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CN114832812A - Method for preparing hydrogen catalyst from graphene-Ru formic acid - Google Patents

Method for preparing hydrogen catalyst from graphene-Ru formic acid Download PDF

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CN114832812A
CN114832812A CN202210504473.XA CN202210504473A CN114832812A CN 114832812 A CN114832812 A CN 114832812A CN 202210504473 A CN202210504473 A CN 202210504473A CN 114832812 A CN114832812 A CN 114832812A
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graphene
formic acid
solution
suspension
catalyst
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孙涛
万博识
张建雄
孙艳
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Beijing Huapu Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46Ruthenium, rhodium, osmium or iridium
    • B01J23/462Ruthenium
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015Organic compounds; Solutions thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a method for preparing a catalyst for hydrogen production by graphene-Ru formic acid, which comprises the following steps; firstly, dissolving 5-20g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 10-20ml of 98% formic acid, and fully stirring; secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate; thirdly, performing 3-5 times on the precipitate obtained in the second step to obtain a Ru + solution; fourthly, dissolving 1-5g of nano-scale water-soluble graphene in 100ml of water, adding 0.5-2g of dispersing agent, and dispersing under an ultrasonic disperser; and fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 4-6 hours by ultrasonic waves to prepare a suspension A for later use.

Description

Method for preparing hydrogen catalyst from graphene-Ru formic acid
Technical Field
The invention relates to the technical field of hydrogen production by formic acid, in particular to a method for preparing a graphene-Ru hydrogen production by formic acid.
Background
An increase in energy consumption is a necessary trend. With the exhaustion of fossil energy, the search for new alternative energy is more urgent. Hydrogen, although a clean energy source, produces only water when combusted in a fuel cell, releasing a large amount of energy. However, the problems of safety, economy and storage controllability of hydrogen gas are still to be solved. In the related art, chemical hydrogen storage materials have received a relatively wide attention, including formic acid.
Formic acid is a promising hydrogen storage tank, has the advantages of no toxicity and convenient transportation and storage, is a safe medium for retaining hydrogen, and is very efficient to use because hydrogen generated by formic acid can be stored by catalysis. In addition, formic acid is widely found in nature and is a major byproduct of certain refining processes (e.g., oil refining and biomass conversion), while it can also be produced from sugars and their related polymers by decomposition into smaller molecules.
At present, the preparation process of a plurality of catalysts with excellent activity for producing hydrogen by formic acid is relatively complicated. For example, the preparation of the catalyst carrier needs to be carried out under the protection of nitrogen or even argon, the preparation temperature also needs to be 700-1000 ℃, and the defect of high preparation temperature exists.
Formic acid is one of organic liquid media capable of producing hydrogen under the conditions of normal temperature and normal pressure, and has the good properties of low toxicity, low harm, nonflammability and the like, so that the formic acid becomes an excellent hydrogen energy carrier and can meet the requirements of people on mobile hydrogen storage. Under the circumstance that automobile energy development begins to advance to hydrogen fuel cell technology, the hydrogen production technology by formic acid reforming has been greatly improved in recent years, but the overall performance of the hydrogen production reactor does not meet the requirement of large-scale commercial application. One of the limiting factors is that the performance of the formic acid reforming catalyst is still in the technical critical stage, and the main problems of low catalytic efficiency, serious catalyst consumption, poor stability, difficult control of conversion rate and the like are faced at present.
Therefore, the research on the hydrogen production by formic acid becomes particularly important, the formic acid is simple and easy to obtain and is a catalyst which is not consumed, the most key technology in the industry field is that the formic acid is used as a hydrogen carrier, and the method has practical significance, combines the hydrogen production by formic acid with waste energy under the influence of large environment, and provides a new idea for energy conservation and carbon reduction of the country with the field of new energy.
Disclosure of Invention
The invention provides a method for preparing a hydrogen production catalyst from graphene-Ru formic acid, aiming at making up for the defects of the prior art, wherein the formic acid is liquid during feeding, has a good compression energy consumption ratio, and has the conditions of subsequent pressurization and purification.
The invention aims to provide a method for preparing a catalyst for hydrogen production from graphene-Ru formic acid, which comprises the following steps;
firstly, dissolving 5-20g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 10-20ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3-5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 1-5g of nano-scale water-soluble graphene in 100ml of water, adding 0.5-2g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 4-6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.05-0.5g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 6000-;
and step eight, placing the suspension C in the step seven into a three-hole flask, heating to 110-150 ℃, and continuously adding the formic acid solution, wherein the solution becomes wine red liquid after about 3-4 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is finished.
A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 15g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 15.5ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 2g of nano-scale water-soluble graphene in 100ml of water, adding 0.8g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 5 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.2g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 8000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 120 ℃, continuously adding a formic acid solution, wherein the solution is changed into wine red liquid in about 3 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is completed.
A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 16g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 13ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 3g of nano-scale water-soluble graphene in 100ml of water, adding 1g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.3g of wetting auxiliary agent, and fully stirring for 1H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 7500r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 110 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
Further, the dispersant is a BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
Further, the ratio of the BYK dispersant to the graphene is 0.45:1 or 0.5: 1.
Furthermore, the wetting auxiliary agent is added with pine tar in an amount of 0.05-0.5 g.
Furthermore, the adhesion auxiliary agent is guar gum, and Ru + and the graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
Further, the ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The application of the graphene-Ru hydrogen production catalyst from formic acid comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 105 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produces 30L-40L H2+ co2 mixed gas per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
And sixthly, amplifying in the same proportion to meet the requirement of a high-temperature fuel cell with higher power.
The application of the graphene-Ru hydrogen production catalyst from formic acid comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 101.2 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produced 35L H2+ co2 of air mixture per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
Compared with the prior art, the invention has the beneficial effects that: formic acid is used as a liquid hydrogen carrier, has the advantages of good transportation, easy hydrogen release, high risk predictability, no toxicity and no harm, and simultaneously needs to be gasified (such as methanol) with other hydrogen-containing carriers or is different from a gaseous state, the formic acid is liquid during feeding, has good compression energy consumption ratio and subsequent pressurizing and purifying conditions, and the graphene has the advantages of large specific surface area, strong dispersibility, good ductility, good conductivity and the like; ru ions greatly help the normal-temperature decomposition of formic acid, and Ru + and graphene are tightly combined in a certain mode and have the common characteristics of the Ru ions and the graphene, so that a catalyst with large reaction surface area and no consumption is achieved;
the preparation of the formic acid can be obtained in multiple ways, particularly, the formic acid with low cost is prepared from waste high-temperature waste heat, waste carbon dioxide and waste carbon powder (waste coal powder obtained by coking and screening) of a steel mill, and is a model for recycling waste industrial energy. Meanwhile, the formic acid is generated by electrolytic hydration and carbon dioxide, and the method has practical significance and economic benefit under the condition of price adjustment of specific waste wind and light electricity and is a green novel energy source;
the hydrogen production by formic acid has low energy consumption, carbon dioxide can be captured in the process of preparing formic acid, and hydrogen is not used for producing formic acid, so that a plurality of high energy consumption processes of firstly producing hydrogen, then synthesizing a hydrogen carrier and then releasing the hydrogen carrier are avoided;
the hydrogen production by formic acid can well combine waste energy sources, and provides a new idea for energy conservation and carbon reduction of the country with the field of new energy sources.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 5-20g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 10-20ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3-5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 1-5g of nano-scale water-soluble graphene in 100ml of water, adding 0.5-2g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 4-6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.05-0.5g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 6000-;
and step eight, placing the suspension C in the step seven into a three-hole flask, heating to 110-150 ℃, and continuously adding the formic acid solution, wherein the solution becomes wine red liquid after about 3-4 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is finished.
A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 15g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 15.5ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 2g of nano-scale water-soluble graphene in 100ml of water, adding 0.8g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 5 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.2g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 8000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 120 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 16g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 13ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 3g of nano-scale water-soluble graphene in 100ml of water, adding 1g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.3g of wetting auxiliary agent, and fully stirring for 1H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 7500r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 110 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
According to a further preferable embodiment of the invention, the dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
A further preferred embodiment of the present invention is that the BYK dispersant to graphene ratio is 0.45:1 or 0.5: 1.
A further preferred embodiment of the invention is that the wetting aid is pine tar added in an amount of 0.05-0.5 g.
In a further preferred embodiment of the present invention, the adhesion aid is guar gum, and the adhesion aid promotes the Ru + to be tightly combined with the graphene particles to form Ru-graphene stably adhered to the surface of the carrier graphene particles.
A further preferred embodiment of the invention is where the ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The application of the graphene-Ru hydrogen production catalyst from formic acid comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 105 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produces 30L-40L H2+ co2 mixed gas per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
And sixthly, amplifying in the same proportion to meet the requirement of a high-temperature fuel cell with higher power.
The application of the graphene-Ru hydrogen production catalyst from formic acid comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 101.2 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produced 35L H2+ co2 of air mixture per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
The first embodiment is as follows:
a method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 15g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 15.5ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 2g of nano-scale water-soluble graphene in 100ml of water, adding 0.8g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 5 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.2g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 8000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 120 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
According to a further preferable embodiment of the invention, the dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
The ratio of the BYK dispersing agent to the graphene is 0.45:1 or 0.5: 1.
The wetting auxiliary agent is added with pine tar, and the adding amount is 0.05-0.5 g.
The adhesion auxiliary agent is guar gum, and Ru + and graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
The ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The second embodiment is as follows:
a method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, dissolving 12g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 10ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 1g of nano-scale water-soluble graphene in 100ml of water, adding 0.5g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 4 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.05g of wetting auxiliary agent, and fully stirring for 30min to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 6000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 110 ℃, continuously adding a formic acid solution, wherein the solution is changed into a wine red liquid after about 3-4 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is finished.
The dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
The ratio of the BYK dispersing agent to the graphene is 0.45:1 or 0.5: 1.
The wetting auxiliary agent is added with pine tar, and the adding amount is 0.05-0.5 g.
The adhesion auxiliary agent is guar gum, and Ru + and graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
The ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The third concrete embodiment:
a method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, 18g of nanoscale Rucl3 or ruthenium acetate is dissolved in 150ml of deionized water, 20ml of 98 percent formic acid is added, and the mixture is fully stirred;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 5g of nano-scale water-soluble graphene in 100ml of water, adding 2g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.5g of wetting auxiliary agent, and fully stirring for 2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at a rotating speed of 8000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 150 ℃, continuously adding formic acid solution, wherein the solution is changed into wine red liquid in about 4 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is completed.
The dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
The ratio of the BYK dispersing agent to the graphene is 0.45:1 or 0.5: 1.
The wetting auxiliary agent is added with pine tar, and the adding amount is 0.05-0.5 g.
The adhesion auxiliary agent is guar gum, and Ru + and graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
The ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The fourth concrete embodiment:
a method for preparing a catalyst for hydrogen production from graphene-Ru formic acid comprises the following steps;
firstly, 20g of nanoscale Rucl3 or ruthenium acetate is dissolved in 150ml of deionized water, 20ml of 98 percent formic acid is added, and the mixture is fully stirred;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 5g of nano-scale water-soluble graphene in 100ml of water, adding 2g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.4g of wetting auxiliary agent, and fully stirring for 1.5H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 6000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 120 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3-4 hours.
According to a further preferable embodiment of the invention, the dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
The ratio of the BYK dispersing agent to the graphene is 0.45:1 or 0.5: 1.
The wetting auxiliary agent is added with pine tar, and the adding amount is 0.05-0.5 g.
The adhesion auxiliary agent is guar gum, and Ru + and graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
The ultrasonic disperser time is greater than 4 hours and less than 24 hours.
The fifth concrete example:
the application of the graphene-Ru hydrogen production formic acid catalyst comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 101.2 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produced 35L H2+ co2 of air mixture per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
The sixth specific embodiment:
the application of the graphene-Ru hydrogen production catalyst from formic acid comprises the following steps;
in the first step, 3L of catalyst was charged into a reactor having a pressure resistance of 15 MPa.
In the second step, the mixture was heated to 103 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step produced 40L H2+ co2 gas mixtures per minute.
And fourthly, through twice condensation, CO2 is changed into liquid to be removed, and the purity of the residual H2 is about > 95%, so that the use of a 3KW high-temperature fuel cell is completely met.
And fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A method for preparing a catalyst for hydrogen production from graphene-Ru formic acid is characterized by comprising the following steps;
firstly, dissolving 5-20g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 10-20ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3-5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 1-5g of nano-scale water-soluble graphene in 100ml of water, adding 0.5-2g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 4-6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.05-0.5g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 6000-;
and step eight, placing the suspension C in the step seven into a three-hole flask, heating to 110-150 ℃, and continuously adding the formic acid solution, wherein the solution becomes wine red liquid after about 3-4 hours, and the preparation of the homogeneous formic acid hydrogen production catalyst is finished.
2. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 1, which is characterized in that: comprises the following steps;
firstly, dissolving 15g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 15.5ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 3 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 2g of nano-scale water-soluble graphene in 100ml of water, adding 0.8g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 5 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.2g of wetting auxiliary agent, and fully stirring for 30min-2H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 8000r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 120 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
3. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 1, which is characterized in that: comprises the following steps;
firstly, dissolving 16g of nanoscale Rucl3 or ruthenium acetate in 150ml of deionized water, adding 13ml of 98% formic acid, and fully stirring;
secondly, adding 0.1mol/L silver nitrate solution into the mixed solution in the first step, standing overnight to form Agcl precipitate;
thirdly, performing 5 times on the precipitate obtained in the second step to obtain a Ru + solution;
fourthly, dissolving 3g of nano-scale water-soluble graphene in 100ml of water, adding 1g of dispersing agent, and dispersing under an ultrasonic disperser;
fifthly, adding the stirred Ru + solution into the dispersed graphene solution, and continuing dispersing for 6 hours by ultrasonic waves to prepare a suspension A for later use;
sixthly, preparing 50ml of water, adding 0.2g of adhesion auxiliary agent and 0.3g of wetting auxiliary agent, and fully stirring for 1H to prepare suspension B for later use;
seventhly, adding the suspension A-Ru-graphene solution stirred in the fifth step into the suspension B, and fully stirring at the rotating speed of 7500r/min under the action of a high-speed dispersion machine to prepare a suspension C;
and eighthly, placing the suspension C in the seventh step into a three-hole flask, heating to 110 ℃, continuously adding a formic acid solution, and completing the preparation of the homogeneous formic acid hydrogen production catalyst when the solution is changed into a wine red liquid in about 3 hours.
4. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 1, which is characterized in that: the dispersant is BYK dispersant, and the ratio of the BYK dispersant to the graphene is 0.4-0.5: 1.
5. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 4, wherein the method comprises the following steps: the ratio of the BYK dispersing agent to the graphene is 0.45:1 or 0.5: 1.
6. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 4, wherein the method comprises the following steps: the wetting auxiliary agent is added with pine tar, and the adding amount is 0.05-0.5 g.
7. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 4, wherein the method comprises the following steps: the adhesion auxiliary agent is guar gum, and Ru + and graphene particles are enabled to be tightly combined through the adhesion auxiliary agent to form Ru-graphene which is stably adhered to the surfaces of the carrier graphene particles.
8. The method for preparing the catalyst for hydrogen production from graphene-Ru formic acid according to claim 4, wherein the method comprises the following steps: the ultrasonic disperser time is greater than 4 hours and less than 24 hours.
9. The application of the graphene-Ru hydrogen formate-producing catalyst according to any one of claims 1-8, wherein the catalyst is characterized in that: comprises the following steps;
firstly, adding 3L of catalyst into a reactor with the pressure resistance of 15 Mpa;
in the second step, the mixture was heated to 105 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step is to generate 30L-40L H2+ co2 mixed gas per minute;
fourthly, through twice condensation, CO2 is changed into liquid to be removed, the purity of the residual H2 is about more than 95 percent, and the use of a 3KW high-temperature fuel cell is completely met;
and fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the generated power as a standby power supply or a mobile power supply station.
And sixthly, amplifying in the same proportion to meet the requirement of a high-temperature fuel cell with higher power.
10. The application of the graphene-Ru hydrogen formate production catalyst according to claim 9 is characterized in that: comprises the following steps;
firstly, adding 3L of catalyst into a reactor with the pressure resistance of 15 Mpa;
in the second step, the mixture was heated to 101.2 ℃ and 94% formic acid was added at a rate of 18 ml/min.
The third step generates 35L H2+ co2 mixed gas every minute;
fourthly, through twice condensation, CO2 is changed into liquid to be removed, the purity of the residual H2 is about more than 95 percent, and the use of a 3KW high-temperature fuel cell is completely met;
and fifthly, generating power by the purified hydrogen through a high-temperature fuel cell, and using the power as a standby power supply or a mobile power supply station.
CN202210504473.XA 2022-05-10 2022-05-10 Method for preparing hydrogen catalyst from graphene-Ru formic acid Pending CN114832812A (en)

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