CN112138654A - Carbon dioxide hydromethanation reaction catalyst and application thereof - Google Patents

Carbon dioxide hydromethanation reaction catalyst and application thereof Download PDF

Info

Publication number
CN112138654A
CN112138654A CN202010953141.0A CN202010953141A CN112138654A CN 112138654 A CN112138654 A CN 112138654A CN 202010953141 A CN202010953141 A CN 202010953141A CN 112138654 A CN112138654 A CN 112138654A
Authority
CN
China
Prior art keywords
carbon dioxide
catalyst
solution
powder
reaction
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.)
Granted
Application number
CN202010953141.0A
Other languages
Chinese (zh)
Other versions
CN112138654B (en
Inventor
杨郅栋
行智华
行丽华
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN202010953141.0A priority Critical patent/CN112138654B/en
Publication of CN112138654A publication Critical patent/CN112138654A/en
Application granted granted Critical
Publication of CN112138654B publication Critical patent/CN112138654B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst for carbon dioxide hydrogenation methanation reaction and application thereof, wherein a catalyst carrier contains TiO2、ZrO2MgO and metal powder, wherein TiO2、ZrO2The mass ratio of MgO to metal powder is 50-80:5-30:1-10:1-10, and the metal powder is one or more of zinc powder, aluminum powder or tin powder. Dripping liquid-phase titanium salt into deionized water in an ice water bath to form a transparent solution, mixing the transparent solution with a zirconium and magnesium metal salt solution to obtain a uniform solution, adding alkali liquor to precipitate completely, filtering and washing the obtained suspension, collecting a titanium-zirconium-magnesium compound, adding metal powder, uniformly mixing, pressing and molding, and drying to obtain a catalyst carrier; loading an active component and an auxiliary agent to the obtained carrier, drying, roasting, and treating with a dilute NaOH solution to obtain the carbon dioxide methanation catalyst, wherein the active component element is one or more of Pt, Ru, Ni and Co, and the auxiliary agent element is one of Re, Ir, B or P. The catalyst is applied to carbon dioxide hydromethanation in the gas regeneration technology in the cabin of the underwater vehicle, enrichment carbon dioxide hydromethanation in a methane purification process, and carbon dioxide hydromethanation in the purification of synthesis ammonia raw gas.

Description

Carbon dioxide hydromethanation reaction catalyst and application thereof
Technical Field
The invention belongs to the field of catalysts and preparation methods and applications thereof, and particularly relates to a carbon dioxide hydromethanation reaction catalyst and a preparation method and application thereof.
Background
It is widely accepted by the academia today that the greenhouse gas CO formed from the combustion of fossil fuels2The global climate change problem caused by the emission is increasingly intensified, and becomes a great threat to human beings and the global ecosystem. This results in, on the one hand, a constantly decreasing reserve of non-renewable energy and a risk of exhaustion, and, on the other hand, also a large carbon dioxide emission. In response to the global warming problem caused by the greenhouse effect, governments and united nations worldwide have taken a great deal of relevant international plans and actions over the past decades. Wherein, one potential solution is to utilize hydrogen produced by water electrolysis of renewable energy sources such as photovoltaic energy, wind power energy and the like, capture carbon dioxide generated in production and life as a carbon source, and pass CO2To produce useful chemicals or fuels by catalytic hydrogenation. The scheme can help solve the problem of CO in the atmosphere2Environmental problems caused by increased concentration, and can relieve excessive dependence on fossil fuel and storage of renewable energyTo give a title.
The most typical example of carbon dioxide hydromethanation is the study of processes for the conversion of synthesis gas. The process belongs to a high-temperature high-pressure reaction process, and the catalytic system is used for solving the problems of synthetic gas, pyrolysis gas, coke oven gas and other gases containing carbon oxides and hydrogen, and carrying out industrial-scale hydromethanation reaction after the carbon-hydrogen ratio is adjusted through purification and transformation. There have been a number of research reports on catalysts and methods of preparation in this field, focusing on Ni-based methanation catalysts in the syngas conversion process. The catalyst has good activity at high temperature, but is easy to sinter and deactivate, and the activity at low temperature is not high.
In the field of biomass, the components of biogas mainly comprise methane (50% -60%) and carbon dioxide (40% -50%), and in the process of purifying and converting biogas into natural gas, the content and energy density of methane in biogas can be improved mainly by removing carbon dioxide, nitrogen, sulfur and other micromolecular impurity gas components in biogas, so that high-quality biogas is prepared. The refined biogas can be used as automobile and train fuel after being prepared by pressurization. The method for removing the carbon dioxide in the biogas can be realized by various methods, such as an absorption method, a pressure swing adsorption method and the like. The carbon dioxide after desorption and absorption can realize the enrichment of methane gas through catalytic conversion, and further utilize the carbon resource therein.
Under the special closed environment of an underwater vehicle and the like, the gas regeneration technology of the environment-friendly and environment-friendly system is to collect and concentrate carbon dioxide generated by system personnel in an cabin, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the carbon dioxide and hydrogen can be reacted and hydrogenated and reduced to generate methane and water, and the water is supplied to an electrolysis system for electrolysis to generate oxygen. The oxygen generated by water electrolysis can be used as electrolytic water, and the generated hydrogen can be supplied to the heterogeneous catalytic reaction system for reduction reaction as the consumption of system personnel in the cabin. The use of such a closed system will greatly reduce the amount of make-up of consumable materials, with the water, oxygen and carbon dioxide absorbents essentially forming a closed loop.
Through the analysis, the carbon dioxide hydromethanation is the core technology in the application field. Because carbon dioxide has high thermodynamic stability and strong chemical inertness, in order to realize the activation of carbon dioxide, a catalyst is the key of the activation of carbon dioxide, and the reaction process is as follows:
Figure BDA0002677693390000021
the methanation reaction of carbon dioxide is a violent exothermic chemical reaction, but the chemical inertness of carbon dioxide causes the corresponding reaction activation energy to be higher, and the process needs to be promoted to be smooth from two aspects of increasing the reaction temperature to promote the activation and adopting a high-activity catalyst to reduce the activation energy.
In the prior art, carbon dioxide hydromethanation catalysts all need an additional hydrogen source, and are subjected to a reduction activation step under a heating condition; the activity of the carbon dioxide methanation catalyst is not high at low temperature (200-; meanwhile, the methanation catalytic reaction temperature is higher and is generally higher than 400 ℃ (CN 106268858), the methanation catalyst has poor stability under the high-temperature condition, and crystal grains are easy to aggregate and grow, so that the catalyst is sintered and deactivated; in the application of carbon dioxide hydromethanation, the reaction selectivity is difficult to reach 100 percent, and the process of purifying and converting methane into natural gas is difficult to realize synchronization with a natural gas pipeline; the application of the gas regeneration technology in an environment-friendly and life-saving system is difficult to realize by adopting a small amount of carbon monoxide in the process of carbon dioxide hydrogenation methanation by using the existing catalyst.
Disclosure of Invention
In order to further improve the activity of the carbon dioxide hydromethanation reaction catalyst, the invention aims to solve the technical problem of providing an in-situ pore-forming reduction method, a carbon dioxide hydromethanation catalyst with high and low temperature activity and high temperature stability and application thereof.
Therefore, the preparation method of the carbon dioxide hydromethanation reaction catalyst provided by the invention comprises the following steps:
a. preparing a mixed aqueous solution containing a liquid-phase titanium salt precursor, zirconium metal salt and magnesium metal salt, and adding alkali liquor into the prepared mixed solution to mix to obtain a suspension;
b. centrifuging the suspension obtained in the step a, collecting precipitates, adding metal powder into the precipitates, uniformly mixing, molding, drying and roasting to obtain a catalyst carrier; the metal powder is one or more of zinc powder, aluminum powder or tin powder, and the obtained catalyst carrier contains TiO2,ZrO2MgO and metal powder, the TiO2,ZrO2The mass ratio of MgO to metal powder is 50-80:5-30:1-10: 1-10;
c. loading an active component metal element and an auxiliary agent element on the carrier obtained in the step B, drying and roasting to obtain a catalyst precursor, wherein the active component is one or more of Pt, Ru, Ni and Co, and the auxiliary agent element is one of Re, Ir, B or P;
d. and d, treating the catalyst precursor obtained in the step c by adopting a NaOH solution to obtain the carbon dioxide methanation catalyst.
Further, the step a includes: firstly, dripping a liquid-phase titanium salt precursor into deionized water under the ice-water bath condition to form a transparent solution; then, the zirconium-containing metal salt and the magnesium-containing metal salt are dissolved in the transparent solution to obtain a mixed aqueous solution.
Optionally, the liquid-phase titanium salt precursor is TiCl4Tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate. TiCl may be preferred4Or tetraethyl titanate.
Optionally, the zirconium metal salt is ZrOCl2Or ZrOCl2A hydrate.
Optionally, the magnesium metal salt is Mg (NO)3)2Or MgCl2。
Optionally, the alkali solution is one of an aqueous NaOH solution, an aqueous KOH solution or an aqueous ammonia solution, and the alkali solution is added to precipitate until the pH is 12 to 14, preferably an aqueous ammonia solution.
Optionally, the mass concentration of the NaOH solution in the step d is 8-20%.
Preferably, the calcination temperature in the step b is 200-600 ℃, and preferably 300-450 ℃.
Preferably, the loading amount of the active component metal element is 0.5-10.0 wt.%, and can be preferably 1.0-5.0 wt.% of the catalyst carrier; the total loading of the promoter elements is from 0.5 to 5.0 wt.%, preferably from 1.0 to 3.0 wt.%, of the catalyst support.
Optionally, in the step c, an isovolumetric impregnation method, an excess impregnation method or an alkali precipitation method is adopted to load the active component metal elements and the auxiliary agent metal elements onto the solid solution carrier obtained in the step b.
Optionally, the catalyst precursor is treated with a NaOH solution, the mass concentration of which is 8% -20%, preferably 10% -15%.
The invention provides application of the carbon dioxide hydromethanation catalyst, and the catalyst is applied to carbon dioxide hydromethanation reaction in the purification of synthesis ammonia raw material gas and carbon dioxide enrichment hydromethanation reaction in a biogas purification process, in particular to the carbon dioxide hydromethanation reaction of a gas regeneration technology in an underwater vehicle cabin.
According to the carbon dioxide hydromethanation reaction, the carbon source obtained by separating and purifying the methane can be used as the carbon source of the carbon dioxide raw material, and in the methane separation and purification process, the selective adsorption characteristic of an adsorbent (such as a molecular sieve) on the carbon dioxide is utilized, namely the carbon dioxide on the adsorbent has a higher separation coefficient relative to other gaseous components, so that the aim of removing the carbon dioxide in the methane is fulfilled. In the adsorption process, carbon dioxide in the raw material gas is adsorbed in the adsorption tower under the pressurization condition, other weakly-adsorptive gases such as methane and the like are discharged as purified gas, and after the adsorption is saturated, the adsorption column is decompressed and even vacuumized to release the adsorbed carbon dioxide.
According to the carbon dioxide hydromethanation reaction, the carbon dioxide raw material can be carbon dioxide generated by metabolism of personnel in an underwater vehicle, the carbon dioxide is collected and concentrated, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the carbon dioxide and hydrogen can be reacted, hydrogenated and reduced to generate methane and water, and the water is supplied to an electrolysis system for electrolysis to generate oxygen; the oxygen generated by water electrolysis can be used as electrolytic water, and the generated hydrogen can be supplied to the heterogeneous catalytic reaction system for reduction reaction as the consumption of system personnel in the cabin. The use of such a closed system will greatly reduce the amount of make-up of consumable materials, with the water, oxygen and carbon dioxide absorbents essentially forming a closed loop.
The invention uses the high-efficiency composite oxide catalyst carrier, and adopts the solid solution form to cause the titanium dioxide of the catalyst carrier to generate surface defects, thereby promoting the formation of intermediate species with stronger reaction activity, such as excited molecules, free radical ions and the like in a reaction system; active components and catalytic assistants are added, and the surface energy level structure and the free radical reaction process of the catalyst in the reaction system are changed through the influence of the active components and the catalytic assistants on electron spin, so that the method is more favorable for CO2Polarization and ionization of molecules, and CO realization under mild reaction conditions and low energy consumption2High efficiency transformation of (1). CO of the invention2The technical level of the hydromethanation reaction is improved, on one hand, a high-efficiency catalyst can be used, and on the other hand, the limitation of the traditional thermal catalysis process can be broken through; for example, while controlling the catalytic reaction by using the conventional parameters such as temperature, pressure and airspeed, the auxiliary external field such as magnetic field, illumination and the like can be applied to the reaction system, so as to optimize the catalytic reaction path and promote CO2Efficient transformation provides greater development space. Specifically, the method comprises the following steps:
(1) in the design of the carbon dioxide hydromethanation catalyst, the metal powder is Al powder, Zn powder or Sn powder, when the catalyst is treated with a NaOH solution, the metal powder and NaOH generate an oxidation-reduction reaction, and a new pore area is generated after the metal powder reacts, so that effective pores are provided for diffusion of methanation catalytic reactants and products, the rate of the hydromethanation reaction on the inner surface and the outer surface of the catalyst is favorably improved, the methanation selectivity is further improved, and the selectivity reaches 100%;
(2) al powder, Zn powder or Sn powder and NaOH dilute solution react to generate a large amount of active hydrogen, and metal active components such as Pt, Ru, Ni and Co can be reduced under the action of active hydrogen atoms in a hydrogen atmosphere, so that the active components can be directly used for carbon dioxide hydromethanation reaction, an additional hydrogen source is not needed, and the reduction activation step is omitted;
(3) the carbon dioxide methanation catalyst has high activity at low temperature (200-;
(4) in the application of carbon dioxide hydromethanation, the reaction selectivity is difficult to reach 100 percent, and the process of purifying and converting methane into natural gas is difficult to realize synchronization with a natural gas pipeline;
(5) carbon monoxide is not generated in the carbon dioxide hydromethanation process, and the application of the gas regeneration technology of the environment-friendly and life-saving system in the underwater vehicle to the carbon dioxide hydromethanation reaction can be realized.
Detailed Description
According to the design of the carbon dioxide hydromethanation catalyst, the metal powder is Al powder, Zn powder or Sn powder, when the catalyst is treated with a NaOH solution, the metal powder and NaOH generate an oxidation-reduction reaction, and a new pore area is generated after the metal powder is reacted, so that effective pores are provided for diffusion of methanation catalytic reactants and products, the rate of the hydromethanation reaction on the inner surface and the outer surface of the catalyst is increased, and the methanation selectivity is further improved; meanwhile, Al powder, Zn powder or Sn powder and NaOH dilute solution react to generate a large amount of active hydrogen, and Pt, Ru, Ni, Co and other metal active components can be reduced under the action of active hydrogen atoms in hydrogen atmosphere, so that the catalyst is directly used for carbon dioxide hydromethanation reaction, an additional hydrogen source is not needed, the reduction activation step is omitted, and the reaction principle of the Al powder, Zn powder or Sn powder and NaOH dilute solution is as follows:
2Al+2NaOH+2H2O→2NaAlO2+3H2↑；
Zn+2NaOH→2NaZnO2+H2↑；
Sn+2NaOH→2NaSnO2+H2↑。
the present invention is further illustrated by the following examples, but is not limited thereto.
Example 1:
mixing TiCl4(0.876mol,166.2g) was added dropwise to 180.0ml of deionized water in an ice-water bath, mixed vigorously, and ZrOCl was added thereto2(0.122mol,21.7g)、MgCl2(0.122mol,11.8g) was dissolved in the solution to give a homogeneous mixed solution, which was sufficiently stirred and mixed to give a homogeneous solution, howeverDropwise adding NaOH aqueous solution with the mass concentration of 26.0% at room temperature, controlling the dropwise adding amount per minute to be 1.0ml, continuously stirring until the pH value of the suspension is 14, filtering the formed slurry, fully washing the slurry with deionized water to be neutral to obtain a titanium-zirconium-magnesium composite, adding aluminum powder, and counting TiO by mass parts2:ZrO2MgO and Al are 70:15:5:5, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and formed, and then dried at 120 ℃ for 12 hours and roasted at 400 ℃ for 8 hours to prepare a catalyst carrier;
adding RuCl3·3H2O (0.061mol,15.9g) and NaBO2·4H2Dissolving O (0.189mol,26.1g) into 200mL of ethanol water solution with the volume fraction of 50%; then adding 205g of the catalyst carrier, strongly stirring and dipping for 16 h; the solvent was evaporated from the resulting material, then dried at 60 ℃ for 8h and calcined at 380 ℃ for 8 h. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 3 hours at 90 ℃ by using a 15% NaOH solution to obtain the carbon dioxide methanation catalyst A.
Example 2:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 1 in that: mixing TiCl4(1.064mol,201.7g) was added dropwise to 180.0ml of deionized water in an ice-water bath, mixed vigorously, and ZrOCl was added thereto2(0.162mol,28.9g)、MgCl2(0.07mol,7.08g) is dissolved in the solution, 26.0 percent ammonia water solution is adopted for precipitation to prepare titanium zirconium magnesium compound, zinc powder is added, and TiO is calculated according to the mass portion2:ZrO2Adding graphite powder as a release agent into MgO, Zn and the like in a ratio of 85:20:3:8, uniformly mixing, performing compression molding, and roasting at 350 ℃ for 5 hours to obtain a catalyst carrier;
then RuCl is added by an impregnation method3·3H2O (0.122mol,31.8g) and NaBO2·4H2O (0.114mol,15.7g) to 245.7g of catalyst carrier, drying and roasting, and then treating for 6 hours at 85 ℃ by using 10% NaOH solution to obtain the carbon dioxide methanation catalyst B.
Example 3:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 1 in that: mixing TiCl4(0.751mol,142.4g) in iceDropping into 180.0ml deionized water in water bath, mixing vigorously, and adding ZrOCl2(0.202mol,36.1g)、MgCl2(0.124mol,11.8g) is dissolved in the solution, 15.0 percent KOH aqueous solution is adopted for precipitation to prepare titanium-zirconium-magnesium compound, tin powder is added, and TiO is calculated according to the mass portion2:ZrO2Adding graphite powder as a release agent into MgO, Sn and the like in a ratio of 60:25:5:3, uniformly mixing, performing compression molding, and roasting at 350 ℃ for 5 hours to obtain a catalyst carrier;
then RuCl is added by an impregnation method3·3H2O (0.05mol,12.9g) and NaBO2·4H2O (0.0.462mol,63.7g) is put on 250g of catalyst carrier, dried and roasted, and then treated by 10 percent NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst C.
Example 4:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 1 in that: mixing TiCl4(0.688mol,130.6g) was added in 180.0ml deionized water by dropping in an ice-water bath, mixed vigorously, and ZrOCl was added2(0.243mol,43.4g)、MgCl2(0.248mol,23.6g) is dissolved in the solution, 15.0 percent KOH aqueous solution is adopted for precipitation to prepare titanium-zirconium-magnesium compound, tin powder is added, and TiO is calculated according to the mass portion2:ZrO2Adding graphite powder as a release agent into MgO, Sn and the like in a ratio of 55:30:10:5, uniformly mixing, performing compression molding, and roasting at 350 ℃ for 5 hours to obtain a catalyst carrier;
then RuCl is added by an impregnation method3·3H2O (0.146mol,38.4g) and NaBO2·4H2O (0.274mol,37.8g) is put on 296g of catalyst carrier, dried and roasted, and then treated by 10 percent NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst D.
Example 5:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 1 in that: mixing TiCl4(1.12mol,213.6g) was added dropwise to 180.0ml of deionized water in an ice-water bath, mixed vigorously, and ZrOCl was added2(0.081mol,14.4g)、MgCl2(0.198mol,18.9g) is dissolved in the solution, a 15.0 percent KOH aqueous solution is adopted for precipitation to prepare a titanium-zirconium-magnesium compound, aluminum powder is added, and Ti is counted by weight portionO2:ZrO2MgO, Al, is 90:10:8:5, graphite powder is added as a release agent, the mixture is uniformly mixed, pressed and molded, and roasted for 5 hours at 350 ℃ to prepare a catalyst carrier; then RuCl is added by an impregnation method3·3H2O (0.099mol,26.1g) and NaBO2·4H2O (0.233mol,32.1g) to 252g of catalyst carrier, drying, roasting, and then treating with 15% NaOH solution at 85 ℃ for 6 hours to obtain the carbon dioxide methanation catalyst E.
Example 6:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 5 in that: mixing Pt (NO)3)2(0.063mol,20.1g) and NaBO2(0.114mol,15.7g) is dissolved in 23.5mL of ethanol water solution with 50 percent of volume fraction; then 245.7g of catalyst carrier is added, stirred intensively and dipped for 16 h; the solvent was evaporated from the resulting material, then dried at 50 ℃ for 8h and calcined at 400 ℃ for 8 h. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 6 hours at 85 ℃ by using 8% NaOH solution to obtain the carbon dioxide methanation catalyst F.
Example 7:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 5 in that: mixing NiCl2·6H2O (0.416mol,99.1g) and NH4ReO7(0.013mol,3.54g) was dissolved in 23.5mL of 50% by volume aqueous ethanol; then 245.7g of catalyst carrier is added, stirred intensively and dipped for 16 h; the solvent was then evaporated from the resulting material, dried at 70 ℃ for 6h and calcined at 360 ℃ for 12 h. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 5 hours at the temperature of 60 ℃ by using a 20% NaOH solution to obtain the carbon dioxide methanation catalyst G.
Example 8:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 5 in that: adding CoCl2·6H2O (0.416mol,99.1g) and (NH)4)2IrCl6(0.026mol,11.3g) was dissolved in 23.5mL of 50% by volume aqueous ethanol solution; then 245.7g of catalyst carrier is added, stirred intensively and dipped for 16 h; evaporating the solvent to dryness, drying at 70 deg.C for 6 hr, and heating to 360 deg.CAnd (5) roasting for 12 hours. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 5 hours at the temperature of 60 ℃ by using a 15% NaOH solution to obtain the carbon dioxide methanation catalyst H.
Example 9:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 5 in that: adding RuCl3·3H2O (0.122mol,31.8g) and (NH)4)2HPO4(0.079mol,10.5g) was dissolved in 23.5mL of 50% by volume aqueous ethanol; then 245.7g of catalyst carrier is added, stirred intensively and dipped for 16 h; the solvent was evaporated from the resulting material, then dried at 60 ℃ for 8h and calcined at 380 ℃ for 8 h. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 3 hours at 90 ℃ by using a 15% NaOH solution to obtain the carbon dioxide methanation catalyst I.
Example 10:
the preparation method of the titanium-zirconium-magnesium composite carrier is different from that of the example 5 in that: adding RuCl3·3H2O (0.073mol,19.1g) and NH4ReO7(0.04mol,10.6g) is dissolved in 23.5mL of ethanol water solution with 50 percent of volume fraction; then 245.7g of catalyst carrier is added, stirred intensively and dipped for 16 h; the solvent was then evaporated from the resulting material, dried at 70 ℃ for 6h and calcined at 360 ℃ for 12 h. And taking out the roasted catalyst precursor, and treating the catalyst precursor for 5 hours at the temperature of 60 ℃ by using a 20% NaOH solution to obtain the carbon dioxide methanation catalyst J.
Example 11:
in the process of purifying and converting the biogas into the natural gas, the purpose of removing the carbon dioxide in the biogas is achieved by utilizing the selective adsorption characteristic of an adsorbent (such as a molecular sieve) on the carbon dioxide, namely the carbon dioxide on the adsorbent has a higher separation coefficient relative to other gaseous components. In the adsorption process, carbon dioxide in the raw material gas is adsorbed in the adsorption tower under the pressurization condition, other weakly-adsorptive gases such as methane and the like are discharged as purified gas, and after the adsorption is saturated, the adsorption column is decompressed and even vacuumized to release the adsorbed carbon dioxide.
Separating and purifying the methane, and resolving to obtain CO295.4 percent of volume content, and the balance of nitrogen and nitrogenSulfur small molecule gas, CO at volume flow2/H2/N21/4/4, total space velocity of 18000--1·h-1And then, raising the temperature of the reactor to 200-350 ℃ to carry out the carbon dioxide hydrogenation methanation reaction.
The catalyst evaluation was carried out using a fixed bed reactor having dimensions of 400 mm. times. phi.10 mm. times.1 mm. The reaction is carried out under 0.1MPa, 0.25g of catalyst is filled, the particle size of the catalyst is 0.25-0.4mm, the reactor is heated to the specified temperature for carrying out the carbon dioxide hydromethanation reaction, the product gas composition is analyzed by gas chromatography, and the performance data of the obtained catalyst is the result after the reaction is stable. The results are shown in Table 1 below.
TABLE 1
Figure BDA0002677693390000081
Example 12:
under special closed environments such as an underwater simulation aircraft and the like, collecting and concentrating carbon dioxide generated by metabolism of personnel in the underwater simulation aircraft, supplying the collected carbon dioxide to a heterogeneous catalytic reaction system, and performing CO (carbon dioxide) treatment at volume flow2/H2/N21/4/5, total space velocity 22000--1·h-1Then, the reactor was heated to 200-300 ℃ to perform the carbon dioxide hydromethanation reaction, the product gas composition was analyzed by gas chromatography, and the catalyst evaluation method was the same as in example 11, and the results are shown in Table 2 below.
TABLE 2
Figure BDA0002677693390000082
Figure BDA0002677693390000091
Example 13:
under special closed environments such as an underwater simulated aircraft and the like, carbon dioxide generated by metabolism of personnel in the underwater aircraft is collected and concentrated, the collected carbon dioxide is supplied to a heterogeneous catalytic reaction system, the reaction conditions are the same as those in example 12, the composition of product gas is analyzed through gas chromatography, the evaluation mode of a catalyst is the same as that in example 11, and the results are shown in table 3 below.
TABLE 3
Figure BDA0002677693390000092

Claims (9)

1. A carbon dioxide hydromethanation reaction catalyst is characterized in that the preparation method of the catalyst comprises the following steps:
a. preparing a mixed aqueous solution containing a liquid-phase titanium salt precursor, zirconium metal salt and magnesium metal salt, and adding alkali liquor into the prepared mixed solution to mix to obtain a suspension;
b. centrifuging the suspension obtained in the step a, collecting precipitates, adding metal powder into the precipitates, uniformly mixing, molding, drying and roasting to obtain a catalyst carrier; the metal powder is one or more of zinc powder, aluminum powder or tin powder, and the obtained catalyst carrier contains TiO2,ZrO2MgO and metal powder, the TiO2,ZrO2The mass ratio of MgO to metal powder is 50-80:5-30:1-10: 1-10;
c. loading an active component metal element and an auxiliary agent element on the carrier obtained in the step B, drying and roasting to obtain a catalyst precursor, wherein the active component is one or more of Pt, Ru, Ni and Co, and the auxiliary agent element is one of Re, Ir, B or P;
d. and c, treating the catalyst precursor obtained in the step c by using a NaOH solution to obtain the carbon dioxide methanation catalyst.
2. The carbon dioxide hydromethanation reaction catalyst of claim 1, wherein step a comprises: firstly, dripping a liquid-phase titanium salt precursor into deionized water under the ice-water bath condition to form a transparent solution; then, the zirconium-containing metal salt and the magnesium-containing metal salt are dissolved in the transparent solution to obtain a mixed aqueous solution.
3. The carbon dioxide hydromethanation catalyst of claim 1, wherein the liquid phase titanium salt precursor is TiCl4Tetrabutyl titanate, tetraethyl titanate or tetraisopropyl titanate; the zirconium metal salt is ZrOCl2Or ZrOCl2A hydrate; the magnesium metal salt is Mg (NO)3)2Or MgCl2。
4. The carbon dioxide hydromethanation catalyst according to claim 1, wherein the alkali solution is one of an aqueous NaOH solution, an aqueous KOH solution or an aqueous ammonia solution, and the alkali solution is added to precipitate until the pH value is 12-14.
5. The carbon dioxide hydromethanation reaction catalyst according to claim 1, wherein the mass concentration of the NaOH solution in step d is 8-20%.
6. The carbon dioxide hydromethanation reaction catalyst as claimed in claim 1, wherein the calcination temperature in step b is 200-600 ℃.
7. The carbon dioxide hydromethanation reaction catalyst of claim 1, wherein the loading of the active component metal element is from 0.5 wt.% to 10.0 wt.% of the catalyst support; the total loading of the auxiliary elements is 0.5-5.0 wt.% of the catalyst carrier.
8. The carbon dioxide hydromethanation reaction catalyst according to claim 1, wherein in the step c, an equivalent volume impregnation method, an excess impregnation method or an alkali precipitation method is adopted to load the active component metal element and the auxiliary agent metal element on the solid solution carrier obtained in the step b.
9. Use of a catalyst according to any one of claims 1 to 8 as a catalyst in a carbon dioxide hydromethanation reaction comprising: the method comprises the steps of gas regeneration reaction in the closed space of the underwater vehicle, gas regeneration reaction of an environment-friendly life-support system, carbon dioxide hydromethanation reaction in the purification of synthesis ammonia raw material gas or carbon dioxide hydromethanation reaction enriched in a methane purification process.
CN202010953141.0A 2020-09-11 2020-09-11 Catalyst for hydromethanation of carbon dioxide and application thereof Active CN112138654B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010953141.0A CN112138654B (en) 2020-09-11 2020-09-11 Catalyst for hydromethanation of carbon dioxide and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010953141.0A CN112138654B (en) 2020-09-11 2020-09-11 Catalyst for hydromethanation of carbon dioxide and application thereof

Publications (2)

Publication Number Publication Date
CN112138654A true CN112138654A (en) 2020-12-29
CN112138654B CN112138654B (en) 2023-06-27

Family

ID=73890242

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010953141.0A Active CN112138654B (en) 2020-09-11 2020-09-11 Catalyst for hydromethanation of carbon dioxide and application thereof

Country Status (1)

Country Link
CN (1) CN112138654B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113649021A (en) * 2021-09-09 2021-11-16 濮阳圣恺环保新材料科技股份有限公司 Preparation method of copper hydrogenation catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101703933A (en) * 2009-11-06 2010-05-12 山西大学 Bimetal methanation catalyst and preparation method thereof
CN103191749A (en) * 2013-04-08 2013-07-10 西北化工研究院 Methanation catalyst for synthesizing substitute natural gas and preparation method thereof
CN104923225A (en) * 2014-03-18 2015-09-23 中国科学院大连化学物理研究所 Supported noble metal catalyst and preparation and application thereof
CN105618157A (en) * 2014-12-01 2016-06-01 中国科学院大连化学物理研究所 Composite oxide carrier with bimodal mesopores, as well as preparation method and application of composite oxide carrier
CN106311242A (en) * 2015-07-06 2017-01-11 中国石油化工股份有限公司 Carbon dioxide methanation catalyst and preparation method thereof
WO2017085593A2 (en) * 2015-11-16 2017-05-26 Sabic Global Technologies B.V. High temperature methods for hydrogenation of co2 to syngas for production of olefins

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101703933A (en) * 2009-11-06 2010-05-12 山西大学 Bimetal methanation catalyst and preparation method thereof
CN103191749A (en) * 2013-04-08 2013-07-10 西北化工研究院 Methanation catalyst for synthesizing substitute natural gas and preparation method thereof
CN104923225A (en) * 2014-03-18 2015-09-23 中国科学院大连化学物理研究所 Supported noble metal catalyst and preparation and application thereof
CN105618157A (en) * 2014-12-01 2016-06-01 中国科学院大连化学物理研究所 Composite oxide carrier with bimodal mesopores, as well as preparation method and application of composite oxide carrier
CN106311242A (en) * 2015-07-06 2017-01-11 中国石油化工股份有限公司 Carbon dioxide methanation catalyst and preparation method thereof
WO2017085593A2 (en) * 2015-11-16 2017-05-26 Sabic Global Technologies B.V. High temperature methods for hydrogenation of co2 to syngas for production of olefins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113649021A (en) * 2021-09-09 2021-11-16 濮阳圣恺环保新材料科技股份有限公司 Preparation method of copper hydrogenation catalyst
CN113649021B (en) * 2021-09-09 2023-12-01 濮阳圣恺环保新材料科技股份有限公司 Preparation method of copper hydrogenation catalyst

Also Published As

Publication number Publication date
CN112138654B (en) 2023-06-27

Similar Documents

Publication Publication Date Title
Kojima et al. Hydrogen generation by hydrolysis reaction of magnesium hydride.
CN103582522B (en) Sulphur trioxide decomposition catalyst and silicol process
CN116139867B (en) MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof
Jo et al. Coke-promoted Ni/CaO catal-sorbents in the production of cyclic CO and syngas
WO2012091168A1 (en) Catalyst for Decomposition of Sulfur Trioxide and Hydrogen Production Process
CN114272950A (en) CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof
Wang et al. Double adjustment of Ni and Co in CeO2/La2Ni2-xCoxO6 double perovskite type oxygen carriers for chemical looping steam methane reforming
CN112138654B (en) Catalyst for hydromethanation of carbon dioxide and application thereof
Gao et al. Modification strategies of heterogeneous catalysts for water–gas shift reactions
CN108328574B (en) Method for preparing hydrogen by phenol adsorption enhanced reforming
CN106423171B (en) A kind of Ni/Cu/M catalyst and preparation method thereof for catalysis methanol synthetic reaction
Singh et al. Hypes and hopes on the materials development strategies to produce ammonia at mild conditions
Natewong et al. Fibrous platelet carbon nanofibers-silica fiber composite supports for a Co-based catalyst in the steam reforming of acetic acid
CN113120859A (en) Water-vapor transformation reaction method and platinum catalyst with hybrid nano structure
Hu et al. Recyclable NiMnOx/NaF catalysts: Hydrogen generation via steam reforming of formaldehyde
CN111266113A (en) Oxygen carrier for chemical chain combustion and cracking and preparation method and application thereof
KR101487387B1 (en) Preparation Method of Metal Carbide Methane Reforming Catalyst and Methane Reforming Catalyst Prepared by the Method
CN106824201A (en) A kind of catalyst and preparation method for synthesizing gas by reforming methane with co 2
Sang et al. Preparation of ZnO/ASC by electrochemical deposition and evaluation of its desulphurisation performance
CN114177904B (en) Preparation method of Al-combined hydrothermal modified sepiolite group mineral supported Pt single-atom catalyst
Zhang et al. Recent progress and prospects in active anion-bearing C12A7-mediated chemical reactions
WO2021153738A1 (en) Ammonia synthesis catalyst
AU2022315453A1 (en) Steam reforming catalyst for heavy hydrocarbon feeds
CN117563617A (en) Preparation method and application of reverse water gas shift catalyst
WO2021152116A1 (en) Reforming catalyst

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