CN114950444A - Supported nickel catalyst and preparation method thereof - Google Patents
Supported nickel catalyst and preparation method thereof Download PDFInfo
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- CN114950444A CN114950444A CN202210619522.4A CN202210619522A CN114950444A CN 114950444 A CN114950444 A CN 114950444A CN 202210619522 A CN202210619522 A CN 202210619522A CN 114950444 A CN114950444 A CN 114950444A
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- cobalt
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- nickel
- potassium
- zinc
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- -1 cobalt-aluminum-zinc Chemical compound 0.000 claims abstract description 58
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 58
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 58
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 45
- 239000011591 potassium Substances 0.000 claims abstract description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- XOXMKTHMAHFOGE-UHFFFAOYSA-N [K].[Co]=O Chemical compound [K].[Co]=O XOXMKTHMAHFOGE-UHFFFAOYSA-N 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003345 natural gas Substances 0.000 claims abstract description 17
- 239000004480 active ingredient Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 229910001868 water Inorganic materials 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 51
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 46
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 36
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 21
- 239000004323 potassium nitrate Substances 0.000 claims description 18
- 235000010333 potassium nitrate Nutrition 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 17
- 238000006057 reforming reaction Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
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- 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, the supported nickel catalyst takes a nickel-iron oxide as an active ingredient, takes a cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium as a carrier, and 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 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.
Description
Technical Field
The invention relates to a supported nickel catalyst and a preparation method thereof, belonging to the technical field of catalyst preparation.
Background
The hydrogen is an important industrial raw material, is clean, environment-friendly and pollution-free, and is a fuel with bright application prospect. At present, the raw material used for preparing hydrogen is mainly natural gas, and a catalyst is needed for realizing hydrogen production by natural gas cracking. However, the hydrogen production process is accompanied by carbon growth, carbon deposition is serious, the deactivation rate of the existing catalyst is high, the replacement period of the catalyst is short, and in addition, the conversion rate of the existing catalyst for the hydrogen production of natural gas is low, the raw material consumption is high, and the tail gas carbon emission treatment capacity is high. In order to meet the requirements of energy-saving, environment-friendly and high-yield production development of enterprises, the invention provides a supported nickel catalyst and a preparation method thereof, which improve the yield of converting natural gas into hydrogen, prolong the replacement period of the catalyst, reduce the consumption of raw materials and reduce the energy consumption, thereby achieving the purpose 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, 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 purpose, the invention adopts the following technical scheme: a supported nickel catalyst takes a nickel-iron oxide as an active ingredient, takes a cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium as a carrier, and takes the weight of the active ingredient as 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 is 58-65% of the weight of the carrier.
Preferably, the supported nickel-based catalyst takes nickel-iron oxide as an active component, takes potassium-cobalt-aluminum-zinc hydrotalcite oxide as a carrier, and the weight of the active component accounts for 20.76 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.25:1.8:0.5:1, and the weight of potassium-cobalt oxide accounts for 61.88 percent of the weight of the carrier.
Preferably, the supported nickel-based catalyst takes nickel-iron oxide as an active component, takes potassium-cobalt-aluminum-zinc hydrotalcite oxide as a carrier, and the weight of the active component accounts for 22.08 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:2:0.5:1, and the weight of 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 of hydrogen production by catalyzing natural gas steam.
Furthermore, the supported nickel catalyst is used for reforming reaction at a temperature of 580-720 ℃.
Furthermore, the supported nickel-based 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 in a molar ratio of 1: 3-4.4, mixing and dissolving, adding gamma-alumina which has a molar ratio of 1:1 to zinc nitrate and is roasted at 500-550 ℃ for 2.5-3 h, uniformly mixing, continuously stirring, adjusting the pH value of the mixed solution to 8-9 by using 5% ammonia water, quickly stirring at 60-65 ℃ for 1h, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting at 500-550 ℃ for 2.5-3.5 h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) dissolving potassium nitrate with a molar ratio of 0.4-0.6: 1 to zinc nitrate in pure water, uniformly mixing the cobalt-aluminum-zinc hydrotalcite oxide obtained in the step (1), rapidly stirring at 60-65 ℃ for 30min, 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 a potassium-loaded cobalt-aluminum-zinc hydrotalcite oxide, 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 a molar ratio of 2-3: 0.8, mixing and dissolving, adding the carrier obtained in the step (2), uniformly mixing, quickly stirring for 45min at 60-65 ℃, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting to obtain the supported nickel catalyst, wherein the active ingredient is nickel iron oxide, and the weight of the active ingredient 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 from natural gas, improves the hydrogen yield, and reduces the consumption of raw materials;
2. the supported nickel catalyst of the invention simultaneously promotes soot combustion, reduces carbon deposition, prolongs the service cycle of the catalyst, reduces tail gas emission and reduces carbon emission treatment capacity;
3. the supported nickel catalyst also reduces the heat energy required by reforming reaction and shift catalytic reaction for hydrogen production from natural gas, and saves energy consumption;
4. 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 purpose of improving economic benefits in the hydrogen production from natural gas, and has good application prospects.
Detailed Description
In order to more clearly and completely illustrate the present invention, the following examples are given by way of illustration of the present invention, and are not intended to limit the present invention.
Examples
The specific preparation steps of the supported nickel catalyst are as follows:
(1) adding zinc nitrate and cobalt nitrate into pure water at a molar ratio of 1: 3-5, mixing and dissolving, then adding gamma-alumina at a molar ratio of 1:1 to zinc nitrate and roasting at 500-550 ℃ for 2.5-3 h, uniformly mixing, continuously stirring, adjusting the pH value of the mixed solution to 8-9 by using 5% ammonia water, then quickly stirring at 60-65 ℃ for 1h, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and then roasting at 500-550 ℃ for 2.5-3.5 h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding potassium nitrate with the molar ratio of the potassium nitrate to zinc nitrate of 0.4-0.6: 1 into pure water for dissolving, then uniformly mixing the cobalt-aluminum-zinc hydrotalcite oxide, quickly stirring for 30min at 60-65 ℃, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and then roasting for 2-2.5 h at 500-550 ℃ to obtain a carrier, wherein the carrier is a potassium-loaded cobalt-aluminum-zinc hydrotalcite oxide, 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 a molar ratio of 2-3: 0.8, mixing and dissolving, adding the carrier, uniformly mixing, quickly stirring at 60-65 ℃ for 45min, heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting at 600-700 ℃ for 2.5-3 h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 15-30% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina calcined at 500 ℃ for 3h, treating according to the method of the embodiment, and then calcining at 500 ℃ for 3.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.3mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the way of the example, and then roasting at 500 ℃ for 2.5h to obtain a carrier, wherein the carrier is the cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium, and the potassium-cobalt oxide accounts for 58.33% 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, uniformly mixing, treating according to the method of the embodiment, and roasting at 700 ℃ for 2.5 hours to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, and the weight of the active component accounts for 28.05% of the total weight of the supported nickel-based catalyst, wherein the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 520 ℃ for 3h, treating according to the method of the embodiment, and roasting at 520 ℃ for 3h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.25mol of potassium nitrate into pure water for dissolving, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 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 method of the embodiment, and roasting at 650 ℃ for 2.8h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 25.11% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 520 ℃ for 2h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.2mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 potassium-cobalt oxide accounts for 63.82% of the weight 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 method of the embodiment, and roasting at 650 ℃ for 2.8h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 22.08 percent of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 2mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 520 ℃ for 3h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.2mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 potassium-cobalt oxide accounts for 63.82% of the weight of the carrier;
(3) 0.7125mol of nickel nitrate and 0.228mol of ferric nitrate are added into pure water to be mixed and dissolved, the carrier is added and evenly mixed, then the treatment is carried out according to the mode of the embodiment, and then the mixture is roasted for 2.8h at 650 ℃, so as to obtain the supported nickel catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 22.08 percent of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina calcined at 550 ℃ for 2.5h, treating according to the method of the embodiment, and then calcining at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.25mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the way of the example, and then 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 potassium-cobalt oxide accounts for 61.88% of the weight 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 method of the embodiment, and roasting at 600 ℃ for 2.5h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 20.76% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 550 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.25mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the way of the example, and then 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 potassium-cobalt oxide accounts for 61.88% of the weight 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, and roasting at 600 ℃ for 2.5h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 17.32% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina calcined at 550 ℃ for 2.5h, treating according to the method of the embodiment, and then calcining at 550 ℃ for 3h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.25mol of potassium nitrate into pure water for dissolving, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then roasting at 550 ℃ for 3 hours to obtain a carrier, wherein the carrier is potassium-loaded cobalt-aluminum-zinc hydrotalcite oxide, and the potassium-cobalt oxide accounts for 61.88% of the weight 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, uniformly mixing, treating according to the method of the embodiment, and roasting at 600 ℃ for 3h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 15.11 percent of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 2.1mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 500 ℃ for 2.2h, treating according to the method of the embodiment, and roasting at 500 ℃ for 2.2h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.2mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the way of the example, and then roasting at 500 ℃ for 2.2h to obtain a carrier, wherein the carrier is the cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium, and the potassium-cobalt oxide accounts for 64.88% of the weight of the carrier;
(3) 0.52455mol of nickel nitrate and 0.1736mol of ferric nitrate are added into pure water to be mixed and dissolved, the carrier is added and evenly mixed, then the treatment is carried out according to the mode of the embodiment, and then the mixture is roasted for 2.5h at 700 ℃, so as to obtain the supported nickel catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 17.32 percent of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 500 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 500 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.28mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 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 method of the embodiment, and roasting at 700 ℃ for 3h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 17.78% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.7mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina calcined at 550 ℃ for 3 hours, treating according to the method of the embodiment, and then calcining at 550 ℃ for 2.5 hours to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.25mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 potassium-cobalt oxide accounts for 60.63% of the weight of the carrier;
(3) 1.0136mol of nickel nitrate and 0.2896mol of ferric nitrate are added into pure water to be mixed and dissolved, the carrier is added and evenly mixed, then the mixture is treated according to the method of the embodiment, and then the mixture is roasted for 2 hours at 600 ℃, so as to obtain the supported nickel catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 29.91 percent of the total weight of the supported nickel catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 2.2mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 550 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.3mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 potassium-cobalt oxide accounts for 66.45 percent 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 method of the embodiment, and roasting at 600 ℃ for 2.5h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 20.94% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 550 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.2mol of potassium nitrate into pure water for dissolving, then treating the cobalt-aluminum-zinc hydrotalcite oxide according to the method of the embodiment, and then 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 potassium-cobalt oxide accounts for 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 method of the embodiment, and roasting at 600 ℃ for 2.5h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 25.16% of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.8mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 550 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.22mol of potassium nitrate into pure water for dissolving, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 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, and roasting at 600 ℃ for 2.5h to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 14.43 percent of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based catalyst of the present example are as follows:
(1) adding 0.5mol of zinc nitrate and 1.5mol of cobalt nitrate into pure water, mixing and dissolving, adding 0.5mol of gamma-alumina roasted at 550 ℃ for 2.5h, treating according to the method of the embodiment, and roasting at 550 ℃ for 2.5h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) adding 0.28mol of potassium nitrate into pure water to be dissolved, then treating the cobalt-aluminum-zinc hydrotalcite oxide in the manner of the example, and then 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 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, uniformly mixing, treating according to the method of the embodiment, and roasting at 600 ℃ for 2.5 hours to obtain the supported nickel-based catalyst, wherein the active component is nickel iron oxide, the weight of the active component accounts for 31.51 percent of the total weight of the supported nickel-based catalyst, the molar ratio of nickel to iron in the active component 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-based 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 catalyst of the comparative example are respectively placed in a heat exchange type reforming reactor with the dosage of 10g, then the system is purged by high-purity nitrogen at the flow rate of 80 mL/for 10min, then the nitrogen flow rate is kept unchanged, the reactor is heated to 250 ℃ and kept for 30min, then the reactor is heated to 300 ℃ and kept for 6min, finally the nitrogen is closed, the product of the pipeline natural gas treated by a desulfurization reactor is mixed with water vapor from a steam generator, after preheating, the mixture of the product enters the heat exchange type reforming reactor to react with the catalyst, the operating pressure in the reforming reactor is 0.5MPa, the reaction temperature is 580-720 ℃, the water-carbon ratio is 3.0, and the mixture of hydrogen, methane, carbon monoxide, carbon dioxide and water is generated, and the composition results of the reformed product are shown in Table 1, Tables 2 and 3 show.
TABLE 1 temperature 580 deg.C for reforming reactions
TABLE 2 temperature of reforming reaction 650 deg.C
TABLE 3 temperature of 720 ℃ for reforming reaction
Effect example 2
Before the test, the supported nickel catalysts of examples 1 to 14 and the supported nickel catalyst of the comparative example, which were used in an amount of 2.5g, were placed in a heat exchange type reforming reactor, respectively, the system was purged with high purity nitrogen at a flow rate of 80 mL/for 10min, the nitrogen flow rate was maintained, the temperature was raised to 250 ℃ for 30min, the temperature was raised to 300 ℃ for 6min, and finally the nitrogen was turned off, the reformate of example 1 was mixed with steam from a steam generator, preheated, and fed into a shift catalyst reactor to react with the catalyst, the shift catalyst reactor was set at 0.5MPa and a reaction temperature of 180 to 250 ℃, a mixture of hydrogen, carbon dioxide and water was produced, and the conversion results of the conversion rate of carbon monoxide in the shift catalyst are shown in table 4.
TABLE 4 temperatures of 180 deg.C, 220 deg.C, 250 deg.C for shift catalytic reactions
As shown in tables 1, 2, 3 and 4, compared with examples 11 to 14, examples 1 to 10 have higher conversion rate of hydrogen production from natural gas and higher hydrogen yield, the hydrogen yield in the reforming reaction process is greater than 76.5%, and the carbon monoxide conversion rate in the shift catalytic reaction process is greater than 87%, so that the supported nickel-based catalyst prepared by the invention has the advantages that the weight of active ingredients accounts for 15 to 30% of the total weight of the supported nickel-based catalyst, wherein the molar ratio of nickel to iron in the active ingredients is 2 to 3:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2 to 0.3:1.5 to 2.2:0.5:1, and the weight of potassium cobalt oxide accounts for 58 to 65% of the weight of the carrier; more preferably, the weight of the active component accounts for 20.76 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and 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 component accounts for 22.08 percent of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and 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 aspect, the preparation method of the supported nickel-based catalyst can improve the utilization rate of raw materials and reduce the consumption of the raw materials.
Further, it is found that, compared with the comparative example, the supported nickel catalysts prepared in examples 1 to 10 promote soot combustion in the reforming reaction process of hydrogen production from natural gas, reduce carbon deposition, further prolong the service life of the catalyst, further promote soot combustion, and reduce the exhaust emission of the exhaust, thereby reducing the carbon emission treatment capacity.
In addition, it is further found that in the preparation of the supported nickel catalysts in examples 1 to 10, the yield of hydrogen produced by the reforming reaction at 580 to 720 ℃ is greater than 76.5%, and the conversion rate of carbon monoxide produced by the shift catalytic reaction at 180 to 250 ℃ is greater than 87%, so that the heat energy required by the reforming reaction and the shift catalytic reaction is reduced, and the energy consumption is effectively reduced.
In conclusion, the preparation process is simple and convenient to operate, the prepared supported nickel catalyst is stable in performance, the product is convenient to achieve the purpose of improving economic benefits in natural gas hydrogen production, and the preparation method has a good application prospect.
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the present invention without departing from the spirit and scope of the present invention, and all modifications or partial substitutions should be covered by the scope of the claims of the present invention.
Claims (8)
1. The supported nickel catalyst is characterized in that a nickel-iron oxide is used as an active ingredient, a cobalt-aluminum-zinc hydrotalcite oxide loaded with potassium is used as a carrier, and 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.
2. The supported nickel-based catalyst according to claim 1, wherein the supported nickel-based catalyst comprises a nickel-iron oxide as an active component, a potassium-cobalt-aluminum-zinc hydrotalcite oxide as a carrier, and the weight of the active component accounts for 20.76% of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and 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.
3. The supported nickel-based catalyst according to claim 1, wherein the supported nickel-based catalyst comprises a nickel-iron oxide as an active component, a potassium-cobalt-aluminum-zinc hydrotalcite oxide as a carrier, and the weight of the active component accounts for 22.08% of the total weight of the catalyst, wherein the molar ratio of nickel to iron in the active component is 2.5:0.8, the molar ratio of potassium, cobalt, zinc and aluminum in the carrier is 0.2:2:0.5:1, and the weight of the potassium-cobalt oxide accounts for 63.82% of the weight of the carrier.
4. The supported nickel-based catalyst according to any one of claims 1 to 3, wherein the supported nickel-based catalyst is suitable for a reforming reaction and a shift catalytic reaction for catalyzing hydrogen production from natural gas by steam.
5. The supported nickel-based catalyst according to claim 4, wherein the supported nickel-based catalyst is used for reforming reaction at a temperature of 580-720 ℃.
6. The supported nickel-based catalyst according to claim 4, wherein the supported nickel-based catalyst is used for shift catalytic reaction at a temperature of 180-250 ℃.
7. A method for preparing a supported nickel-based catalyst according to claim 1, comprising the steps of:
(1) adding zinc nitrate and cobalt nitrate into pure water in a molar ratio of 1: 3-4.4, mixing and dissolving, adding gamma-alumina which has a molar ratio of 1:1 to zinc nitrate and is roasted at 500-550 ℃ for 2.5-3 h, uniformly mixing, continuously stirring, adjusting the pH value of the mixed solution to 8-9 by using 5% ammonia water, quickly stirring at 60-65 ℃ for 1h, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting at 500-550 ℃ for 2.5-3.5 h to obtain cobalt-aluminum-zinc hydrotalcite oxide;
(2) dissolving potassium nitrate with a molar ratio of 0.4-0.6: 1 to zinc nitrate in pure water, uniformly mixing the cobalt-aluminum-zinc hydrotalcite oxide obtained in the step (1), rapidly stirring at 60-65 ℃ for 30min, 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 a potassium-loaded cobalt-aluminum-zinc hydrotalcite oxide, 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 a molar ratio of 2-3: 0.8, mixing and dissolving, adding the carrier obtained in the step (2), uniformly mixing, quickly stirring for 45min at 60-65 ℃, then heating to 70-75 ℃, stirring and concentrating, cooling, filtering, washing, drying, and roasting to obtain the supported nickel catalyst, wherein the active ingredient is nickel iron oxide, and the weight of the active ingredient accounts for 15-30% of the total weight of the supported nickel catalyst.
8. The method for preparing the supported nickel-based catalyst according to claim 7, wherein the calcination temperature in the step (3) is 600 to 700 ℃ and the calcination time is 2.5 to 3 hours.
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| 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 |
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