invention is applied to a propane steam reforming hydrogen production system, the single pass conversion rate is 40-60%, the hydrogen selectivity is up to 75%, the content of 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 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 bulk composition of the catalyst, preparing nickel gallium hydroxide loaded on the carbon black carrier by adopting a deposition-precipitation method, filtering and cleaning, drying in a vacuum drying oven, and then reducing in a reducing atmosphere to obtain the catalyst. The carrier in the invention is pretreated carbon black; the nickel salt is nickel dichloride, nickel nitrate hexahydrate and nickel acetate; the gallium salt is gallium trichloride, gallium nitrate hydrate and gallium acetate.
The catalyst is applied to the steam reforming hydrogen production of propane, the catalyst needs to be subjected to reduction and annealing pretreatment before use, the reaction temperature is 300-600 ℃, the molar ratio of water to propane is 9-3, and the reaction mass airspeed is 0.5-3.0 h -1 。
The invention is further illustrated by, but is not limited to, the following examples. The specific experimental conditions and methods not specified in the following examples are generally conventional means well known to those skilled in the art.
Example 1:
the supported nickel-gallium catalyst in this embodiment contains the following components in mass percent: 5% of active component and 95% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
1055mg of carbon black was weighed and added to a 20% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered and washed, and dried in a vacuum oven for 12 hours. 160.5mg of gallium nitrate hydrate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 5, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then 125.1mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH value to 9 and then reacts for 1h, the nickel gallium hydroxide deposited on the carbon black carrier is obtained, the nickel gallium hydroxide is dried for 12h in a vacuum drying oven, then reduced for 2h at 700 ℃ in hydrogen, finally argon is introduced to anneal for 12h at 800 ℃.
The catalyst of the embodiment is used in a propane 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 in this embodiment contains the following components in mass percent: 10% of active component and 90% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
1000mg of carbon black was weighed, added to a 10% nitric acid solution, heated to 70℃and stirred for 6 hours, filtered and washed, and dried in a vacuum oven for 12 hours. 320.9mg of gallium acetate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 7, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then 250.2mg of nickel acetate was weighed, pH was adjusted to 9 by adding 2M sodium hydroxide, and then the reaction was carried out for 1 hour to obtain nickel gallium hydroxide deposited on a carbon black support, which was dried in a vacuum oven for 12 hours, and then reduced in hydrogen at 700℃for 2 hours.
The catalyst of the embodiment is used in a propane 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 in this embodiment contains the following components in mass percent: 15% of active component and 85% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
944mg of carbon black was weighed and added to a 20% nitric acid solution, heated to 70℃and stirred for 6 hours, and then dried in a vacuum oven for 12 hours after filtration and washing. 481.3mg of gallium nitrate hydrate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 4, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then 375.3mg of nickel nitrate hexahydrate is weighed, added with 2M sodium hydroxide to adjust the pH value to 8 and then reacted for 1h to obtain nickel gallium hydroxide deposited on a carbon black carrier, dried for 12h in a vacuum drying oven, reduced for 2h at 400 ℃ in 5% hydrogen, finally introduced with argon and annealed for 12h at 800 ℃.
The catalyst of the embodiment is used in a propane 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 in this embodiment contains the following components in mass percent: 20% of active component and 80% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
889mg of carbon black was weighed and added to a 20% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered and washed, and dried in a vacuum oven for 12 hours. 641.8mg of gallium nitrate hydrate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 7, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then, 500.4mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH to 9 and then reacts for 1h, the nickel gallium hydroxide deposited on the carbon black carrier is obtained, the nickel gallium hydroxide is dried for 12h in a vacuum drying oven, then reduced for 2h at 500 ℃ in hydrogen, finally argon is introduced to anneal for 12h at 300 ℃.
The catalyst of the embodiment is used in a propane 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 in this embodiment contains the following components in mass percent: 7% of active component and 93% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
1033mg of carbon black is weighed and added into a 20% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered and washed, 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. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 2, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then 175.1mg of nickel dichloride was weighed, pH was adjusted to 7 by adding 2M sodium hydroxide, and then the reaction was carried out for 1 hour to obtain nickel gallium hydroxide deposited on a carbon black support, which was dried in a vacuum oven for 12 hours, and then reduced in hydrogen at 700℃for 2 hours.
The catalyst of the embodiment is used in a propane steam reforming hydrogen production system, the reaction temperature is 500 ℃, and the mole ratio of water to propane isThe ratio is 9:1, and the reaction mass space velocity is 0.5h -1 。
Example 6: the supported nickel-gallium catalyst in this embodiment contains the following components in mass percent: 13% of active component and 87% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
967mg of carbon black was weighed, added to a 10% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered and washed, and dried in a vacuum oven for 12 hours. 417.2mg of gallium nitrate hydrate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 5, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then, 325.3mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH to 9 and then reacts for 1h, the nickel gallium hydroxide deposited on the carbon black carrier is obtained, the nickel gallium hydroxide is dried for 12h in a vacuum drying oven, then reduced for 2h at 700 ℃ in hydrogen, finally argon is introduced to anneal for 12h at 300 ℃.
The catalyst of the embodiment is used in a propane 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 in this embodiment contains the following components in mass percent: 17% of active component and 83% of carbon black carrier, and the preparation method is a deposition-precipitation method, and comprises the following specific steps:
922mg of carbon black is weighed, added into a 20% nitric acid solution, heated to 70 ℃, stirred for 6 hours, filtered and washed, and dried in a vacuum drying oven for 12 hours. 545.5mg of gallium nitrate hydrate was weighed and dissolved in a small amount of deionized water. The mixture was heated to 80 ℃, 2M sodium hydroxide was added to adjust pH to 5, and then the treated carbon black support was added to react for 1 hour, to prepare gallium hydroxide deposited on the carbon black support. Then, 425.3mg of nickel nitrate hexahydrate is weighed, 2M sodium hydroxide is added to adjust the pH to 9 and then reacts for 1h, the nickel gallium hydroxide deposited on the carbon black carrier is obtained, the nickel gallium hydroxide is dried for 12h in a vacuum drying oven, then reduced for 2h at 700 ℃ in hydrogen, finally argon is introduced to anneal for 12h at 800 ℃.
The catalyst of the embodiment is used in a propane 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 producing hydrogen by steam reforming of propane comprises the following active components in percentage by mass of 10% and 90% of carrier; the active component nickel, the carrier is carbon black.
The preparation method of the nickel catalyst for producing hydrogen from propane, which is described in the present comparative example, is a deposition-precipitation method, which specifically comprises the following steps: 1000mg of carbon black was weighed, added to a 10% nitric acid solution, heated to 70℃and stirred for 6 hours, filtered and washed, and dried in a vacuum 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, and the mixture was washed with deionized water and filtered three times to prepare a nickel hydroxide deposited on a carbon black support. The nickel hydroxide obtained was dried in a vacuum oven for 12h and then reduced in a hydrogen atmosphere at 400 ℃ for 2h.
The catalyst of the embodiment 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 airspeed is 0.5h -1 。
Comparative example 2:
a nickel-gallium catalyst for preparing hydrogen by propane steam reforming comprises the following components in percentage by mass of 10% of active components and 90% of carrier; the active component Ni 3 Ga, the carrier is silicon dioxide.
The preparation method of the nickel-gallium catalyst for producing hydrogen from propane 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 nickel salt and gallium salt mixture solution. And immersing 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 12 hours, reducing the silicon dioxide carrier for 2 hours at 700 ℃ in a hydrogen atmosphere, and then annealing the silicon dioxide carrier for 12 hours at 700 ℃ in an argon atmosphere to obtain the silicon dioxide-loaded nickel-gallium intermetallic compound catalyst.
The catalyst of the embodiment 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 airspeed is 0.5h -1 。
Catalysts for steam reforming of propane to produce hydrogen were prepared according to the methods described in examples 1 to 7 and comparative examples 1 to 2, respectively, and their catalytic performance was tested in a gas phase fixed bed reactor according to the corresponding reaction conditions of the steam reforming of propane to produce hydrogen, carbon dioxide, carbon monoxide and methane products were quantitatively analyzed by a gas chromatograph, and the conversion rate of propane and the content of the products were calculated according to the conventional methods, with specific results shown in table 1.
Table 1 propane conversion and the contents of hydrogen, carbon dioxide, carbon monoxide and methane in the product of a steam reforming propane hydrogen production process using a catalyst.
As can be seen from the results of the steam reforming reaction of propane in Table 1 and examples and comparative examples, the carbon black-supported nickel-gallium catalyst provided by the invention is applied to steam reforming hydrogen production of propane, remarkably improves the conversion rate of propane, and maintains high selectivity and purity of hydrogen.
The foregoing detailed description of the preferred embodiments of the invention has been presented in order to illustrate and not to limit the invention, but to limit the invention to the form and detail, all modifications, equivalents, and improvements made within the spirit and principles of the invention.
Claims (4)
1. The method for synthesizing the 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 C by mass percent of a carbon black carrier, and the method for synthesizing the supported nickel-gallium intermetallic compound catalyst comprises the following steps:
step 1, carbon black carrier treatment: 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, preparing gallium hydroxide: dissolving gallium salt in deionized water, heating to 20-95 ℃, then adding 0.1-4M sodium hydroxide to adjust the pH to 2-9, adding 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 deionized water into the gallium hydroxide solution obtained in the step 2, then adding 0.1-4M sodium hydroxide to adjust the pH to 2-9, and reacting for 30 min-1 h to obtain nickel gallium hydroxide;
step 4, reduction treatment: drying the nickel gallium hydroxide obtained in the step 3 in a vacuum drying oven for 2-36 h, and then reducing the nickel gallium hydroxide in a mixed gas atmosphere of hydrogen and argon at 400-800 ℃ to obtain a pure-phase ordered supported nickel gallium intermetallic compound catalyst;
the concentration of hydrogen in the mixed gas atmosphere of the hydrogen and the argon is 2-100% of the volume fraction of the argon, and the reduction time is 30 min-12 h;
step 5, annealing treatment: and (3) annealing the supported nickel-gallium intermetallic compound catalyst obtained in the step (4) for 2-12 hours at 300-800 ℃ in an argon atmosphere.
2. The method for synthesizing the supported nickel-gallium catalyst according to claim 1, wherein the nickel salt in the 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 the step 2 is gallium trichloride, gallium nitrate hydrate or gallium acetate.
4. The use of the supported nickel gallium catalyst synthesized by the method of claim 1, wherein the negative electrodeApplication of supported nickel-gallium intermetallic compound catalyst in propane steam reforming reaction hydrogen production system, wherein the reaction temperature is 300-600 ℃, the molar ratio of water to propane is 3-9, and the reaction mass airspeed is 0.5-3.0 h -1 The reaction time was 20h.
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