CN113522328A - Nano solid-phase catalyst for hydrogen production from formic acid and preparation method thereof - Google Patents

Nano solid-phase catalyst for hydrogen production from formic acid and preparation method thereof Download PDF

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CN113522328A
CN113522328A CN202010290458.0A CN202010290458A CN113522328A CN 113522328 A CN113522328 A CN 113522328A CN 202010290458 A CN202010290458 A CN 202010290458A CN 113522328 A CN113522328 A CN 113522328A
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catalyst
metal
carrier
hydrogen production
formic acid
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CN113522328B (en
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康鹏
汪秀萍
申晓楠
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Carbon Energy Technology Beijing Co ltd
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • B01J23/6482—Vanadium
    • B01J35/23—
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds

Abstract

The invention provides a nano solid-phase catalyst for hydrogen production by formic acid, which is supported nano RuxMyThe N-C catalyst comprises a carrier and a carrier. The general formula of the load is RuxMyThe load contains bimetal Ru and M, and the load is roasted to form nano alloy which is fixed on nitrogen and/or carbon sites (N-C)) The metal M is an oxophilic metal. The catalyst improves the dehydrogenation efficiency of the formic acid and reduces the generation of by-product CO. The invention also provides a preparation method of the catalyst, which takes a homogeneous metal organic complex as an impregnation liquid, and greatly improves the distribution uniformity of metal ruthenium and metal M in the catalyst. Meanwhile, nitrogen and carbon sites formed in the roasting process of the organic complex are used as metal fixing sites, so that the dispersity of metal and the specific surface area of the catalyst are improved, and the catalyst has high-efficiency hydrogen production activity.

Description

Nano solid-phase catalyst for hydrogen production from formic acid and preparation method thereof
Technical Field
The invention relates to the technical field of solid phase catalysts, in particular to a nanometer solid phase catalyst for hydrogen production by formic acid and a preparation method of the catalyst.
Background
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, poor stability, difficult control of conversion rate and the like are faced at present.
Ruthenium is being investigated as an element which is relatively frequently used in formic acid reforming catalysts to improve the performance thereof. Ruthenium-based formic acid reforming catalysts are mainly classified into two major classes, homogeneous catalysts and solid-phase catalysts. The phosphine-coordinated homogeneous ruthenium catalyst is one of reported catalysts capable of efficiently preparing high-purity hydrogen, and the homogeneous catalyst has a large contact area with formic acid, so that the conversion speed is high. However, the effective separation of the formic acid liquid phase system and the catalyst is difficult to realize, so that the conversion speed is difficult to control, and the requirement of quick start and stop cannot be realized. Compared with a homogeneous catalyst, the ruthenium-based heterogeneous catalyst has the greatest advantage of high stability, and can meet the hydrogen supply requirement of quick start and stop, so that the reformer is safer and more easily controlled, and the practicability is stronger. Meanwhile, compared with other noble metal catalysts such as nano palladium, nano iridium, nano palladium-gold alloy and the like, the ruthenium metal has obvious advantage in cost. However, the method has the defects of low hydrogen production speed of the catalyst per unit mass, high catalyst consumption for improving the hydrogen production amount and the like, and has the problem of high relative content of the byproduct CO, thereby limiting the application of the method. As in the literature (Ruthenium Clusters on Carbon Nanofibers for chemical Acid composition: Effect of Doping the Support with Nitrogen, ChemCat chem2015,7,2910-2917.), a Carbon nanofiber supported Ruthenium cluster catalyst was prepared with a Carbon monoxide selectivity as high as 8%. Meanwhile, in the aspect of performance evaluation of the catalyst, the evaluation basis mainly focuses on the hydrogen production efficiency under a short-time test, and the evaluation on the aspects of stability and the like is rarely reported.
Therefore, in order to overcome the defects of the ruthenium-based solid-phase catalyst, the overall performance of the ruthenium-based solid-phase catalyst needs to be improved from multiple aspects of optimizing the active composition, improving the dispersion degree and specific surface area of the active components, improving the stability of the active components and the like, so that the industrial process of the hydrogen production technology by formic acid reforming is accelerated.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nano solid-phase catalyst for hydrogen production from formic acid.
The second object of the present invention is to provide a method for preparing the above catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a nano solid-phase catalyst for hydrogen production by formic acid, which is a supported nano RuxMyA/N-C catalyst comprising a support and a carrier, the support being supported on the carrier, the support having the general formula RuxMyN-C, wherein 0<x<1，0<y is less than or equal to 0.5, the load contains bimetal Ru and M, the metal M carries out active modification on the metal ruthenium, and the nanometer Ru is formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites (N-C), and the metal M is an oxophilic metal selected from any one of Ti, V, Sc and W.
Preferably, the ratio of x to y is 1 (0.001-0.3).
Preferably, the sum of the mass of the metal ruthenium and the mass of the metal M accounts for RuxMy0.1 to 40 percent of the total mass of the/N-C, preferably 10 to 35 percent.
Preferably, theIn the catalyst, the RuxMyThe mass of the/N-C accounts for 0.05-50% of the total mass of the catalyst.
Preferably, the nitrogen and/or carbon sites (N-C) are derived from a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyridine, 4' -bipyridine, 2-bipyridine, 1, 10-orthophenanthrene.
Preferably, the carrier is at least one selected from carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomite and kaolin.
The invention also relates to a preparation method of the nano solid-phase catalyst for hydrogen production from formic acid, which comprises the following steps:
1) preparing a metal precursor solution: dissolving a compound containing a metal element in a solvent, adding a complex, and stirring until the complex is dissolved.
Preferably, the compounds containing the metal element are ruthenium-containing compounds and M-containing compounds, and the molar ratio of the metal element to the complex is 1 (1-5).
Preferably, the complex is a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 ″ -terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyridine, 1, 10-phenanthridine.
Preferably, the solvent is a mixed solvent containing water and an organic solvent.
Preferably, the organic solvent is selected from any one of alcohol, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and acetonitrile; the alcohol is at least one selected from methanol, ethanol, ethylene glycol, glycerol and butanediol.
Preferably, the volume ratio of the water to the organic solvent in the mixed solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) pickling and drying the carrier, roasting, and then cooling to room temperature for later use.
Preferably, the pickling is carried out with an acid solution selected from HNO3、HCl、H2SO4And at least one of HF, the concentration of the acid solution is 0.1-3mol/L, the acid washing time is 5-120min, and the roasting is carried out in the air atmosphere for 1-4 h.
3) Carrier impregnation: and under an inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying.
Preferably, the impregnation is carried out under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
4) Roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
Preferably, the acid washing is to soak the roasted carrier in acid liquor, stir and wash the carrier, then wash the carrier by deionized water until the carrier is neutral, and then dry the carrier;
preferably, the acid liquor is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid solution concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
preferably, the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
The invention has the beneficial effects that:
the invention provides a nano solid-phase catalyst for hydrogen production from formic acid, which comprises a load and a carrier, wherein the general formula of the load is RuxMythe/N-C, the load contains bimetal Ru and M, and the metal is fixed on nitrogen and/or carbon sites after roasting treatment. The oxophilic metal M is used for carrying out active modification on the metal Ru, and by means of the strong binding force of the oxophilic metal and the oxygen element in the formic acid, the dehydrogenation efficiency of the formic acid is improved, and the generation of a byproduct CO is reduced.
The invention also provides a preparation method of the catalyst, which takes a homogeneous metal organic complex as an impregnation liquid, and greatly improves the distribution uniformity of metal ruthenium and metal M in the catalyst. Meanwhile, nitrogen and carbon sites formed in the roasting process of the organic complex are used as metal fixing sites, so that the dispersity of metal and the specific surface area of the catalyst are improved, and the catalyst has high-efficiency hydrogen production activity. Meanwhile, the utilization rate of metal is improved, the dosage of the catalyst is reduced, and the preparation cost is effectively reduced.
In addition, the benzene heterocyclic organic ligand in the complex is cracked after being roasted in inert atmosphere and polymerized on the surface of the carrier, so that the surface immobilization of metal elements is stabilized, and the long-term stability of the catalyst is improved.
Drawings
FIG. 1 is a RuV carbon powder load0.1Transmission electron microscope picture of the/N-C catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
[ catalyst ]
The embodiment of the invention relates to a nano solid-phase catalyst for hydrogen production by formic acid, which is supported nano RuxMya/N-C catalyst. The catalyst can stably exist in the air for a long time, and keeps good activity and stability.
Specifically, the catalyst comprises a carrier and a support supported on the carrier. The general formula of the load is RuxMyN-C, wherein 0<x<1，0<y is less than or equal to 0.5, and the load contains bimetal Ru and M. Wherein, ruthenium metal is an active component, and the metal M carries out active modification on ruthenium. Nano-grade Ru formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites (N-C).
In the support, the metal M is an oxophilic metal and is selected from any one of Ti, V, Sc and W. The affinity between the metal and oxygen is stronger, and the formed oxide is more stable. The oxophilic metal has stronger binding force with oxygen element in formic acid, so that the dehydrogenation efficiency of the formic acid can be improved, and the generation of by-products CO is reduced.
x and y are relative molar amounts of Ru and M, and the ratio of x to y is preferably 1 (0.001-0.3).
In one embodiment of the present invention, the sum of the mass of the metal ruthenium and the metal M accounts for RuxMy0.1-40% of the total mass of the/N-C. That is, the total mass of the ruthenium metal and the M metal in the supported material is 0.1 to 40%, preferably 10 to 35% of the total mass of the supported material.
RuxMyThe mass of the catalyst is 0.05-50% of the total mass of the catalyst.
In one embodiment of the invention, the nitrogen and/or carbon sites (N-C) are derived from heterocyclic compounds containing a nitrogen heteroatom. The heterocyclic compound is selected from any one of bipyridine, bipyrimidine, dipyrrole, biimidazole, azaphenanthrene, azaindene and derivatives thereof, and is specifically selected from any one of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-dipyrrole and 1, 10-o-diazaphenanthryl.
In one embodiment of the present invention, the carrier is selected from at least one of carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomaceous earth, kaolin.
[ catalyst preparation ]
The invention also relates to a preparation method of the nano solid-phase catalyst for hydrogen production from formic acid, which comprises the following steps:
1) preparing a metal precursor solution: dissolving a compound containing a metal element in a solvent, adding a complex, and stirring until the complex is dissolved.
Further, the ruthenium-containing compound and the M-containing compound are dissolved in a solvent in a molar ratio of metal ruthenium to metal M.
In one embodiment of the present invention, the molar ratio of the metal element to the complex is 1 (1-5), and the metal is the sum of the metal ruthenium and the metal M.
In one embodiment of the present invention, the ruthenium-containing compound is a water-soluble salt of ruthenium, and may be selected from any one of chlorides, sulfates, nitrates, and acetates of ruthenium. The M-containing compound is a water-soluble salt of metal M, and can be selected from any one of chloride, sulfate, nitrate and acetate of M.
In one embodiment of the invention, the complex is a heterocyclic compound containing a nitrogen heteroatom, the heterocyclic compound being selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 ″ -terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyrrole, 1, 10-phenanthridine.
In one embodiment of the present invention, the solvent is a mixed solvent containing water and an organic solvent, and functions to allow the inorganic metal compound and the organic complex to be simultaneously dissolved to form a highly dispersed uniform phase.
In one embodiment of the present invention, the organic solvent is selected from any one of alcohol, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile; the alcohol is at least one selected from methanol, ethanol, ethylene glycol, glycerol and butanediol.
In one embodiment of the present invention, the volume ratio of water to the organic solvent in the mixed solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) pickling and drying the carrier, roasting, and then cooling to room temperature for later use.
In one embodiment of the invention, the pickling is carried out with an acid solution selected from HNO3、HCl、H2SO4At least one of HF, acid solution concentration of 0.1-3mol/L, acid washing time of 5-120min, roasting in air atmosphere at 300-700 deg.c for 1-4 hr.
3) Carrier impregnation: and under an inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying.
In one embodiment of the present invention, the impregnation is performed under an inert atmosphere, which is intended to isolate air and prevent the valence state change of ruthenium ions in the metallic ruthenium ion complex.
In one embodiment of the invention, the impregnation is carried out under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
4) Roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
In one embodiment of the invention, the impregnated carrier is roasted in an inert atmosphere and then is subjected to acid washing, so that metallorganics which are not completely decomposed in the roasting process and metal M which is separately formed in the roasting process can be removed, and then the nano solid-phase catalyst for hydrogen production by formic acid is obtained.
In one embodiment of the invention, the acid washing is to soak the calcined carrier in acid liquor, stir and wash the calcined carrier, then wash the calcined carrier with deionized water until the calcined carrier is neutral, and then dry the calcined carrier. The acid solution is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid liquor concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
in one embodiment of the present invention, the calcination temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
In one embodiment of the present invention, the catalyst is prepared by the following steps: 1) pretreatment of a catalyst carrier: pickling the carrier in 0.1-3mol/L nitric acid solution at room temperature for 5-120min, drying, roasting at the temperature of 300-700 ℃ in air atmosphere for 1-4h, and cooling to room temperature for later use. 2) Preparing and impregnating a metal precursor solution: weighing a ruthenium-containing compound and a M-containing compound according to the molar ratio of metal ruthenium to metal M, dissolving the ruthenium-containing compound and the M-containing compound in a mixed solvent containing water and an organic solvent, adding a complex, and stirring until the complex is dissolved. Adding the pretreated carrier, condensing and refluxing at 40-120 deg.C for 3-12h under the protection of inert atmosphere, and oven drying at 50-150 deg.C. 3) Roasting: roasting and acid washing the dried carrier in inert atmosphere to directly obtain the carrier-supported nano RuxMyThe catalyst can also be obtained by further acid washing after roasting.
The invention also relates to a hydrogen production method by formic acid, which adopts the nano solid-phase catalyst for hydrogen production by formic acid provided by the invention to decompose formic acid in a water phase system, thereby obtaining hydrogen.
Example 1
Ultrasonically soaking carbon powder in a nitric acid solution with the concentration of 0.5mol/L for 1h, repeatedly cleaning and drying the carbon powder by using deionized water, and roasting the carbon powder in a muffle furnace for 2h at the temperature of 400 ℃ under the air condition for later use. Then 0.45g of anhydrous ruthenium trichloride, 0.034g of vanadium trichloride and 1.12g of bipyridine are weighed according to the molar ratio of 1:0.1 of metal ruthenium to metal vanadium and the molar ratio of total metal to bipyridine is 1:3, and are stirred and dissolved in a mixed solvent consisting of 6ml of deionized water and 28ml of N, N-dimethylformamide. Adding 1g of treated carbon powder into the mixed solvent, condensing and refluxing for 5h under the protection of argon at 50 ℃, filtering out the carbon powder and drying at 70 ℃. Weighing 1.19g of the powder, placing the powder in a tubular furnace, introducing Ar gas for protection, roasting the powder at 550 ℃ for 2 hours, soaking the powder in 3mol/L formic acid solution, stirring the solution at 50 ℃ for 5 hours, filtering the solution, washing the solution with deionized water to be neutral, and drying the solution to obtain RuV loaded with 1.11g of carbon powder0.1and/N-C. FIG. 1 is a transmission electron microscope image of the substance, and it can be known that Ru and V in the catalyst prepared by the invention are both in nanometer level.
Prepared 1.11g of carbon powder loaded nanometer RuV0.1the/N-C catalyst is filled in a reactor, formic acid solution is prepared by using 85 mass percent of formic acid and potassium formate, wherein the molar ratio of the formic acid to the potassium formate is 3: 1. Adding 50ml of formic acid solution into a reaction kettle, controlling the reaction temperature to be 95 ℃, and after hydrogen production is started, continuously dropwise adding 85% formic acid to maintain the molar ratio of formic acid to potassium formate in the reaction kettle to be 3: 1. The generated mixed gas passes through an activated carbon adsorption column to remove formic acid vapor, passes through an alkali absorption tank to remove carbon dioxide, and then the hydrogen production rate is measured by a drainage method. Detection of H by gas chromatography2Volume fraction of CO by-product in the gas volume.
Table 1 shows the performance of the catalyst for producing hydrogen for 48 hours. Wherein the hydrogen production rate is RuV0.1Calculated as hydrogen production per mass of metal in the N-C catalyst, the percentage by volume of CO is calculated as CO in H2And the volume fraction of the total gas volume of CO. As can be seen from Table 1, the percentage by volume of CO is low within 1h of start-up and rises slowly with timeThen, the concentration is maintained below 0.0034%, and the hydrogen production rate is maintained at about 0.25 ml/min/mg.
TABLE 1 carbon powder loaded RuV0.1Performance of N-C catalyst for preparing hydrogen for 48h
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.254 0.0014
5 0.248 0.0021
12 0.252 0.0034
24 0.247 0.0031
36 0.251 0.0029
48 0.252 0.0031
Comparative example 1
0.45g of anhydrous ruthenium trichloride and 1.02g of bipyridine are weighed according to the molar ratio of the metal ruthenium to the bipyridine of 1:3, and are stirred and dissolved in a mixed solvent consisting of 6ml of deionized water and 28ml of N, N-dimethylformamide. 1.06g of a Ru/N-C catalyst supported on carbon powder was obtained in the same manner as in example 1 by adding 1g of carbon powder pretreated in the same manner as in example 1.
The catalyst was filled in a reactor, and hydrogen gas was produced by the same operation and hydrogen production conditions as in example 1. Table 2 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production speed fluctuates about 0.14 ml/min-mg in 48 hours, and the volume percentage content of the impurity CO is up to 0.05%.
TABLE 2 carbon powder loaded Ru/N-C catalyst hydrogen production time 48h performance
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.14 0.053
5 0.142 0.049
12 0.145 0.05
24 0.138 0.041
36 0.143 0.048
48 0.137 0.044
Example 2
0.45g of anhydrous ruthenium trichloride, 0.06g of titanium tetrachloride and 1.06g of bipyridine are weighed respectively according to the molar ratio of the metal ruthenium to the metal titanium of 1:0.15 and the molar ratio of the total metal to the bipyridine of 1:3, and are stirred and dissolved in a mixed solvent consisting of 4ml of deionized water and 30ml of N, N-dimethylformamide. Adding 1g of carbon powder pretreated according to the method of the embodiment 1, condensing and refluxing for 8 hours under the protection of argon at 50 ℃, filtering out the carbon powder and drying. Weighing 1.23g of RuTi, placing in a tube furnace, introducing Ar gas for protection, and roasting at 500 deg.C for 2h to obtain 1.16g of carbon powder loaded RuTi0.15a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 3 shows that the catalyst has the performance of producing hydrogen for 48h, the hydrogen production speed is more than 0.22 ml/min. mg within 48h, the hydrogen production speed is relatively stable, and the volume percentage content of impurity CO is less than 0.0051%.
TABLE 3 carbon powder loaded RuTi0.15The hydrogen production time of the N-C catalyst is 48h
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.22 0.0041
5 0.21 0.0051
12 0.227 0.0043
24 0.236 0.0041
36 0.225 0.0049
48 0.217 0.0044
Example 3
According to the molar ratio of metal ruthenium to metal vanadium of 1:0.3 and the molar ratio of total metal to bipyridine of 1:3, 0.45g of anhydrous ruthenium trichloride, 0.1g of vanadium trichloride and 1.31g of bipyridine are respectively weighed, stirred and dissolved in a mixed solvent consisting of 4ml of deionized water and 30ml of N, N-dimethylformamide, 1g of carbon powder pretreated according to the method in the embodiment 1 is added, and the carbon powder is filtered after condensation and reflux are carried out for 5 hours under the protection of argon gas at the temperature of 50 ℃.Weighing 1.24g after drying, placing the powder in a tube furnace, introducing Ar gas for protection, roasting the powder for 2 hours at 550 ℃, then carrying out acid cleaning on the roasted carbon powder according to the method in the embodiment 1, and drying the powder to obtain RuV loaded by 1.2g of carbon powder0.3a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 4 shows the performance of the catalyst for preparing hydrogen for 48 hours, the hydrogen production speed is maintained to be more than 0.18ml/min & mg, and the CO content is reduced to be less than 0.0021 percent.
TABLE 4 carbon powder loading RuV0.3Performance of N-C catalyst for preparing hydrogen for 48h
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.176 0.0024
5 0.184 0.0021
12 0.186 0.0024
24 0.181 0.0026
36 0.179 0.0023
48 0.182 0.0021
Example 4
A metal precursor solution was prepared according to the method of example 1, wherein phenanthroline was used as a complex, and the molar ratio of the total metal to phenanthroline was 1: 3. 1g of carbon powder pretreated according to the method of example 1 was added thereto, and then, the mixture was condensed and refluxed for 4 hours under the protection of argon gas at 50 ℃ and the carbon powder was filtered out. Weighing 1.36g, placing in a tube furnace, introducing Ar gas for protection, and calcining at 650 deg.C for 2h to obtain 1.25g of RuTi loaded with carbon powder0.05a/N-C catalyst.
The catalyst was filled in a quartz tube reactor, and hydrogen was produced by the same operation and hydrogen production conditions as in example 1. Table 5 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production speed is maintained to be more than 0.22 ml/min. mg, and the CO content is as low as 0.0071%.
TABLE 5 carbon powder loaded RuT0.05Performance of N-C catalyst for preparing hydrogen for 48h
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.226 0.0071
5 0.224 0.0073
12 0.221 0.0074
24 0.223 0.0079
36 0.219 0.0081
48 0.22 0.008
Example 5
According to the molar ratio of metal ruthenium to metal scandium of 1:0.1 and the molar ratio of total metal to bipyridine of 1:3, 0.45g of anhydrous ruthenium trichloride, 0.056g of scandium trichloride hexahydrate and 1.12g of bipyridine are respectively weighed, stirred and dissolved in a mixed solvent consisting of 5ml of deionized water and 20ml of nitrogen-methyl pyrrolidone, 1g of carbon powder pretreated according to the method of example 1 is added, the mixture is condensed and refluxed for 5 hours under the protection of argon gas at 50 ℃, the carbon powder is filtered out, and the dried mixture is weighed to have the mass of 1.46 g. Then placing the mixture in a tube furnace, introducing Ar gas for protection, and roasting the mixture for 2 hours at the temperature of 600 ℃ to obtain 1.32g of RuSc loaded by carbon powder0.1a/N-C catalyst.
The catalyst was filled in a reactor, and hydrogen gas was produced by the same operation and hydrogen production conditions as in example 1. Table 6 shows the performance of the catalyst for producing hydrogen for 48 hours, the hydrogen production rate is maintained to be more than 0.4 ml/min. mg, and the CO content is as low as 0.01 percent.
TABLE 6 RuSc carbon powder Loading0.1Performance of N-C catalyst for preparing hydrogen for 48h
Time/h Hydrogen production rate/ml/min mg Content of CO/%)
1 0.436 0.011
5 0.424 0.013
12 0.415 0.010
24 0.417 0.009
36 0.390 0.011
48 0.40 0.008
The above examples and test results show that the nano solid-phase catalyst for hydrogen production from formic acid can efficiently catalyze the decomposition of formic acid to generate hydrogen and carbon dioxide under the conditions of low temperature, normal pressure and water phase. Due to the presence of the bimetallic in the catalyst, a gas mixture was obtained with a CO content of < 0.015%. While comparative example 1 does not use oxophilic metals, the CO content in the hydrogen production product is > 0.04%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. The nanometer solid-phase catalyst for hydrogen production from formic acid is characterized in that the catalyst is supported nanometer RuxMyan/N-C catalyst comprising a support and a carrier, the support being supported on the carrier,
the general formula of the load is RuxMyN-C, wherein 0<x<1，0<y is less than or equal to 0.5, the load contains bimetal Ru and M, the metal M carries out active modification on the metal ruthenium, and the nanometer Ru is formed after roasting treatmentxMyThe alloy is fixed on nitrogen and/or carbon sites;
the metal M is an oxophilic metal and is selected from any one of Ti, V, Sc and W.
2. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the ratio of x to y is 1 (0.001-0.3).
3. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the sum of the mass of metal ruthenium and metal M is RuxMy0.1 to 40 percent of the total mass of the/N-C, preferably 10 to 35 percent.
4. According toThe nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the Ru is contained in the catalystxMyThe mass of the/N-C accounts for 0.05-50% of the total mass of the catalyst.
5. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the nitrogen and/or carbon site N-C is derived from a heterocyclic compound containing nitrogen heteroatom, and the heterocyclic compound is selected from any one of 2,2 '-bipyridine, 4' -bipyridine, 2':6',2 "-terpyridine, 2 '-bipyridine, 4' -bipyridine, 2-bipyridine, and 1, 10-phenanthridine.
6. The nano solid-phase catalyst for hydrogen production from formic acid as defined in claim 1, wherein the carrier is at least one selected from carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomaceous earth, and kaolin.
7. The preparation method of the nano solid-phase catalyst for hydrogen production from formic acid as defined in any one of claims 1 to 6, comprising the steps of:
1) preparing a metal precursor solution: dissolving a compound containing metal elements in a solvent, adding a complex, and stirring until the complex is dissolved;
2) pretreatment of the carrier: pickling and drying the carrier, roasting, and then cooling to room temperature for later use;
3) carrier impregnation: under inert atmosphere, putting the pretreated carrier into a metal precursor solution for dipping, and then drying;
4) roasting and acid washing: roasting the impregnated carrier in an inert atmosphere, and then carrying out acid washing to obtain the nano solid-phase catalyst for hydrogen production by formic acid.
8. The preparation method according to claim 6, wherein in the step 1), the molar ratio of the metal element to the complex is 1 (1-5);
and/or the complex is a heterocyclic compound containing nitrogen heteroatom, the heterocyclic compound is selected from any one of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyridine, 4' -bipyridine, 2-dipyrrole and 1, 10-o-diazaphenanthryl;
and/or the solvent is a mixed solvent containing water and an organic solvent, and the volume ratio of the water to the organic solvent in the mixed solvent is 1 (1-50).
9. The preparation method according to claim 6, wherein in the step 3), the impregnation is performed under reflux conditions, the temperature of condensation reflux is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
10. The preparation method according to claim 6, wherein in the step 4), the acid washing is to soak the roasted carrier in acid liquor, stir and wash the carrier, then wash the carrier with deionized water to be neutral, and then dry the carrier;
and/or the acid liquor is selected from HNO3、HCl、H2SO4At least one of HF and HCOOH, wherein the acid solution concentration is 0.05-20mol/L, the acid pickling temperature is 10-90 ℃, and the acid pickling time is 0.5-10 h;
and/or the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
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