CN114950444B - Supported nickel catalyst and preparation method thereof - Google Patents

Supported nickel catalyst and preparation method thereof Download PDF

Info

Publication number
CN114950444B
CN114950444B CN202210619522.4A CN202210619522A CN114950444B CN 114950444 B CN114950444 B CN 114950444B CN 202210619522 A CN202210619522 A CN 202210619522A CN 114950444 B CN114950444 B CN 114950444B
Authority
CN
China
Prior art keywords
cobalt
carrier
potassium
weight
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210619522.4A
Other languages
Chinese (zh)
Other versions
CN114950444A (en
Inventor
郑永耀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shiyou Chemical Yangzhou Co ltd
Original Assignee
Shiyou Chemical Yangzhou Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shiyou Chemical Yangzhou Co ltd filed Critical Shiyou Chemical Yangzhou Co ltd
Priority to CN202210619522.4A priority Critical patent/CN114950444B/en
Publication of CN114950444A publication Critical patent/CN114950444A/en
Application granted granted Critical
Publication of CN114950444B publication Critical patent/CN114950444B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/12—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
    • C01B2203/1241—Natural gas or methane
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a supported nickel catalyst and a preparation method thereof, wherein the supported nickel catalyst takes nickel-iron oxide as an active ingredient, cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium as a carrier, the weight of the active ingredient accounts for 15-30% of the total weight of the supported nickel catalyst, wherein the molar ratio of nickel to iron in the active ingredient is 2-3:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2-0.3:1.5-2.2:0.5:1, and the weight of the potassium-cobalt oxide accounts for 58-65% of the weight of the carrier. The supported nickel catalyst can improve the yield of the hydrogen converted from the natural gas, reduce byproducts, improve the product yield, and simultaneously shorten the catalyst replacement period in the hydrogen production process of the natural gas.

Description

Supported nickel catalyst and preparation method thereof
Technical Field
The invention relates to a supported nickel catalyst and a preparation method thereof, belonging to the technical field of catalyst preparation.
Background
Hydrogen is an important industrial raw material, clean, environment-friendly and pollution-free, and is a fuel with bright application prospect. At present, the raw material used for preparing the hydrogen is mainly natural gas, and a catalyst is needed for realizing the hydrogen production by natural gas pyrolysis. However, the hydrogen production process is accompanied by carbon growth, so that carbon deposition is serious, the existing catalyst has high deactivation rate, so that the catalyst replacement period is short, in addition, the existing catalyst has low conversion rate of natural gas hydrogen production, so that the raw material consumption is large, and the tail gas carbon emission treatment capability is high. The invention provides a supported nickel catalyst and a preparation method thereof, which are used for improving the yield of hydrogen converted from natural gas, prolonging the catalyst replacement period, reducing the raw material consumption and reducing the energy consumption so as to achieve the aim of improving the economic benefit.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a supported nickel catalyst and a preparation method thereof, wherein the supported nickel catalyst can improve the yield of converting natural gas into hydrogen, reduce byproducts, improve the product yield and shorten the catalyst replacement period in the process of preparing hydrogen from natural gas.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the supported nickel catalyst uses nickel-iron oxide as an active component, cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium as a carrier, and the weight of the active component accounts for 15-30% of the total weight of the supported nickel catalyst, wherein the molar ratio of nickel to iron in the active component is 2-3:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2-0.3:1.5-2.2:0.5:1, and the weight of the potassium-cobalt oxide accounts for 58-65% of the weight of the carrier.
Preferably, the supported nickel catalyst takes nickel-iron oxide as an active ingredient, potassium-cobalt-aluminum-zinc hydrotalcite oxide as a carrier, and the weight of the active ingredient accounts for 20.76% of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.25:1.8:0.5:1, and the weight of the potassium-cobalt oxide accounts for 61.88% of the weight of the carrier.
Preferably, the supported nickel catalyst takes nickel-iron oxide as an active ingredient, potassium cobalt aluminum zinc hydrotalcite oxide as a carrier, and the weight of the active ingredient accounts for 22.08 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.2:2:0.5:1, and the weight of the potassium cobalt oxide accounts for 63.82 percent of the weight of the carrier.
The supported nickel catalyst is suitable for reforming reaction and shift catalytic reaction for catalyzing natural gas steam to prepare hydrogen.
Further, the supported nickel catalyst is used for reforming reaction, and the reaction temperature is 580-720 ℃.
Further, the supported nickel catalyst is used for a shift catalytic reaction, and the reaction temperature is 180-250 ℃.
The invention also provides a preparation method of the supported nickel catalyst, which comprises the following steps:
(1) Adding zinc nitrate and cobalt nitrate into pure water according to a molar ratio of 1:3-4.4, mixing and dissolving, adding gamma-alumina with a molar ratio of 1:1 and roasting for 2.5-3 hours at 500-550 ℃, uniformly mixing, continuously stirring, regulating the pH value of the mixed solution to 8-9 by using 5% ammonia water, rapidly stirring for 1 hour at 60-65 ℃, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting for 2.5-3.5 hours at 500-550 ℃ to obtain cobalt aluminum zinc hydrotalcite oxide;
(2) Adding potassium nitrate with the molar ratio of 0.4-0.6:1 to pure water for dissolution, then uniformly mixing the cobalt aluminum zinc hydrotalcite oxide obtained in the step (1), rapidly stirring for 30min at 60-65 ℃, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting at 500-550 ℃ for 2-2.5 h to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 58-65% of the weight of the carrier;
(3) Adding nickel nitrate and ferric nitrate into pure water according to the molar ratio of 2-3:0.8, mixing and dissolving, adding the carrier obtained in the step (2), mixing uniformly, stirring rapidly at 60-65 ℃ for 45min, heating to 70-75 ℃ and stirring and concentrating, cooling, filtering, washing, drying and roasting to obtain the supported nickel catalyst, wherein the active component is nickel-iron oxide, and the weight of the active component accounts for 15-30% of the total weight of the supported nickel catalyst.
Wherein the roasting temperature in the step (3) is 600-700 ℃ and the roasting time is 2.5-3 h.
The invention has the beneficial effects that:
1. the supported nickel catalyst improves the conversion rate of hydrogen production by natural gas, improves the hydrogen yield and reduces the consumption of raw materials;
2. the supported nickel catalyst disclosed by the invention can promote soot combustion, reduce carbon deposition, prolong the service cycle of the catalyst, reduce the exhaust emission and reduce the carbon emission treatment capacity;
3. the supported nickel catalyst also reduces the heat energy required by reforming reaction and conversion catalytic reaction of natural gas hydrogen production, and saves energy consumption;
4. the preparation process is simple, the operation is convenient, the performance of the prepared supported nickel catalyst product is stable, and the product can conveniently achieve the aim of improving the economic benefit when used for preparing hydrogen from natural gas, and has good application prospect.
Detailed Description
The invention will now be more clearly and more fully described by way of the following specific examples, which are not intended to be limiting.
Examples
The specific preparation steps of the supported nickel catalyst provided by the invention are as follows:
(1) Adding zinc nitrate and cobalt nitrate into pure water according to a molar ratio of 1:3-5, mixing and dissolving, adding gamma-alumina with a molar ratio of 1:1 with zinc nitrate and roasting for 2.5-3 h at 500-550 ℃, uniformly mixing, continuously stirring, regulating the pH value of the mixed solution to 8-9 by using 5% ammonia water, rapidly stirring for 1h at 60-65 ℃, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting for 2.5-3.5 h at 500-550 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding potassium nitrate with the molar ratio of 0.4-0.6:1 with zinc nitrate into pure water for dissolution, then uniformly mixing the cobalt aluminum zinc hydrotalcite oxide, rapidly stirring for 30min at 60-65 ℃, heating to 70-75 ℃, stirring for concentration, cooling, filtering, washing, drying, roasting at 500-550 ℃ for 2-2.5 h to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the potassium cobalt oxide accounts for 58-65% of the weight of the carrier;
(3) Adding nickel nitrate and ferric nitrate into pure water according to the molar ratio of 2-3:0.8, mixing and dissolving, adding the carrier, mixing uniformly, stirring rapidly at 60-65 ℃ for 45min, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, roasting at 600-700 ℃ for 2.5-3 h to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 15-30% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2-3:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2-0.3:1.5-2.2:0.5:1.
Example 1
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted for 3 hours at 500 ℃, treating according to the mode of the embodiment, and roasting for 3.5 hours at 500 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.3mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 500 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the potassium-loaded cobalt aluminum zinc hydrotalcite oxide, and the weight of the potassium cobalt oxide is 58.33% of that of the carrier;
(3) Adding 0.8mol of nickel nitrate and 0.32mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 700 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 28.05% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.3:1.5:0.5:1.
Example 2
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is baked for 3 hours at 520 ℃, treating according to the mode of the embodiment, and then baking for 3 hours at 520 ℃ to obtain cobalt aluminum zinc hydrotalcite oxide;
(2) Adding 0.25mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 520 ℃ for 2.8 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 64.15% of the weight of the carrier;
(3) Adding 0.8mol of nickel nitrate and 0.32mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 650 ℃ for 2.8 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 25.11% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:2:0.5:1.
Example 3
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted for 2 hours at 520 ℃, treating according to the mode of the embodiment, and roasting for 2.5 hours at 550 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.2mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 63.82% of that of the carrier;
(3) Adding 0.744mol of nickel nitrate and 0.1984mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 650 ℃ for 2.8 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 22.08% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 3:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:2:0.5:1.
Example 4
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is baked for 3 hours at 520 ℃, treating according to the mode of the embodiment, and then baking for 2.5 hours at 550 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.2mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 63.82% of that of the carrier;
(3) Adding 0.7125mol of nickel nitrate and 0.228mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 650 ℃ for 2.8 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 22.08% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:2:0.5:1.
Example 5
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.25mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 61.88% of that of the carrier;
(3) Adding 0.625mol of nickel nitrate and 0.2mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 20.76% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:1.8:0.5:1.
Example 6
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.25mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 61.88% of that of the carrier;
(3) Adding 0.5mol of nickel nitrate and 0.16mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 17.32% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:1.8:0.5:1.
Example 7
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 3 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.25mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 3 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 61.88% of that of the carrier;
(3) Adding 0.425mol of nickel nitrate and 0.136mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 3 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 15.11% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:1.8:0.5:1.
Example 8
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 2.1mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted for 2.2 hours at 500 ℃, treating according to the mode of the embodiment, and roasting for 2.2 hours at 500 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.2mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 500 ℃ for 2.2 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 64.88% of the weight of the carrier;
(3) Adding 0.52455mol of nickel nitrate and 0.1736mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 700 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 17.32% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:2.1:0.5:1.
Example 9
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 500 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 500 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.28mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 500 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 58.15% of the weight of the carrier;
(3) Adding 0.46mol of nickel nitrate and 0.16mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 700 ℃ for 3 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 17.78% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.3:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.28:1.5:0.5:1.
Example 10
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.7mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is baked for 3 hours at 550 ℃, treating according to the mode of the embodiment, and then baking for 2.5 hours at 550 ℃ to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.25mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 60.63% of the weight of the carrier;
(3) Adding 1.0136mol of nickel nitrate and 0.2896mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, uniformly mixing, treating according to the mode of the embodiment, roasting at 600 ℃ for 2 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 29.91% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.8:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:1.7:0.5:1.
Example 11
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 2.2mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.3mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 66.45% of that of the carrier;
(3) Adding 0.75mol of nickel nitrate and 0.2mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 20.94% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 3:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.3:2.2:0.5:1.
Example 12
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.2mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide is 57.42% of the weight of the carrier;
(3) Adding 0.75mol of nickel nitrate and 0.2mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 25.16% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 3:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:1.5:0.5:1.
Example 13
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.22mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 61.65% of the weight of the carrier;
(3) Adding 0.4mol of nickel nitrate and 0.128mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 14.43% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.22:1.8:0.5:1.
Example 14
The specific preparation steps of the supported nickel catalyst in this example include:
(1) Adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water for mixed dissolution, adding 0.5mol of gamma-alumina which is roasted at 550 ℃ for 2.5 hours, treating according to the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) Adding 0.28mol of potassium nitrate into pure water for dissolution, treating the cobalt aluminum zinc hydrotalcite oxide in the mode of the embodiment, and roasting at 550 ℃ for 2.5 hours to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 58.15% of the weight of the carrier;
(3) Adding 0.95 mol of nickel nitrate and 0.304mol of ferric nitrate into pure water, mixing and dissolving, adding the carrier, mixing uniformly, treating according to the mode of the embodiment, roasting at 600 ℃ for 2.5 hours to obtain the supported nickel catalyst, wherein the active ingredient is nickel-iron oxide, the weight of the active ingredient accounts for 31.51% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, and the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.28:1.5:0.5:1.
Comparative example
The supported nickel catalyst of this comparative example was a nickel metal supported on a silica support.
Effect example 1 reforming reaction temperature
Before the test, the supported nickel catalysts of the above examples 1 to 14 and the supported nickel catalysts of the comparative examples were placed in a heat exchange type reforming reactor respectively at an amount of 10g, then a high purity nitrogen gas was used to purge the system at a flow rate of 80 mL/min, then the nitrogen gas flow rate was kept unchanged, the heating was started to raise the temperature to 250 ℃ for 30min, then the heating was continued to 300 ℃ for 6min, finally the nitrogen gas was turned off, the products of the pipeline natural gas treatment by the desulfurization reactor were mixed with steam from the steam generator, and after the preheating, the products were respectively placed in the heat exchange type reforming reactor to react with the above catalysts, the operating pressure in the reforming reactor was 0.5MPa, the reaction temperature was 580 to 720 ℃ and the water-carbon ratio was 3.0, and a mixture of hydrogen, methane, carbon monoxide, carbon dioxide and water was produced, and the composition results of the reformate are shown in table 1, table 2 and table 3.
TABLE 1 reforming reaction temperature 580 deg.C
TABLE 2 reforming reaction temperature 650 DEG C
TABLE 3 reforming reaction temperature 720℃
Effect example 2
Before the test, the supported nickel catalysts of the above examples 1 to 14 and the supported nickel catalyst of the comparative example were placed in a heat exchange type reforming reactor at a dose of 2.5g, respectively, and then a high purity nitrogen gas was used to purge the system at a flow rate of 80 mL/min for 10min, then the nitrogen gas flow rate was kept unchanged, the temperature was raised to 250 ℃ for 30min, then the temperature was raised to 300 ℃ for 6min, finally the nitrogen gas was turned off, the reformate of the above effect example 1 was mixed with steam from a steam generator, and the preheated and fed to a shift catalytic reactor to react with the catalyst, the shift catalytic reactor was at a temperature of 0.5MPa, the reaction temperature was 180 to 250 ℃ to produce a mixture of hydrogen gas, carbon dioxide and water, and the conversion rate of carbon monoxide in the shift catalyst was converted, the results are shown in table 4.
TABLE 4 temperature of the shift catalytic reaction at 180 ℃, 220 ℃, 250 DEG C
As shown in tables 1, 2, 3 and 4, compared with examples 11 to 14, the supported nickel-based catalyst prepared in examples 1 to 10 has higher hydrogen production conversion rate of natural gas, higher hydrogen yield, hydrogen yield of more than 76.5% in reforming reaction process and carbon monoxide conversion rate of more than 87% in shift catalytic reaction process, so that the supported nickel-based catalyst is prepared according to the invention, the weight of active components is selected to be 15-30% of the total weight of the supported nickel-based catalyst, wherein the molar ratio of nickel to iron in the active components is 2-3:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2-0.3:1.5-2.2:0.5:1, and the weight of potassium cobalt oxide is 58-65% of the weight of the carrier; the more preferable selection is that the weight of the active ingredients accounts for 20.76 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredients is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.25:1.8:0.5:1, and the weight of the potassium cobalt oxide accounts for 61.88 percent of the weight of the carrier; or more preferably, the weight of the active ingredients accounts for 22.08 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredients is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.2:2:0.5:1, and the weight of the potassium cobalt oxide accounts for 63.82 percent of the weight of the carrier; from another angle, the preparation method of the supported nickel catalyst can improve the utilization rate of raw materials and reduce the consumption of the raw materials.
It was further found that the preparation of the supported nickel-based catalyst of examples 1 to 10, compared with the comparative example, allows the natural gas hydrogen production to promote soot combustion during the reforming reaction, reduces carbon deposition, further prolongs the catalyst life cycle, further promotes soot combustion, and reduces the exhaust emission of exhaust gas, thereby reducing the carbon emission treatment capacity.
In addition, it was further found that the supported nickel-based catalysts prepared in examples 1 to 10 had a hydrogen yield of more than 76.5% when the reforming reaction was performed at a temperature of 580 to 720 ℃ and a carbon monoxide conversion rate of more than 87% when the shift catalytic reaction was performed at a temperature of 180 to 250 ℃, so that the heat energy required for the reforming reaction and shift catalytic reaction was reduced, and the energy consumption was effectively reduced.
In conclusion, the preparation process is simple, the operation is convenient, the prepared supported nickel catalyst product has stable performance, and the product can conveniently achieve the aim of improving economic benefit in natural gas hydrogen production, and has good application prospect.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution of the present invention, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the present invention may be modified or equivalently replaced without departing from the spirit and scope of the present invention, and any modification or partial replacement thereof should be included in the scope of the claims of the present invention.

Claims (5)

1. The supported nickel catalyst is characterized in that nickel-iron oxide is used as an active ingredient, cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium is used as a carrier, the weight of the active ingredient accounts for 15-30% of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active ingredient is 2-3:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.2-0.3:1.5-2.2:0.5:1, and potassium to cobalt oxide accounts for 58-65% of the weight of the carrier;
the supported nickel catalyst is suitable for reforming reaction and shift catalytic reaction for catalyzing natural gas steam to prepare hydrogen;
the supported nickel catalyst is used for reforming reaction, and the reaction temperature is 580-720 ℃;
the supported nickel catalyst is used for transformation catalytic reaction, and the reaction temperature is 180-250 ℃.
2. The supported nickel catalyst according to claim 1, wherein the supported nickel catalyst uses nickel-iron oxide as an active ingredient, potassium cobalt aluminum zinc hydrotalcite oxide as a carrier, and the weight of the active ingredient accounts for 20.76% of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.25:1.8:0.5:1, and the weight of the potassium to cobalt oxide accounts for 61.88% of the weight of the carrier.
3. The supported nickel catalyst according to claim 1, wherein the supported nickel catalyst uses nickel-iron oxide as an active ingredient, potassium cobalt aluminum zinc hydrotalcite oxide as a carrier, and the weight of the active ingredient accounts for 22.08% of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active ingredient is 2.5:0.8, the molar ratio of potassium to cobalt to zinc to aluminum in the carrier is 0.2:2:0.5:1, and the weight of the potassium to cobalt oxide accounts for 63.82% of the weight of the carrier.
4. A method for preparing the supported nickel-based catalyst according to claim 1, comprising the steps of:
(1) Adding zinc nitrate and cobalt nitrate into pure water according to a molar ratio of 1:3-4.4, mixing and dissolving, adding gamma-alumina with a molar ratio of 1:1 and roasting for 2.5-3 hours at 500-550 ℃, uniformly mixing, continuously stirring, regulating the pH value of the mixed solution to 8-9 by using 5% ammonia water, rapidly stirring for 1 hour at 60-65 ℃, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting for 2.5-3.5 hours at 500-550 ℃ to obtain cobalt aluminum zinc hydrotalcite oxide;
(2) Adding potassium nitrate with the molar ratio of 0.4-0.6:1 to pure water for dissolution, then uniformly mixing the cobalt aluminum zinc hydrotalcite oxide obtained in the step (1), rapidly stirring for 30min at 60-65 ℃, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting at 500-550 ℃ for 2-2.5 h to obtain a carrier, wherein the carrier is the cobalt aluminum zinc hydrotalcite oxide loaded with potassium, and the weight of the potassium cobalt oxide accounts for 58-65% of the weight of the carrier;
(3) Adding nickel nitrate and ferric nitrate into pure water according to the molar ratio of 2-3:0.8, mixing and dissolving, adding the carrier obtained in the step (2), mixing uniformly, stirring rapidly at 60-65 ℃ for 45min, heating to 70-75 ℃ and stirring and concentrating, cooling, filtering, washing, drying and roasting to obtain the supported nickel catalyst, wherein the active component is nickel-iron oxide, and the weight of the active component accounts for 15-30% of the total weight of the supported nickel catalyst.
5. The method for producing a supported nickel catalyst according to claim 4, wherein the calcination temperature in the step (3) is 600 to 700℃and the calcination time is 2.5 to 3 hours.
CN202210619522.4A 2022-06-02 2022-06-02 Supported nickel catalyst and preparation method thereof Active CN114950444B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210619522.4A CN114950444B (en) 2022-06-02 2022-06-02 Supported nickel catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210619522.4A CN114950444B (en) 2022-06-02 2022-06-02 Supported nickel catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114950444A CN114950444A (en) 2022-08-30
CN114950444B true CN114950444B (en) 2024-03-29

Family

ID=82960011

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210619522.4A Active CN114950444B (en) 2022-06-02 2022-06-02 Supported nickel catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114950444B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB534970A (en) * 1939-06-22 1941-03-25 Ernest Alexander Ocon Process for refining hydrocarbon oils and derivatives
GB791094A (en) * 1954-11-23 1958-02-26 Universal Oil Prod Co Improvements in or relating to the manufacture and use of supported molybdenum-containing catalysts
JPS5299974A (en) * 1976-02-13 1977-08-22 Davy Powergas Ltd Catalytic process
WO1997047380A1 (en) * 1996-06-12 1997-12-18 Project Earth Industries, Inc. Acid contacted enhanced adsorbent and/or catalyst and binder system
CN101126032A (en) * 2007-09-29 2008-02-20 华中农业大学 Method for preparing biological diesel oil by using solid acid base double-function catalyst
CN104399471A (en) * 2014-09-29 2015-03-11 中国科学院上海高等研究院 Nickel-based catalyst and moulding method and application thereof
WO2017090864A1 (en) * 2015-11-24 2017-06-01 한국화학연구원 Cobalt-supported catalyst for low-temperature reforming reaction and production method therefor
CN108110263A (en) * 2017-12-20 2018-06-01 新奥科技发展有限公司 A kind of SMR catalyst and solid oxide fuel cell anode material
CN111167460A (en) * 2019-12-31 2020-05-19 四川天采科技有限责任公司 Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB534970A (en) * 1939-06-22 1941-03-25 Ernest Alexander Ocon Process for refining hydrocarbon oils and derivatives
GB791094A (en) * 1954-11-23 1958-02-26 Universal Oil Prod Co Improvements in or relating to the manufacture and use of supported molybdenum-containing catalysts
JPS5299974A (en) * 1976-02-13 1977-08-22 Davy Powergas Ltd Catalytic process
WO1997047380A1 (en) * 1996-06-12 1997-12-18 Project Earth Industries, Inc. Acid contacted enhanced adsorbent and/or catalyst and binder system
CN101126032A (en) * 2007-09-29 2008-02-20 华中农业大学 Method for preparing biological diesel oil by using solid acid base double-function catalyst
CN104399471A (en) * 2014-09-29 2015-03-11 中国科学院上海高等研究院 Nickel-based catalyst and moulding method and application thereof
WO2017090864A1 (en) * 2015-11-24 2017-06-01 한국화학연구원 Cobalt-supported catalyst for low-temperature reforming reaction and production method therefor
CN108110263A (en) * 2017-12-20 2018-06-01 新奥科技发展有限公司 A kind of SMR catalyst and solid oxide fuel cell anode material
CN111167460A (en) * 2019-12-31 2020-05-19 四川天采科技有限责任公司 Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof

Also Published As

Publication number Publication date
CN114950444A (en) 2022-08-30

Similar Documents

Publication Publication Date Title
CN105618061B (en) A kind of slurry bed system carbon dioxide methanation bimetallic catalyst and its preparation method and application
CN109529935B (en) Method for catalyzing formaldehyde dehydrogenation by using Pd @ CoO-CNx core-shell type catalyst
CN111111675A (en) Ni-CeO2Process for preparing catalyst
CN111097441A (en) Catalyst for reforming methane and carbon dioxide to prepare synthesis gas and preparation method thereof
JP2014506183A (en) Method for producing methane synthesis catalyst and catalyst precursor
CN110090641A (en) A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine
CN111389405B (en) Method for preactivating methane vapor hydrogen production catalyst
CN111167460A (en) Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof
CN115837275A (en) Perovskite type high-entropy oxide and preparation method and application thereof
CN113842914B (en) Catalyst for synthesizing methanol from carbon dioxide, and preparation method and application thereof
CN114950444B (en) Supported nickel catalyst and preparation method thereof
CN114505069A (en) Hydrolysis catalyst for removing carbonyl sulfide in coal gas at low temperature and preparation method thereof
CN114100661A (en) Catalyst for preparing hydrogen by decomposing molybdenum-based ammonia and preparation method thereof
CN113368861A (en) Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application thereof
CN116273013B (en) Catalyst for preparing methanol from carbon dioxide-rich synthetic gas and preparation method and application thereof
CN112062673B (en) Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method
CN113731429A (en) Copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof
CN114345351B (en) Preparation method of synthetic gas methanation catalyst carrier
CN111088090A (en) Preparation method of Fe2O3-MgO/Al2O3 oxygen carrier
CN111921530B (en) CaO-multiferroic metal composite catalyst for carbon hydro-gasification and preparation method thereof
CN114632530B (en) Copper-based catalyst for preparing hydrogen by reforming methanol, preparation method and application
CN116037132B (en) For CO2Catalyst for preparing methanol by hydrogenation, preparation method and application thereof
CN114849761B (en) Photocatalytic material and preparation method and application thereof
CN115970703B (en) WFe with photo-thermal catalytic activitymLanOxCatalyst, preparation method and application thereof
CN115069260B (en) Nickel-based hierarchical porous reforming hydrogen production catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant