CN116273090A - Preparation method and application of methane dry reforming catalyst - Google Patents

Preparation method and application of methane dry reforming catalyst Download PDF

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CN116273090A
CN116273090A CN202211706318.2A CN202211706318A CN116273090A CN 116273090 A CN116273090 A CN 116273090A CN 202211706318 A CN202211706318 A CN 202211706318A CN 116273090 A CN116273090 A CN 116273090A
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catalyst
hap
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dry reforming
deionized water
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秦祖赠
宫博
苏通明
纪红兵
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Guangxi University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/1082—Composition of support materials
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a Mg partially substituted hydroxyapatite Mg X Ca 10‑X (PO 4 ) 6 (OH) 2 (X=0, 0.5, 1.0, 1.5, atomic mole ratio is 0-0.18) supported nickel-based catalyst, and its preparation method and application. With Ca (NO) 3 ) 2 ∙4H 2 O、Mg(NO 3 ) 2 ∙6H 2 O、NH 4 H 2 PO 4 And 25 vol% ammonia water to synthesize the catalyst with high activity and high stability through a coprecipitation method. Compared with the pure hydroxyapatite supported nickel catalyst, the magnesium-substituted hydroxyapatite supported nickel catalyst in the method has stronger metal carrier interaction, can effectively inhibit sintering agglomeration of nickel particles, and has higher catalyst activity and stability.

Description

Preparation method and application of methane dry reforming catalyst
Technical Field
The invention relates to a preparation method of a nickel-based catalyst and application of the nickel-based catalyst in methane dry reforming reaction, and belongs to the field of preparation and application of catalysts.
Background
Methane and carbon dioxide are the main roles responsible for the greenhouse effect. Methane dry reforming is one of the most attractive methods for the efficient use of two greenhouse gases, which can convert methane and carbon dioxide into hydrogen and carbon monoxide synthesis gas, which can be further synthesized into a number of high value-added chemicals by fischer-tropsch synthesis, carbonylation, hydroformylation, etc. Related researches show that the noble metals such as Pt, pd, ru, rh, ir have better activity on methane dry reforming reaction, and have better effects on anti-carbon deposition and anti-sintering, and the catalyst has good stability. However, noble metals are expensive and are not suitable for large-scale industrial application. Therefore, the choice of non-noble metals as active components is of paramount importance. Of these, nickel-based and cobalt-based are the most studied non-noble metal catalysts. In particular, a nickel-based catalyst (CN 202011068889.9), which is comparable to noble metal catalysts in activity and inexpensive, can be used on a large scale. However, the deactivation of nickel-based catalysts has limited its commercial application. Since the methane dry reforming reaction is an endothermic reaction, the higher the temperature, the more advantageous the reaction. The high temperatures typically result in sintering of the active metal, and reduced or even deactivated catalyst activity. In addition to catalyst sintering, carbon deposition is another important cause. It is well known that the formation of carbon deposits results mainly from two processes, one being methane decomposition and the other being carbon monoxide disproportionation, carbon deposits mainly resulting from carbon monoxide disproportionation at temperatures below 600 c and carbon deposits produced by carbon monoxide disproportionation above 600 c being negligible and mainly resulting from methane decomposition.
The improvement of the deactivation resistance of the catalyst is generally carried out from two aspects, namely the adjustment of the acid-base properties of the support (CN 202210317980.2); secondly, the particle size of the active component in the catalyst is regulated (CN 201510174271.3). The alkaline carrier can improve the activation capability of carbon dioxide, and oxygen atoms generated after the carbon dioxide is activated can oxidize carbon deposition generated in the dry reforming process of methane; the acidic carrier can improve the cracking capacity of methane, so that the regulation of the acidity and alkalinity of the carrier has great influence on the performance of the catalyst. In general, sintering of the catalyst results in an increase in nickel particle size, the larger the nickel particle size, the more susceptible to carbon deposition. Thus, controlling the size of the nickel particles has a positive effect on preventing catalyst deactivation. The problems of sintering and carbon deposition can be effectively solved by adjusting the interaction between nickel particles and a carrier.
Disclosure of Invention
The invention is characterized in thatAims to solve the problem of catalyst deactivation in the dry reforming process of methane, and takes magnesium modified hydroxyapatite as a carrier (Mg X HAP, x=0, 0.5, 1.0, 1.5, 0 to 0.18 atomic mole ratio of Mg to Ca), nickel loading of 3 wt%, gas space velocity of 30000 mL ∙ g at 750 °c cat -1 ∙h -1 After reaction 100 h under the conditions of (2) the catalyst remained substantially stable.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
(1) Mg X preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 O is mixed and dissolved in 80 mL deionized water, the molar ratio of magnesium to calcium is controlled to be 0-0.18, NH is carried out 4 H 2 PO 4 The solutions were dissolved in 80 mL deionized water, kept (mg+ca)/p=1.67, and each was adjusted to pH 10.5 with 25 vol% aqueous ammonia. NH at room temperature 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 The resulting suspension was stirred at 90℃for 3 h in the O-mixed solution. Centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain Mg X HAP vectors;
(2) Mg X loading of metallic Ni on HAP support:
weigh 0.60 Mg 0.60 g X Adding 60 g deionized water into HAP carrier, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution was used to give a nickel loading of 3 wt%. The pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate. Filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; calcining the dried sample in a muffle furnace at 500 ℃ for 4 h to obtain 3Ni/Mg X HAP catalysts.
Preferably, the molar ratio of magnesium to calcium in the preparation method of the methane dry reforming catalyst is 0.11.
The method for catalyzing by using the methane dry reforming catalyst comprises the following steps: the catalyst was exposed to 10% H at 750 ℃ 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min. Introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure is normal pressure, the reaction temperature is 750 ℃, and the product of the reaction is H 2 And CO.
The invention has the beneficial effects that:
1. the invention uses the magnesium to partially replace calcium ions in the hydroxyapatite as a catalyst carrier, and the basic structure of the hydroxyapatite is not changed by the substitution of the magnesium. The material is easy to prepare and has low cost.
2. The carrier after magnesium substitution has stronger metal-carrier interaction with metal, can effectively inhibit sintering of metal nickel particles and improve the stability of the catalyst. At 750 ℃, the gas space velocity is 30000 mL ∙ g cat -1 ∙h -1 After reaction 100 h under the conditions of (2) the catalyst remained substantially stable.
FIG. 1 is a graph of CO from the methane dry reforming stability test of examples 1 and 4 of the present invention 2 Conversion (FIG. 1 a), CH 4 Conversion (FIG. 1 b), H 2 Ratio of CO (FIG. 1 c) and H 2 Yield (FIG. 1 d) as a function of reaction time.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiment of the present invention is not limited to the range shown in the examples, and as comparative example 4, a catalyst which has not been modified with Mg.
Example 1
(1) Mg 1 Preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 Mixing O and dissolving in 80 mL deionized water, controlling the molar ratio of magnesium to calcium to be 0.11, adding NH 4 H 2 PO 4 Dissolved in 80 of the deionized water of mL,the pH of the two solutions was adjusted to 10.5 with 25 vol% aqueous ammonia, respectively, while maintaining (mg+ca)/p=1.67. NH at room temperature 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 The resulting suspension was stirred at 90℃for 3 h in the O-mixed solution. Centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain Mg 1 HAP vectors;
(2) Mg 1 loading of metallic Ni on HAP support:
weigh 0.60 Mg 0.60 g 1 Adding 60 g deionized water into HAP carrier, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution was used to give a nickel loading of 3 wt%. The pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate. Filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; calcining the dried sample in a muffle furnace at 500 ℃ for 4 h to obtain 3Ni/Mg 1 HAP catalyst, specific surface area of catalyst is shown in Table 1.
Application of the catalyst: weigh 0.04. 0.04 g catalyst in reactor, 10% H at 750deg.C 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min. Introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure was normal pressure, the reaction temperature was 750℃and the results are shown in Table 1. The stability test of the catalyst was carried out under the same reaction conditions with a reaction time of 100 h, and the results are shown in fig. 1.
Example 2
(1) Mg 0.5 Preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 Mixing O and dissolving in 80 mL deionized water, controlling the molar ratio of magnesium to calcium to be 0.05, and adding NH 4 H 2 PO 4 Dissolved in 80 mIn L deionized water, (mg+ca)/p=1.67 was maintained, and the pH of the two solutions was adjusted to 10.5 with 25 vol% aqueous ammonia, respectively. NH at room temperature 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 The resulting suspension was stirred at 90℃for 3 h in the O-mixed solution. Centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain Mg 0.5 HAP vectors;
(2) Mg 0.5 loading of metallic Ni on HAP support:
weigh 0.60 Mg 0.60 g 0.5 Adding 60 g deionized water into HAP carrier, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution was used to give a nickel loading of 3 wt%. The pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate. Filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; calcining the dried sample in a muffle furnace at 500 ℃ for 4 h to obtain 3Ni/Mg 0.5 HAP catalyst, specific surface area of catalyst is shown in Table 1.
Application of the catalyst: weigh 0.04. 0.04 g catalyst in reactor, 10% H at 750deg.C 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min. Introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure was normal pressure, the reaction temperature was 750℃and the results are shown in Table 1.
Example 3
(1) Mg 1.5 Preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 Mixing O and dissolving in 80 mL deionized water, controlling the molar ratio of magnesium to calcium to be 0.18, and adding NH 4 H 2 PO 4 Dissolving in 80 mL deionized water, maintaining (Mg+Ca)/P=1.67, and separating the above two with 25 vol% ammonia waterThe solution was adjusted to pH 10.5. NH at room temperature 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 The resulting suspension was stirred at 90℃for 3 h in the O-mixed solution. Centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain Mg 1.5 HAP vectors;
(2) Mg 1.5 loading of metallic Ni on HAP support:
weigh 0.60 Mg 0.60 g 1.5 Adding 60 g deionized water into HAP carrier, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution was used to give a nickel loading of 3 wt%. The pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate. Filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; calcining the dried sample in a muffle furnace at 500 ℃ for 4 h to obtain 3Ni/Mg 1.5 HAP catalyst, specific surface area of catalyst is shown in Table 1.
Application of the catalyst: weigh 0.04. 0.04 g catalyst in reactor, 10% H at 750deg.C 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min. Introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure was normal pressure, the reaction temperature was 750℃and the results are shown in Table 1.
Example 4
(1) Preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O is dissolved in 80 mL deionized water, NH is added 4 H 2 PO 4 Dissolved in 80 mL deionized water, ca/p=1.67 was maintained, and the pH of each solution was adjusted to 10.5 with 25 vol% aqueous ammonia. At room temperature, NH 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 In O solution, the obtained suspension was stirred at 90℃for 3 h. Centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain an HAP carrier;
(2) Loading of metallic Ni on HAP support:
weighing HAP carrier 0.60 and g, adding deionized water 60 and g, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution was used to give a nickel loading of 3 wt%. The pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate. Filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; the dried sample was calcined in a muffle furnace at 500℃for 4 h to give a 3Ni/HAP catalyst, the specific surface area of which is shown in Table 1.
Application of the catalyst: weigh 0.04. 0.04 g catalyst in reactor, 10% H at 750deg.C 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min. Introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure was normal pressure, the reaction temperature was 750℃and the results are shown in Table 1. The stability test of the catalyst was carried out under the same reaction conditions with a reaction time of 70 h, and the results are shown in fig. 1.
TABLE 1 catalyst Activity test results
Examples Catalyst BET specific surface area (m) 2 ∙g) CO 2 Conversion (%) CH 4 Conversion (%) H 2 Ratio of CO H 2 Yield (%)
1 3Ni/Mg 1 HAP 103.0 99.85 94.27 0.95 86.91
2 3Ni/Mg 0.5 HAP 76.2 97.81 91.44 0.92 83.87
3 3Ni/Mg 1.5 HAP 109.8 96.83 92.13 0.93 85.10
4 3Ni/HAP 64.7 92.10 85.52 0.91 80.28

Claims (3)

1. A preparation method and application of a methane dry reforming catalyst are characterized by comprising the following steps:
(1) Mg X preparation of HAP vector:
ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 O is mixed and dissolved in 80 mL deionized water, the atomic mole ratio of magnesium to calcium is controlled to be 0-0.18, NH is carried out 4 H 2 PO 4 Dissolving in 80 mL deionized water, maintaining (mg+ca)/p=1.67, and adjusting the pH of the two solutions to 10.5 with 25 vol% ammonia water, respectively; NH at room temperature 4 H 2 PO 4 The solution was added dropwise to Ca (NO) 3 ) 2 ∙4H 2 O and Mg (NO) 3 ) 2 ∙6H 2 In the O mixed solution, the obtained suspension is stirred at 90 ℃ for 3 h; centrifuging and washing the precipitate in the suspension to neutrality, and drying overnight in air at 80deg.C; calcining the dried sample in a muffle furnace at 400 ℃ for 4 h to obtain Mg X HAP vectors;
(2) Mg X loading of metallic Ni on HAP support:
weigh 0.60 Mg 0.60 g X Adding 60 g deionized water into HAP carrier, stirring for 10 min, and adding ∙ L at concentration of 0.5 mol -1 Nickel nitrate aqueous solution to make nickel loading 3 wt%; the pH of the mixed solution was adjusted to 10.5 using 25 vol% aqueous ammonia, and stirred at 350 rpm for 3. 3 h to obtain a pale green precipitate; filtering and washing the precipitate to neutrality, and drying in an oven at 80deg.C overnight; the dried sample was calcined in a muffle furnace at 500 ℃ for 4, h to give the desired catalyst.
2. The method for preparing a methane dry reforming catalyst according to claim 1, wherein the atomic molar ratio of magnesium to calcium in (1) is 0.11.
3. The method for using the methane dry reforming catalyst obtained by the preparation method according to claim 1, which is characterized by comprising the following steps: the catalyst was exposed to 10% H at 750 ℃ 2 Reducing for 40 min under Ar; followed by purging with Ar for 40 min; introducing feed gas CH 4 And CO 2 ，N 2 As balance gas, CH 4 、CO 2 、N 2 Is 1:1:2, and the volume space velocity is 30000 mL ∙ g cat -1 ∙h -1 The reaction pressure is normal pressure, the reaction temperature is 750 ℃, and the product of the reaction is H 2 And CO.
CN202211706318.2A 2022-12-29 2022-12-29 Preparation method and application of methane dry reforming catalyst Pending CN116273090A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012258290A1 (en) * 2011-11-22 2013-06-06 Commonwealth Scientific And Industrial Research Organisation Nickel based catalysts for hydrocarbon reforming
US20140339475A1 (en) * 2013-05-16 2014-11-20 Korea Institute Of Science And Technology Alkaline earth metal co-precipitated nickel-based catalyst for steam carbon dioxide reforming of natural gas
CN111375432A (en) * 2018-12-27 2020-07-07 中国科学院大连化学物理研究所 Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof
CN113952970A (en) * 2021-11-10 2022-01-21 中国科学院山西煤炭化学研究所 Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012258290A1 (en) * 2011-11-22 2013-06-06 Commonwealth Scientific And Industrial Research Organisation Nickel based catalysts for hydrocarbon reforming
US20140339475A1 (en) * 2013-05-16 2014-11-20 Korea Institute Of Science And Technology Alkaline earth metal co-precipitated nickel-based catalyst for steam carbon dioxide reforming of natural gas
CN111375432A (en) * 2018-12-27 2020-07-07 中国科学院大连化学物理研究所 Nickel monoatomic catalyst loaded by hydroxyapatite and preparation and application thereof
CN113952970A (en) * 2021-11-10 2022-01-21 中国科学院山西煤炭化学研究所 Catalyst with nickel loaded on hydroxyapatite, preparation method and application thereof

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