CN111841550B - Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst - Google Patents

Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst Download PDF

Info

Publication number
CN111841550B
CN111841550B CN202010829115.7A CN202010829115A CN111841550B CN 111841550 B CN111841550 B CN 111841550B CN 202010829115 A CN202010829115 A CN 202010829115A CN 111841550 B CN111841550 B CN 111841550B
Authority
CN
China
Prior art keywords
alloy
steam reforming
carbon
methane steam
catalyst
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
CN202010829115.7A
Other languages
Chinese (zh)
Other versions
CN111841550A (en
Inventor
柯昌明
林子敬
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.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
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 University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202010829115.7A priority Critical patent/CN111841550B/en
Publication of CN111841550A publication Critical patent/CN111841550A/en
Application granted granted Critical
Publication of CN111841550B publication Critical patent/CN111841550B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

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

Abstract

The invention discloses a bimetallic alloy for an anti-carbon-deposition methane steam reforming catalyst, which consists of two metals, and the general formula of the bimetallic alloy is A x B y Wherein A is one of Fe, co and Ni, and B is one of Ga, zn and Sn; xy satisfies that 3y is more than or equal to x is more than or equal to y; the invention also relates to the application of the bimetallic alloy in the anti-carbon deposition methane steam reforming catalyst. The invention has the advantages that: fe, co, ni and Ga, sn and Zn alloy are used as a methane steam reforming catalyst, so that the price is low; fe. A large amount of stable alloy phases exist in Co, ni, ga, sn and Zn, and the synthesis method is simple; the alloy surface activation site has moderate carbon-oxygen adsorption capacity and higher methane steam reforming activity; because the alloy surface alternately appears on the sites with strong carbon adsorption capacity and the sites with weak adsorption capacity, the carbon atoms on the surface are dispersed on the surface of the catalyst, and the carbon deposition resistance is good.

Description

Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst
Technical Field
The invention relates to a bimetallic alloy, in particular to an application of the bimetallic alloy in an anti-carbon-deposition methane steam reforming catalyst, belonging to the technical field of anti-carbon-deposition methane steam reforming catalysts.
Background
At present, the world is scarce in energy, hydrogen is an important green new energy, and methane steam reforming is more and more concerned by researchers at home and abroad as an economic and efficient hydrogen production method. For example, in Journal of Catalysis,1993,144 (1): 38-49, J.R.Rostrup-Nielsen and J-H.Bak Hansen, ni has high methane steam reforming activity, but the surface is extremely prone to carbon deposition; the noble metals Pt and Pd have good methane steam reforming activity and can resist carbon deposition. However, the price of precious metals limits their use in practical production. Therefore, it is very important to find a cheap and anti-carbon deposition high-efficiency methane steam reforming catalyst.
In addition, in Journal of Power Sources 242 (2013) 762-767, P.Zuo et al, it is proposed to form C by combining C and C on the surface of the catalyst 2 * The anti-carbon deposition performance of the catalyst is judged by the activation energy of the molecules, and is successfully explained by the calculation of a density functional theoryNiAu, niAg and NiCu alloy have the capability of resisting carbon deposition; however, they neglected the fact that NiAu contains precious metals, is expensive, and the NiAg and NiCu alloy phases are not stable.
Disclosure of Invention
Aiming at the problems of the existing catalyst, the bimetallic alloy consisting of (Fe, co, ni) and (Ga, zn and Sn) is used for catalyzing the methane steam reforming, so that the catalyst has the characteristics of high activity, low cost and carbon deposition resistance.
In order to achieve the above object, the present invention adopts the following technical solutions:
a bimetal alloy for an anti-carbon-deposition methane steam reforming catalyst is composed of two metals, and the general formula is A x B y ，
Wherein A is one of Fe, co and Ni, and B is one of Ga, zn and Sn.
Preferably, said bimetallic alloy A x B y And the middle xy satisfies that 3y is more than or equal to x and more than or equal to y.
A catalyst comprising the bimetallic alloy of claim as the primary active material.
The bimetallic alloy is applied to the anti-carbon deposition methane steam reforming catalyst.
The invention has the advantages that:
(1) The invention uses (Fe, co, ni) and (Ga, sn, zn) alloy as methane steam reforming catalyst, and the price is low;
(2) A large amount of stable alloy phases exist in (Fe, co, ni) and (Ga, sn, zn), and the synthetic method is simple;
(3) The alloy surface activation site has moderate carbon and oxygen adsorption capacity and high methane steam reforming activity;
(4) Because the sites with strong carbon adsorption capacity and the sites with weak carbon adsorption on the alloy surface alternately appear, the carbon atoms on the surface are dispersed on the surface of the catalyst, and the carbon deposition resistance is good.
Drawings
FIG. 1 is a schematic illustration of the activity profile of a bimetallic alloy in one embodiment of the invention;
FIG. 2 is a schematic diagram of the distribution of carbon adsorption sites on the surface of a carbon deposition and anti-carbon deposition catalyst.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
A bimetal alloy for an anti-carbon-deposition methane steam reforming catalyst is composed of two metals, and the general formula is A x B y Wherein A is one of Fe, co and Ni, and B is one of Ga, zn and Sn.
To ensure that the alloy activity is higher than that of the noble metal Pt, alloy A x B y Wherein x is more than or equal to y, and x is less than or equal to 3y in order to ensure the anti-carbon deposition performance of the material.
As shown in FIG. 1, the determination of the methane steam reforming activity on the surface of the catalyst can be based on the adsorption energies of carbon and oxygen on the surface thereof, wherein the curve marked with numerical values is an isoactivity line, the numbers on the line are the activities, and the numerical values are represented by Log 10 r is obtained where r is the reaction rate in mol/cm 2 S; according to a widely accepted phase diagram, a large amount of alloy phases with higher activity than Pt exist in an alloy system of Fe, co, ni and Ga, zn and Sn, including FeGa, feSn and Ni 3 Ga、Ni 3 Sn、Co 3 Sn 2 、CoGa、CoSn、NiZn、Ni 5 Ga 3 、Ni 3 Sn 2 、Ni 13 Ga 9 The price of the eleven kinds of high-activity alloys is far lower than that of noble metals such as Pt (the price of the noble metal Ga is about 1/10 of that of Pt).
The surface of Fe, co and Ni metal is easy to deposit carbon, so that the catalyst is damaged. Therefore, in order to achieve the anti-carbon deposition performance, the metal elements should be fully fused to form a stable alloy, so as to prevent a large amount of pure metal phase which is easy to deposit carbon.
The anti-carbon deposition performance comes from the difference of the surface sites of the alloy on the carbon adsorption capacity, so that the preparation method is not required, but the anti-carbon deposition performance of the catalyst can be ensured by the high-purity alloy.
As shown in fig. 2, active surface sites (easy to adsorb carbon atoms) and inactive surface sites (hard to adsorb carbon atoms) similar to NiCu and NiAu on the surface alternately appear, and the surface carbon atoms are dispersed on the surface of the catalyst, so that the catalyst has the carbon deposition resistance.
Next, the application of the bimetallic alloy in the anti-carbon methane steam reforming catalyst is explored, and the alloy Ni is selected from the bimetallic alloy 3 Ga, coGa and NiZn verify the methane steam reforming activity and the carbon deposition resistance of Ga, coGa and NiZn by using a density functional theory.
The methane steam reforming activity of the catalyst is determined by the key reaction step CH * +O * →CHO * The higher the transition energy, the lower the reactivity, as shown in Table 1, the Pt alloy CH * +O * →CHO * The transition energy is higher than that of Ni, so that the methane steam reforming activity of Ni is higher than that of Pt, which is consistent with the results reported in the Journal of Catalysis 144 (1993) 38-49 literature. In addition, ni 3 Ga. CH of CoGa and NiZn * +O * →CHO * The activation energies were all lower than Pt, indicating that they all have better methane steam reforming activity than Pt.
Anti-carbon deposition properties of the catalyst, usually from the catalyst surface C 2 * Activation energy of the molecular formation process was determined as shown in Table 1, C of Pt * +C * →C 2 * The activation energy is much higher than that of Ni, so that the Pt catalyst has the carbon deposition resistance. Likewise, ni 3 Ga, coGa and NiZn surface C 2 * The activation energy of the molecules is equivalent to that of Pt, and the carbon deposition resistance of the molecules is equivalent to that of Pt.
Compared with the existing commercial catalyst, the bimetallic alloy disclosed by the invention has better anti-carbon deposition performance, is much lower in price than the noble metal catalyst with the anti-carbon deposition performance, and is suitable for large-scale practical application.
TABLE 1 Ni, pt, ni 3 Ga. Methane steam reforming activity and anti-carbon deposition performance of CoSn and NiZn
Figure BDA0002637265860000041
Wherein CH * +O * →CHO * Relative energy of transition state is CH * +O * →CHO * The difference between the transition state energy and the initial reactant energy.
It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.

Claims (1)

1. The application of the bimetallic alloy in the anti-carbon deposition methane steam reforming catalyst is characterized in that the bimetallic alloy comprises CoGa.
CN202010829115.7A 2020-08-18 2020-08-18 Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst Active CN111841550B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010829115.7A CN111841550B (en) 2020-08-18 2020-08-18 Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010829115.7A CN111841550B (en) 2020-08-18 2020-08-18 Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst

Publications (2)

Publication Number Publication Date
CN111841550A CN111841550A (en) 2020-10-30
CN111841550B true CN111841550B (en) 2022-12-30

Family

ID=72970200

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010829115.7A Active CN111841550B (en) 2020-08-18 2020-08-18 Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst

Country Status (1)

Country Link
CN (1) CN111841550B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105073254A (en) * 2013-02-25 2015-11-18 日产自动车株式会社 Catalyst particles for fuel cells and method for producing same
CN108380218A (en) * 2018-03-16 2018-08-10 福州大学 A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1104285A (en) * 1964-08-14 1968-02-21 Power Gas Ltd Steam reforming of hydrocarbons
CN100383269C (en) * 2006-06-12 2008-04-23 北京科技大学 Method for preparing high content stannum-cobalt alloy lithium ion battery cathode material
GB201111781D0 (en) * 2011-07-08 2011-08-24 Isis Innovation Stream reforming of methanol
KR101885247B1 (en) * 2012-07-26 2018-08-03 삼성전자주식회사 Co2 reforming catalyst, method preparing the same and method reforming co2
KR101680049B1 (en) * 2015-01-07 2016-11-28 한국과학기술연구원 Dry reforming catalyst, manufacturing method thereof and dry reforming method using the catalyst
CN106944078B (en) * 2016-01-07 2018-11-06 中国石油化工股份有限公司 A kind of preparation method for catalyst for hydrogen production from methane vapor reforming
CN107321352B (en) * 2017-07-19 2021-04-09 武汉凯迪工程技术研究总院有限公司 Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof
WO2019028018A1 (en) * 2017-08-01 2019-02-07 Purdue Research Foundation Nickel alloy catalysts for light alkane dehydrogenation
JP6903324B2 (en) * 2017-08-10 2021-07-14 国立研究開発法人物質・材料研究機構 Hydrogen production catalyst, its production method, and hydrogen production equipment using it
CN108671929B (en) * 2018-05-02 2021-05-11 大连理工大学 Preparation method of ultra-small nano alloy catalyst for electrocatalytic water decomposition oxygen evolution reaction
CN110586111A (en) * 2019-09-17 2019-12-20 大连海事大学 Preparation method of composite catalyst for hydrogen production by methane steam reforming

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105073254A (en) * 2013-02-25 2015-11-18 日产自动车株式会社 Catalyst particles for fuel cells and method for producing same
CN108380218A (en) * 2018-03-16 2018-08-10 福州大学 A kind of uniform nickel cobalt (alloy) catalyst of support type and preparation method thereof

Also Published As

Publication number Publication date
CN111841550A (en) 2020-10-30

Similar Documents

Publication Publication Date Title
Wang et al. Hydrolysis of ammonia-borane over Ni/ZIF-8 nanocatalyst: high efficiency, mechanism, and controlled hydrogen release
Zhao et al. NiCo alloy decorated on porous N-doped carbon derived from ZnCo-ZIF as highly efficient and magnetically recyclable catalyst for hydrogen evolution from ammonia borane
Lu et al. Co3O4/CuMoO4 hybrid microflowers composed of nanorods with rich particle boundaries as a highly active catalyst for ammonia borane hydrolysis
He et al. The oxygen reduction reaction on graphitic carbon nitride supported single Ce atom and CexPt6-x cluster catalysts from first-principles
Mathe et al. Methanol oxidation reaction activity of microwave-irradiated and heat-treated Pt/Co and Pt/Ni nano-electrocatalysts
CN113224334A (en) Preparation method of platinum-containing high-entropy alloy/MXene composite catalyst
Kim et al. Recent progress in Pt-based electrocatalysts for ammonia oxidation reaction
Zhao et al. La1− xKxFe0. 7Ni0. 3O3 catalyst for ethanol steam reforming—The effect of K-doping
Liu et al. Cyanogel‐Induced PdCu Alloy with Pd‐Enriched Surface for Formic Acid Oxidation and Oxygen Reduction
Wei et al. Pt-based catalyst decorated by bimetallic FeNi2P with outstanding CO tolerance and catalytic activity for methanol electrooxidation
Li et al. Tri-metallic PtPdAu mesoporous nanoelectrocatalysts
Zhu et al. Advances and Regulation Strategies of the Active Moiety in Dual‐Atom Site Catalysts for Efficient Electrocatalysis
CN104261347A (en) Method for producing hydrogen by hydrolyzing ammonia borane
Zhang et al. Identifying the crystal and electronic structure evolution in tri‐component transition metal oxide nanosheets for efficient electrocatalytic oxygen evolution
EP2872252A1 (en) Carbendazim-based catalytic materials
CN102614880A (en) Preparation and application of carbon-supported amorphous metallic nickel
CN111841550B (en) Application of bimetallic alloy in anti-carbon deposition methane steam reforming catalyst
Jiang et al. (1 1 0) Facet of pentlandite with Fe-Ni heterostructure for promising electrocatalytic water splitting
Wang et al. Significantly enhanced oxygen evolution reaction performance by tuning surface states of Co through Cu modification in alloy structure
Chen et al. Rational design of a Fe/S/N/C catalyst from ZIF-8 for efficient oxygen reduction reaction
Nabi et al. Ab initio random structure searching and catalytic properties of copper-based nanocluster with Earth-abundant metals for the electrocatalytic CO2-to-CO conversion
Huang et al. Boosting the anti-poisoning ability of palladium towards electrocatalytic formic acid oxidation via polyphosphide chemistry
CN114733477A (en) Thermal plasma coupling catalysis natural gas and CO2Method for preparing synthetic gas by reforming dry gas
CN114768746A (en) Metal catalytic reactor, preparation thereof and application thereof in natural gas and CO2Application of dry gas reforming to synthesis gas
Zhang et al. Construction of Co–Se–W at Interfaces of Phase‐Mixed Cobalt Selenide via Spontaneous Phase Transition for Platinum‐Like Hydrogen Evolution Activity and Long‐Term Durability in Alkaline and Acidic Media

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