CN113522328B - Nanometer solid phase catalyst for producing hydrogen from formic acid and preparation method thereof - Google Patents

Nanometer solid phase catalyst for producing hydrogen from formic acid and preparation method thereof Download PDF

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CN113522328B
CN113522328B CN202010290458.0A CN202010290458A CN113522328B CN 113522328 B CN113522328 B CN 113522328B CN 202010290458 A CN202010290458 A CN 202010290458A CN 113522328 B CN113522328 B CN 113522328B
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formic acid
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CN113522328A (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 preparing hydrogen from formic acid, which is supported nano Ru x M y N-C catalysts comprise a support and a carrier. The general formula of the load is Ru x M y and/N-C, wherein the load contains bimetallic Ru and M, nano alloy is formed by roasting treatment and is fixed on nitrogen and/or carbon sites (N-C), and the metal M is an aerophilic metal. The catalyst improves the dehydrogenation efficiency of formic acid and reduces the generation of byproduct CO. The invention also provides a preparation method of the catalyst, which takes the homogeneous metal organic complex as the impregnating solution, thereby greatly improving the distribution uniformity of the metal ruthenium and the 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

Nanometer solid phase catalyst for producing hydrogen from formic acid and preparation method thereof
Technical Field
The invention relates to the technical field of solid phase catalysts, in particular to a nano solid phase catalyst for hydrogen production from formic acid and a preparation method of the catalyst.
Background
Formic acid is one of organic liquid mediums capable of producing hydrogen under 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. In the large environment where the development of automobile energy starts to advance to hydrogen fuel cell technology, the technology of producing hydrogen by reforming formic acid has been greatly advanced in recent years, but the overall performance of the hydrogen production reactor has not yet reached the requirements 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 attack stage, and the main problems of lower catalytic efficiency, poor stability, difficult control of conversion speed and the like are faced at present.
Ruthenium is an element used in relatively large amounts in formic acid reforming catalysts, and research for improving the performance thereof has been under investigation. Ruthenium-based formic acid reforming catalysts are largely divided into two broad categories, homogeneous catalysts and solid phase catalysts. The phosphine coordinated homogeneous ruthenium catalyst is one of the reported catalysts capable of efficiently preparing high-purity hydrogen, and the contact area of the homogeneous catalyst and formic acid is large, 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 met. Compared with a homogeneous catalyst, the ruthenium-based heterogeneous catalyst has the greatest advantages of high stability, and can meet the hydrogen supply requirement of quick start and stop, so that the reformer is safer, easy to control and higher in practicability. Meanwhile, ruthenium metal has obvious advantages in cost compared with other noble metal catalysts such as nano palladium, nano iridium, nano palladium-gold alloy and the like. However, besides the defects of low hydrogen production rate of catalyst per unit mass, high catalyst consumption for improving hydrogen production, the method has the problem of relatively high content of byproduct CO, so that the application of the method is limited. As in literature (Ruthenium Clusters on Carbon Nanofibers for Formic Acid Decomposition: effect of Doping the Support with Nitrogen, chemCatChem2015,7, 2910-2917.), the carbon nanofiber-supported ruthenium cluster catalyst prepared has a carbon monoxide selectivity of up to 8%. Meanwhile, in the aspect of performance evaluation of the catalyst, the evaluation is based on hydrogen production efficiency mainly concentrated on short-time test, but the evaluation on 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 in multiple aspects of optimizing the active composition, improving the dispersity and specific surface area of the active components, improving the stability of the active components and the like, so that the industrialization process of the formic acid reforming hydrogen production technology is accelerated.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the invention is to provide a nano solid phase catalyst for hydrogen production from formic acid.
A second object of the present invention is to provide a process for preparing the above catalyst.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention relates to a nano solid phase catalyst for preparing hydrogen from formic acid, which is supported nano Ru x M y A N-C catalyst comprising a support and a carrier, wherein the support is supported on the carrier and the support has the general formula Ru x M y N-C, wherein 0<x<1，0<y is less than or equal to 0.5, the load contains bimetallic Ru and M, the metal M carries out active modification on the metal Ru, and nano Ru is formed after roasting treatment x M y The alloy is fixed on nitrogen and/or carbon sites (N-C), and the metal M is an oxygen-philic metal and is selected from any one of Ti, V, sc, 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 Ru x M y 0.1-40%, preferably 10-35% of the total mass of N-C.
Preferably, in the catalyst, the Ru x M y The mass of the N-C accounts for 0.05 to 50 percent of the total mass of the catalyst.
Preferably, the nitrogen and/or carbon sites (N-C) are derived from a heterocyclic compound containing an nitrogen heteroatom, said heterocyclic compound being selected from the group consisting of 2,2' -bipyridine, 4' -bipyridine, 2': any one of 6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-bipyrrole, 1, 10-o-diaza-fiveline.
Preferably, the carrier is at least one selected from carbon powder, activated carbon particles, carbon felt, porous ceramics, diatomite and kaolin.
The invention also relates to a preparation method of the nanometer solid phase catalyst for hydrogen production by formic acid, which comprises the following steps:
1) Preparing a metal precursor solution: the compound containing the metal element is dissolved in the solvent, and then the complex is added and stirred until the compound is dissolved.
Preferably, the compound containing the metal element is a ruthenium-containing compound and an M-containing compound, and the molar ratio of the metal element to the complex is 1 (1-5).
Preferably, the complex is a heterocyclic compound containing an nitrogen heteroatom selected from the group consisting of 2,2' -bipyridine, 4' -bipyridine, 2': any one of 6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-bipyrrole, 1, 10-o-diaza-fiveline.
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-methyl pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and acetonitrile; the alcohol is at least one selected from methanol, ethanol, ethylene glycol, glycerol and butanediol.
Preferably, in the mixed solvent, the volume ratio of water to the organic solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) acid washing, drying and roasting the carrier, and then cooling to room temperature for standby.
Preferably, the acid washing is performed with an acid solution selected from HNO 3 、HCl、H 2 SO 4 At least one of HF, acid liquor concentration is 0.1-3mol/L, acid washing time is 5-120min, roasting is carried out in air atmosphere, and roasting time is 1-4h.
3) And (3) carrier impregnation: the pretreated carrier is immersed in a metal precursor solution under an inert atmosphere, and then dried.
Preferably, the soaking is carried out under reflux conditions, the temperature of condensing 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 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 clean the carrier, then clean the carrier with deionized water to be neutral and dry the carrier;
preferably, the acid solution is selected from HNO 3 、HCl、H 2 SO 4 At least one of HF and HCOOH, wherein the concentration of the acid liquor is 0.05-20mol/L, the pickling temperature is 10-90 ℃, and the pickling time is 0.5-10h;
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 nanometer solid phase catalyst for preparing hydrogen from formic acid, which comprises a carrier and a carrier, wherein the general formula of the carrier is Ru x M y N-C, the support contains bimetallic Ru and M, the metal being immobilized on nitrogen and/or carbon sites after calcination treatment. The oxygen-philic metal M carries out active modification on the metal Ru, and by means of strong binding force between the oxygen-philic metal and oxygen element in 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 the homogeneous metal organic complex as the impregnating solution, thereby greatly improving the distribution uniformity of the metal ruthenium and the 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 catalyst consumption is reduced, and the preparation cost is effectively reduced.
In addition, the benzene heterocyclic organic ligand in the complex is cracked after roasting 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 shows a carbon powder loaded RuV 0.1 N-C catalyst transmission electron microscopy.
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 will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
[ catalyst ]
The embodiment of the invention relates to a nano solid phase catalyst for preparing hydrogen from formic acid, which is supported nano Ru x M y N-C catalyst. The catalyst can exist stably in the air for a long time and maintain good activity and stability.
Specifically, the catalyst comprises a carrier and a carrier supported on the carrier. The general formula of the load is Ru x M y N-C, wherein 0<x<1，0<y is less than or equal to 0.5, and the load contains bimetallic Ru and M. Wherein ruthenium metal is an active ingredient, and metal M carries out active modification on ruthenium. Nanoscale Ru formed after roasting treatment x M y The alloy is immobilized on nitrogen and/or carbon sites (N-C).
In the above-mentioned support, the metal M is an oxygen-philic metal and is selected from any one of Ti, V, sc, W. The affinity between the metal and oxygen element is stronger, and the formed oxide is more stable. The oxygen-philic metal has stronger binding force with oxygen element in formic acid, can improve the dehydrogenation efficiency of formic acid and reduce the generation of byproduct CO.
x and y are the molar relative values of Ru and M, and the ratio of x to y is preferably 1 (0.001-0.3).
In one embodiment of the invention, the sum of the masses of the metal ruthenium and the metal M is Ru x M y 0.1% -40% of the total mass of the N-C. I.e. the sum of the masses of the metal ruthenium and the metal M in the support is 0.1 to 40%, preferably 10 to 35% of the total mass of the support.
Ru x M y The mass of the N-C, namely the mass of the load accounts for 0.05 to 50 percent 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 nitrogen heteroatoms. The heterocyclic compound is derived from any one of bipyridine, bipyrimidine, bipyrrole, biimidazole, azaphenanthrene, azaindene and derivatives thereof, and is specifically selected from 2,2' -bipyridine, 4' -bipyridine, 2': any one of 6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-bipyrrole, 1, 10-o-diaza-fiveline.
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 nanometer solid phase catalyst for hydrogen production by formic acid, which comprises the following steps:
1) Preparing a metal precursor solution: the compound containing the metal element is dissolved in the solvent, and then the complex is added and stirred until the compound is dissolved.
Further, the ruthenium-containing compound and the M-containing compound are dissolved in a solvent in a molar ratio of metallic ruthenium to metallic M.
In one embodiment of the invention, the molar ratio of metal element to complex is 1 (1-5), the metal being 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 chloride, sulfate, nitrate, acetate 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 an nitrogen heteroatom selected from the group consisting of 2,2' -bipyridine, 4' -bipyridine, 2': any one of 6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine, 2-bipyrrole, 1, 10-o-diaza-fiveline.
In one embodiment of the present invention, the solvent is a mixed solvent containing water and an organic solvent, which acts to simultaneously dissolve the inorganic metal compound and the organic complex to form a highly dispersed uniform phase.
In one embodiment of the invention, 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.
In one embodiment of the invention, the volume ratio of water to organic solvent in the mixed solvent is 1 (1-50).
2) Pretreatment of the carrier: and (3) acid washing, drying and roasting the carrier, and then cooling to room temperature for standby.
In one embodiment of the invention, the acid is used for pickling with an acid selected from HNO 3 、HCl、H 2 SO 4 At least one of HF, acid liquor concentration of 0.1-3mol/L, acid washing time of 5-120min, roasting in air atmosphere at 300-700 deg.C for 1-4h.
3) And (3) carrier impregnation: the pretreated carrier is immersed in a metal precursor solution under an inert atmosphere, and then dried.
In one embodiment of the invention, the impregnation is carried out under an inert atmosphere, the purpose of which is to insulate air and prevent the change in valence of the 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 the 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 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 baked in inert atmosphere and then is pickled, so that metal organic matters which are not completely decomposed in the baking process and metal M which is independently formed in the baking process can be removed, and then the nano solid-phase catalyst for producing hydrogen by formic acid is obtained.
In one embodiment of the invention, 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 neutrality and dry the carrier. The acid solution is selected from HNO 3 、HCl、H 2 SO 4 At least one of HF and HCOOH, wherein the concentration of the acid solution is 0.05-20mol/L, the acid washing temperature is 10-90 ℃, and the acid washing time is 0.5-10h;
in one embodiment of the invention, the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from any one of nitrogen, argon and helium.
In one embodiment of the invention, the catalyst is prepared by the steps of: 1) Pretreatment of the catalyst carrier: pickling the carrier in 0.1-3mol/L nitric acid solution at room temperature for 5-120min, baking in air atmosphere at 300-700 deg.c for 1-4 hr, and cooling to room temperature for use. 2) Preparing and impregnating a metal precursor solution: weighing ruthenium-containing compound and M-containing compound according to the molar ratio of metal ruthenium to metal M, dissolving in a mixed solvent containing water and an organic solvent, adding the complex, and stirring until the complex is dissolved. Adding pretreated carrier, condensing and refluxing at 40-120deg.C for 3-12 hr under inert atmosphere protection, and drying the impregnated carrier at 50-150deg.C. 3) Roasting: roasting and pickling the dried carrier in inert atmosphere to obtain carrier loaded nano Ru directly x M y The N-C catalyst can also be obtained by further acid washing after roasting.
The invention also relates to a method for producing hydrogen from formic acid, which adopts the nano solid phase catalyst for producing hydrogen from formic acid provided by the invention to decompose formic acid in an aqueous phase system, thereby obtaining hydrogen.
Example 1
And (3) after the carbon powder is ultrasonically soaked in a nitric acid solution with the concentration of 0.5mol/L for 1h, repeatedly cleaning and drying the carbon powder by deionized water, and then placing the carbon powder in a muffle furnace to bake the carbon powder for 2h under the air condition for later use. Then, according to the molar ratio of metal ruthenium to metal vanadium of 1:0.1 and the molar ratio of total metal to bipyridine of 1:3, respectively weighing 0.45g of anhydrous ruthenium trichloride, 0.034g of vanadium trichloride and 1.12g of bipyridine, and stirring and dissolving 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 the carbon powder andoven drying at 70deg.C. Weighing 1.19g, placing in a tube furnace, introducing Ar gas for protection, roasting at 550 ℃ for 2 hours, soaking in 3mol/L formic acid solution, stirring at 50 ℃ for 5 hours, filtering, washing with deionized water to neutrality, and drying to obtain RuV loaded with 1.11g of carbon powder 0.1 N-C. FIG. 1 is a transmission electron microscope image of the material, and it can be seen that Ru and V in the catalyst prepared by the invention are both nano-scale.
Nano RuV loaded with 1.11g of prepared carbon powder 0.1 The N-C catalyst was filled in the reactor and formic acid solution was prepared with 85% by mass of formic acid and potassium formate, wherein the molar ratio of formic acid to potassium formate was 3:1. 50ml of formic acid solution is added into a reaction kettle, the reaction temperature is controlled to be 95 ℃, and after hydrogen production is started, the molar ratio of formic acid to potassium formate in the reaction kettle is maintained to be 3:1 by continuously dropwise adding 85% formic acid. And sequentially passing the generated mixed gas through an active carbon adsorption column to remove formic acid steam, an alkali absorption tank to remove carbon dioxide, and measuring the hydrogen production speed by a drainage method. Detection of H by gas chromatography 2 The volume 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 RuV 0.1 The hydrogen yield per unit mass of metal in the N-C catalyst is calculated and the volume percent of CO is calculated as the volume percent of CO to H 2 And the volume fraction of the total gas volume of CO. As is clear from Table 1, the volume percentage of CO in the starting time of 1 hour was low, the CO content was gradually increased with time and maintained at 0.0034% or less, and the hydrogen production rate was maintained at about 0.25 ml/min.mg.
TABLE 1 toner loaded RuV 0.1 Performance of N-C catalyst in hydrogen production for 48h
Time/h Hydrogen production rate/ml/min mg CO contentQuantity/%
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 ruthenium metal to 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. 1g of carbon powder pretreated in the same manner as in example 1 was added to obtain 1.06g of carbon powder-supported Ru/N-C catalyst in the same manner as in example 1.
The catalyst was filled in a reactor, and hydrogen was produced in the same procedure and under the same hydrogen production conditions as in example 1. Table 2 shows the hydrogen production performance of the catalyst for 48h, the hydrogen production speed fluctuates within 48h about 0.14 ml/min.mg, and the volume percentage of impurity CO is up to 0.05%.
TABLE 2 Performance of carbon powder Supported Ru/N-C catalyst with Hydrogen production time of 48h
Time/h Hydrogen production rate/ml/min mg CO content/%
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 according to the molar ratio of metal ruthenium to metal titanium of 1:0.15 and the molar ratio of total metal to 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. 1g of carbon powder pretreated in the method of example 1 is added, condensed and refluxed for 8 hours under the protection of argon at 50 ℃, and the carbon powder is filtered and dried. Weighing 1.23g of the powder, placing the powder in a tube furnace, introducing Ar gas for protection, and roasting at 500 ℃ for 2 hours to obtain 1.16g of RuTi loaded with carbon powder 0.15 N-C catalyst.
The catalyst was packed in a quartz tube reactor, and hydrogen was produced in the same procedure and under the same hydrogen production conditions as in example 1. Table 3 shows the hydrogen production performance of the catalyst for 48h, the hydrogen production speed is above 0.22 ml/min.mg in 48h, the catalyst is relatively stable, and the volume percentage of impurity CO is below 0.0051%.
TABLE 3 RuTi loaded with carbon powder 0.15 Performance of N-C catalyst for hydrogen production time of 48h
Time/h Hydrogen production rate/ml/min mg CO content/%
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 being 1:0.3 and the molar ratio of total metal to bipyridine being 1:3, respectively weighing 0.45g of anhydrous ruthenium trichloride, 0.1g of vanadium trichloride and 1.31g of bipyridine, stirring and dissolving 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 example 1, condensing and refluxing for 5 hours under the argon protection condition at 50 ℃, and filtering out the carbon powder. Weighing 1.24g of baked carbon powder, placing in a tube furnace, introducing Ar gas for protection, baking at 550 ℃ for 2 hours, pickling baked carbon powder according to the method of example 1, and baking to obtain RuV loaded with 1.2g of carbon powder 0.3 N-C catalyst.
The catalyst was packed in a quartz tube reactor, and hydrogen was produced in the same procedure and under the same hydrogen production conditions as in example 1. Table 4 shows the hydrogen production performance of the catalyst for 48h, the hydrogen production rate is maintained above 0.18 ml/min.mg, and the CO content is as low as below 0.0021%.
TABLE 4 toner loaded RuV 0.3 Performance of N-C catalyst in hydrogen production for 48h
Time/h Hydrogen production rate/ml/min mg CO content/%
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 as in example 1, wherein phenanthroline was used as a complex, and the molar ratio of total metal to phenanthroline was1:3. To this was added 1g of carbon powder pretreated as in example 1, followed by condensation reflux under argon protection at 50℃for 4 hours, and carbon powder was filtered off. Weighing 1.36g of the powder, placing the powder in a tube furnace, introducing Ar gas for protection, and roasting at 650 ℃ for 2 hours to obtain 1.25g of RuTi loaded with carbon powder 0.05 N-C catalyst.
The catalyst was packed in a quartz tube reactor, and hydrogen was produced in the same procedure and under the same hydrogen production conditions as in example 1. Table 5 shows the hydrogen production performance of the catalyst for 48h, the hydrogen production speed is maintained above 0.22 ml/min.mg, and the CO content is as low as 0.0071%.
TABLE 5 RuT of carbon powder load 0.05 Performance of N-C catalyst in hydrogen production for 48h
Time/h Hydrogen production rate/ml/min mg CO content/%
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 ruthenium metal to scandium metal of 1:0.1 and the molar ratio of total metal to bipyridine of 1:3, respectively weighing 0.45g of anhydrous ruthenium trichloride, 0.056g of scandium trichloride hexahydrate and 1.12g of bipyridine, stirring and dissolving in a mixed solvent consisting of 5ml of deionized water and 20ml of nitrogen-methyl pyrrolidone, adding 1g of carbon powder subjected to pretreatment according to the method of example 1, condensing and refluxing for 5 hours under the protection of argon at 50 ℃, filtering out the carbon powder, and weighing 1.46g after drying. Then placing the mixture in a tube furnace, introducing Ar gas for protection, and roasting at 600 ℃ for 2 hours to obtain 1.32g of RuSc loaded with carbon powder 0.1 N-C catalyst.
The catalyst was filled in a reactor, and hydrogen was produced in the same procedure and under the same hydrogen production conditions as in example 1. Table 6 shows the hydrogen production performance of the catalyst for 48h, the hydrogen production speed is maintained above 0.4 ml/min.mg, and the CO content is as low as 0.01%.
TABLE 6 RuSc carbon powder Supported 0.1 Performance of N-C catalyst in hydrogen production for 48h
Time/h Hydrogen production rate/ml/min mg CO content/%
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 producing hydrogen from formic acid can efficiently catalyze the decomposition of formic acid to produce hydrogen and carbon dioxide under the conditions of low temperature, normal pressure and water phase. The catalyst contains bimetal, so that the CO content in the obtained gas mixture is less than 0.015%. In contrast, comparative example 1, in which no oxophilic metal was used, had a CO content of > 0.04% in the hydrogen production product.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (7)

1. The application of the nano solid phase catalyst in hydrogen production by formic acid is characterized in that the catalyst is supported nano Ru x M y An N-C catalyst comprising a support and a carrier, the support being supported on the carrier,
the general formula of the load is Ru x M y N-C, wherein 0<x<1，0<y is less than or equal to 0.5, and the ratio of x to y is 1 (0.001-0.3); the load contains bimetallic Ru and M, the metal M carries out active modification on the metallic Ru, and nano Ru is formed after roasting treatment x M y The alloy is immobilized on nitrogen and/or carbon sites;
the metal M is an oxygen-philic metal and is selected from one of Ti and Sc;
the carrier is at least one of carbon powder, activated carbon particles, carbon felt, porous ceramic, diatomite and kaolin;
the preparation method of the catalyst comprises the following steps:
1) Preparing a metal precursor solution: dissolving water-soluble salts of ruthenium and metal M in a solvent, adding a complex and stirring until the complex is dissolved; wherein: the complex is a heterocyclic compound containing nitrogen heteroatom, and the heterocyclic compound containing nitrogen heteroatom is selected from one of 2,2' -bipyridine, 4' -bipyridine, 2':6', 2' -terpyridine, 2' -bipyrimidine, 4' -bipyrimidine and 1, 10-o-diaza-film;
2) Pretreatment of the carrier: the carrier is baked after being washed and dried, and then cooled to room temperature for standby;
3) And (3) carrier impregnation: under inert atmosphere, placing the pretreated carrier in a metal precursor solution for dipping, and then drying;
4) Roasting and acid washing: roasting the impregnated carrier in inert atmosphere, and then carrying out acid washing to obtain the catalyst.
2. The nano solid phase catalyst according to claim 1 in formic acid productionThe use of hydrogen is characterized in that the sum of the masses of the metal ruthenium and the metal M is Ru x M y 0.1% -40% of the total mass of the N-C.
3. The application of the nano solid phase catalyst in hydrogen production by formic acid as claimed in claim 2, wherein the sum of the mass of metal ruthenium and metal M accounts for Ru x M y 10% -35% of the total mass of the N-C.
4. The use of the nano solid phase catalyst according to claim 1 for hydrogen production from formic acid, wherein in the catalyst, the Ru x M y The mass of the N-C accounts for 0.05 to 50 percent of the total mass of the catalyst.
5. The use of the nano solid phase catalyst according to claim 1 for hydrogen production from formic acid, wherein in step 1), the molar ratio of the sum of the metallic ruthenium and the metal M to the complex is 1 (1-5);
and/or in the step (1), 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).
6. The use of the nano solid phase catalyst according to claim 1, wherein in the step 3), the impregnation is performed under reflux conditions, the condensing reflux temperature is 40-120 ℃, the reflux time is 3-12h, and the drying temperature is 50-150 ℃.
7. The application of the nano solid phase catalyst in hydrogen production by formic acid according to claim 1, wherein in the step 4), the acid washing is to soak the roasted carrier in acid liquor, stir and wash the carrier, wash the carrier with deionized water to be neutral and then dry the carrier;
the acid liquid is selected from HNO 3 、HCl、H 2 SO 4 At least one of HCOOH, wherein the concentration of the acid liquor is 0.05-20mol/L, the pickling temperature is 10-90 ℃, and the pickling time is 0.5-10h;
and/or in the step (4), the roasting temperature is 400-800 ℃, and the inert atmosphere is selected from one of nitrogen, argon and helium.
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