CN112569965A - Double-transition metal hierarchical pore catalyst and preparation method and application thereof - Google Patents

Double-transition metal hierarchical pore catalyst and preparation method and application thereof Download PDF

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CN112569965A
CN112569965A CN202011543269.6A CN202011543269A CN112569965A CN 112569965 A CN112569965 A CN 112569965A CN 202011543269 A CN202011543269 A CN 202011543269A CN 112569965 A CN112569965 A CN 112569965A
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acid
transition metal
catalyst
furfural
double
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CN112569965B (en
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丁大千
张瑶
兰旭峰
祁园园
陈天嘉
张印民
张永峰
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Inner Mongolia University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B01J35/617—
    • B01J35/643—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention discloses a double-transition metal hierarchical pore catalyst and a preparation method and application thereof2Is a carrier, comprising: 0.1-2wt% of a noble metal component and 10-20wt% of a transition metal component; wherein the noble metal component is one or a mixture of two of Rh, Ru, Pt, Pd, Au, Ir and Os, and the transition metal component is one or a mixture of two of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, In, W and Re. The double-transition metal hierarchical pore catalyst can be realized under the liquid phase condition without an external hydrogen sourceThe furfural catalytic hydrogenation and the cyclic alcohol catalytic dehydrogenation coupling reaction are used for preparing valuable furfuryl alcohol and cyclic ketone products, wherein the conversion rate of the furfural is up to 98%, the selectivity of the hydrogenation product furfuryl alcohol is up to 92%, and the selectivity of the cyclic alcohol dehydrogenation product cyclic ketone is close to 100%.

Description

Double-transition metal hierarchical pore catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of chemical agents, in particular to a double-transition metal hierarchical pore catalyst and a preparation method and application thereof.
Background
At present, furfuryl alcohol is industrially prepared by a furfural catalytic hydrogenation method. China is a large country for producing furfural, and in the subsequent products of furfural deep processing, furfuryl alcohol is one of products with high value, and the chemical name of furfuryl alcohol is 2-hydroxymethyl furan, and the furfuryl alcohol is an important intermediate of spice, flavoring agent, medicine, pesticide and solvent. The furfuryl alcohol can be used for producing levulinic acid, furfural resin, furan resin, modified urea-formaldehyde, phenolic resin and the like, wherein 80-90% of the furfuryl alcohol is consumed in the production of the furan resin.
At present, the industrial preparation of furfuryl alcohol by catalytic hydrogenation of furfural mainly comprises two processes of high-pressure liquid-phase hydrogenation and low-pressure gas-phase hydrogenation, which have respective advantages and disadvantages (such as Chinese patents CN 1876233A, CN 106807423A, CN 106749120A, CN 109776628A and the like), and particularly, the high-pressure liquid-phase hydrogenation method has high requirements on equipment, so that the equipment investment cost is directly increased; the low-pressure gas-phase hydrogenation method has higher requirements on the catalytic activity of the catalyst. At the same time, a common disadvantage of hydrogenation, whether in gas phase or liquid phase, is the large amount of industrial H required2As a source of hydrogen. Meanwhile, dehydrogenation reaction of cyclohexanol, cyclopentanol and other cyclic alcohols is industrially required to be carried out in a fixed bed (such as chinese patents CN 103285848B, CN 103861626A, CN 105218342A and the like) after high-temperature vaporization due to high activation energy and reversibility, side reaction is easily generated, and H is removed2Cannot be utilized. Both of the above processes result in higher energy consumption and equipment costs.
Disclosure of Invention
In order to solve the problems, the invention provides a double-transition metal hierarchical pore catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the double-transition metal hierarchical pore catalyst is prepared with hierarchical pore SiO2Is a carrier, comprising: 0.1-2wt% of a noble metal component and 10-20wt% of a transition metal component; wherein the noble metal component is one or a mixture of two of Rh, Ru, Pt, Pd, Au, Ir and Os, and the transition metal component is one or a mixture of two of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, In, W and Re.
The invention also provides a preparation method of the double-transition metal hierarchical pore catalyst, which comprises the following steps:
mixing the transition metal soluble salt, organosilane, water and organic acid pore-forming agent according to the mass ratio of 1 (15-20) to (25-35) to (5-15), reacting at 60-90 ℃ to generate silicon gel, roasting at 550 ℃ and reducing to obtain the silicon gel.
Further, the transition metal soluble salt is nitrate, chloride or organic acid salt, the organosilane is one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate and tetrabutyl orthosilicate, and the organic acid pore-forming agent is one or a mixture of more of oxalic acid, glycolic acid, citric acid, malonic acid, succinic acid, 1,2,3, 4-butanetetracarboxylic acid, tartaric acid, malic acid, gluconic acid, mucic acid, terephthalic acid, 1,3, 5-benzenetricarboxylic acid, 1,2,4, 5-benzenetetracarboxylic acid and 2, 2-bis (hydroxymethyl) propionic acid.
Further, the specific surface area of the high specific surface area hierarchical pore catalyst is in the range of 300-800 m2The pore diameter of the micropores is 0.7-1.6 nm, the pore diameter of the mesopores is 3-14 nm, and the catalyst contains a large number of micropores and mesopores.
The double-transition metal hierarchical pore catalyst can be used for hydrogenation-dehydrogenation coupling reaction, does not need hydrogen as an external hydrogen source to carry out catalytic hydrogenation on furfural, does not need high-temperature gasification of cyclic alcohol for dehydrogenation, reduces the cost, improves the safety, and greatly reduces the reaction starting temperature, so the process can be regarded as a novel, economical and feasible process and has a certain industrialization prospect; specifically, the method comprises the following steps: mixing biomass furfural, a solvent and cyclic alcohol, adding a double-transition metal hierarchical pore catalyst, wherein the weight ratio of the double-transition metal hierarchical pore catalyst to aldehyde to cyclic alcohol is (1), (1.5-6): (3-12), carrying out a hydrogenation-dehydrogenation coupling process of biomass aldehyde-cyclic alcohol under the condition of liquid phase heating, wherein the reaction temperature is 165-210 ℃, and the reaction time is 4-24 hours; the resulting mixture was then centrifuged in a high speed centrifuge to separate the catalyst from the filtrate.
Further, the biomass furfural is furfural (F:)α-furfural), 5-hydroxymethylfurfural or a mixture of two thereof; the cyclic alcohol subjected to dehydrogenation reaction is taken as a hydrogen source and is one of cyclooctanol, cyclohexanol, cyclopentanol, cyclobutanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol and 1, 3-cyclopentanediol.
Further, the solvent is one of methanol, ethanol, N-butanol, tetrahydrofuran, isopropanol, benzene, alkylbenzene, cyclohexane, dioxane, N-N Dimethylformamide (DMF), ethyl acetate, gama-valerolactone, etc.
The invention has the following beneficial effects:
the method is characterized in that furfural and cyclic alcohol are used as raw materials, a high-specific-surface-area bimetallic hierarchical pore catalyst synthesized in situ is used, furfural catalytic hydrogenation and cyclic alcohol catalytic dehydrogenation coupling reactions are carried out in one kettle, and valuable furfuryl alcohol and cyclic ketone products are prepared. The conversion rate of furfural in the reaction process can reach 98 percent at most, the selectivity of furfuryl alcohol serving as a hydrogenation product can reach 92 percent at most, and the selectivity of cyclic ketone serving as a product of dehydrogenation of cyclic alcohol is close to 100 percent at most. The invention can prepare two products simultaneously in one kettle without intermediate step and other by-products, and can obtain the target product by distilling or rectifying the reaction liquid after centrifugal separation without complex fixed bed gasification transmission and subsequent condensation treatment at lower temperature, thereby increasing economic benefit. The solvent used in the invention can be reused after distillation, even the cyclic ketone product can be used as the solvent, and unreacted cyclic alcohol can be fed again for dehydrogenation, so the environment is not polluted; the product selectivity in the whole process is relatively high, the operation is simple and convenient, the flow is short, the cost is low, the safety is high, and the process is green. Has good industrialized application prospect and important strategic significance for the economic development of China.
Drawings
FIG. 1 is a flow chart of furfural hydrogenation-cyclic alcohol dehydrogenation coupling reaction under catalysis of a bimetallic hierarchical pore catalyst.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A preparation method of a double-transition metal hierarchical pore catalyst comprises the following steps:
mixing the transition metal soluble salt, organosilane, water and organic acid pore-forming agent according to the mass ratio of 1 (15-20) to (25-35) to (5-15), reacting at 60-90 ℃ to generate silicon gel, roasting at 550 ℃ and reducing to obtain the silicon gel.
In this embodiment, the transition metal soluble salt is a nitrate, a chloride or an organic acid salt, the organosilane is one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate and tetrabutyl orthosilicate, and the organic acid pore-forming agent is one or a mixture of oxalic acid, glycolic acid, citric acid, malonic acid, succinic acid, 1,2,3, 4-butanetetracarboxylic acid, tartaric acid, malic acid, gluconic acid, mucic acid, terephthalic acid, 1,3, 5-benzenetricarboxylic acid, 1,2,4, 5-benzenetetracarboxylic acid and 2, 2-bis (hydroxymethyl) propionic acid.
In this embodiment, the specific surface area of the high specific surface area hierarchical pore catalyst is within the range of300-800 m2The pore diameter of the micropores is 0.7-1.6 nm, the pore diameter of the mesopores is 3-14 nm, and the catalyst contains a large number of micropores and mesopores.
Example 2
The double-transition metal hierarchical pore catalyst obtained in example 1 can be used for hydrogenation-dehydrogenation coupling reaction,
as shown in fig. 1, the processes of furfural hydrogenation and cyclic alcohol dehydrogenation are coupled and synchronously performed to simultaneously generate target products of furfuryl alcohol and cyclic ketone, and the whole process is realized in the same reaction kettle by a multi-level pore bimetallic catalyst.
During operation, mixing biomass furfural, a solvent and cyclic alcohol, adding a double-transition metal hierarchical pore catalyst, wherein the weight ratio of the double-transition metal hierarchical pore catalyst to aldehyde to cyclic alcohol is 1 (1.5-6): (3-12), carrying out a hydrogenation-dehydrogenation coupling process of biomass aldehyde-cyclic alcohol under the condition of liquid phase heating, wherein the reaction temperature is 165-210 ℃, and the reaction time is 4-24 hours; the resulting mixture was then centrifuged in a high speed centrifuge to separate the catalyst from the filtrate.
In this embodiment, the biomass furfural is furfural (f)α-furfural), 5-hydroxymethylfurfural or a mixture of two thereof; the cyclic alcohol subjected to dehydrogenation reaction is taken as a hydrogen source and is one of cyclooctanol, cyclohexanol, cyclopentanol, cyclobutanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol and 1, 3-cyclopentanediol.
In this embodiment, the solvent is one of methanol, ethanol, N-butanol, tetrahydrofuran, isopropanol, benzene, alkylbenzene, cyclohexane, dioxane, N-N Dimethylformamide (DMF), ethyl acetate, and gama-valerolactone.
The furfuryl alcohol and cyclic ketone products obtained by the reaction can be distilled and purified with a solvent.
Example 3
After refining the reaction process in example 2, key reaction parameters with different characteristics can be obtained. This example helps the skilled person to understand the effect of a solvent system on the present invention. 1.5g of furfural, 4.5g of cyclohexanol and 0.5g of catalyst (15% Cu-0.5% Pd/SiO)2) Adding the mixture into a high-pressure reaction kettle,a number of different solvent experiments were repeated with each single addition of 10.5g of different solvents. Magnetically stirring the mixture at a high speed at 195 ℃ for reaction for 10 hours, and separating the catalyst from the reaction liquid by using a high-speed centrifuge after the reaction is finished. The conversion rates of furfural and hydrogen source and the selectivity of furfuryl alcohol as hydrogenation product and cyclohexanone as dehydrogenation product are shown in table one.
TABLE 1 Properties of furfuryl alcohol and cyclohexanone prepared from furfuraldehyde and cyclohexanol using different substances as solvents
Solvent(s) Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
Benzene and its derivatives 11.8 91.2 4.5 74.7
Toluene 9.5 74.2 4.0 73.4
Cyclohexane 20.6 59.0 6.1 65.8
Tetrahydrofuran (THF) 23.3 88.8 8.1 81.7
Ethyl acetate 58.9 85.3 20.1 83.1
Ethanol 72.9 63.4 25.6 74.6
Methanol 86.7 68.4 28.3 92.0
Example 4
The reaction materials and procedure were the same as in example 3, and the solvent used was methanol different depending on the kind of the cyclic alcohol added. This example helps the skilled person to understand the impact of the hydrogen source system on the present invention. The conversion rates of furfural and cyclohexanol and the selectivity of furfuryl alcohol and cyclic ketone in the reaction solution were analyzed by gas chromatography, as shown in table 2.
TABLE 2 Furfural alcohol Performance from different cyclic alcohols as Hydrogen Source
Source of cyclic alcohols Furfural conversion (%) Furfuryl alcohol selectivity (%) Conversion of Cyclic alcohol (%) Corresponding Cyclic ketone Selectivity (%)
Cyclo-octanol 69.3 36.5 31.2 60.9
Cycloheptanol 71.3 42.8 30.4 75.6
Cyclohexanol 86.7 68.4 28.3 92.0
1, 4-cyclohexanediols 96.8 92.4 16.4 89.5
Cyclopentanol 79.3 60.1 27.1 90.9
Cyclobutanol 70.9 65.2 38.4 57.7
Example 5
The reaction procedure was the same as in example 3, using methanol as the solvent, except that the reaction temperature was changed. This example is useful to the skilled person in understanding the effect of temperature regimes on the present invention. The conversion rates of furfural and cyclohexanol and the selectivities of furfuryl alcohol and cyclohexanone in the reaction solution by gas chromatography are shown in table 3.
TABLE 3 Furfural and cyclohexanol Properties at different temperatures for furfuryl alcohol and cyclohexanone
Reaction temperature (C)oC） Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
185 62.6 57.4 21.2 95.4
190 71.4 59.8 23.0 96.2
195 86.7 68.4 28.3 92.0
200 95.0 58.6 31.7 95.5
205 95.3 32.2 32.7 95.7
Example 6
The reaction materials and procedure were as in example 3, using methanol as solvent and a reaction temperature of 195 deg.CoC, except that the time of reaction was varied. This example helps the skilled person to understand the effect of reaction time on the present invention. The conversion rates of furfural and cyclohexanol and the selectivities of furfuryl alcohol and cyclohexanone in the reaction solution by gas chromatography are shown in table 4.
TABLE 4 Furfural and cyclohexanol Properties at different reaction times for furfuryl alcohol and Cyclohexanone
Reaction time (h) Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
2 28.1 56.3 10.1 79.2
4 52.9 66.4 17.2 87.1
6 65.9 62.6 21.0 90.5
8 83.7 66.1 27.3 91.5
10 86.7 68.4 28.3 92.0
12 95.2 59.8 31.5 98.0
Example 7
The raw materials and steps of the reaction are the same as those in example 3, and the used solvent is methanol, which is different from that of the solvent in that the metal types loaded on the catalyst are changed (wherein the mass fraction of the noble metal is 0.5 percent, the mass fraction of the non-noble metal is 15 percent, and SiO is used2To 100% by mass). Book (I)The examples help the skilled person to understand the effect of the metal component in the catalyst on the hydrogenation-dehydrogenation performance. The conversion rates of furfural and cyclohexanol and the selectivities of furfuryl alcohol and cyclohexanone in the reaction solution were shown in table 5.
TABLE 5 Properties of furfuryl alcohol and cyclohexanone prepared by loading different noble metals of furfural and cyclohexanol on catalyst
Noble metal component Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
(Cu-)Pd 86.7 68.4 28.3 92.0
(Cu-)Ru 84.9 67.2 27.0 92.7
(Cu-)Pt 89.9 69.7 31.5 94.0
(Cu-)Rh 76.0 58.8 24.7 90.7
Non-noble metal component Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
Co(-Pd) 90.8 76.4 31.0 94.8
Ni(-Pd) 91.9 87.3 33.7 98.5
Zn(-Pd) 74.5 52.1 26.2 92.0
Example 8
The reaction materials and procedure were the same as in example 3, the solvent used was methanol, except that the ratio of the two metals in the catalyst was changed (SiO2To 100% by mass). This example helps the skilled artisan to understand the effect of the relative amount of bimetal on the hydrogenation-dehydrogenation performance in the present invention. The conversion rates of furfural and cyclohexanol and the selectivities of furfuryl alcohol and cyclohexanone in the reaction solution were shown in table 6.
TABLE 6 Furfural alcohol, Cyclohexanone Properties from Furfural and Cyclohexanone in different proportions of metals in the catalyst
Proportion of metals in the catalyst Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
15%Cu-0.25%Pd 65.7 51.3 21.2 92.0
15%Cu-1%Pd 93.9 30.9 32.1 94.2
15%Cu-0.5%Pd 86.7 68.4 28.3 92.0
10%Cu-0.5%Pd 79.7 58.6 22.1 96.3
20%Cu-0.5%Pd 97.0 55.9 33.7 92.5
Example 9
The reaction materials and procedure were the same as in example 3, and the solvent used was methanol, except that the mass of the added catalyst was changed. This example is helpful to the skilled artisan in understanding the effect of catalyst/reactant ratios on the present invention. The conversion rates of furfural and cyclohexanol and the selectivities of furfuryl alcohol and cyclohexanone in the reaction solution were shown in table 7.
TABLE 7 Furfural and Cyclohexanone Properties for Furfural and Cyclohexanone preparation with different catalyst masses
Mass of catalyst (g) Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
0.25 47.3 53.9 16.1 88.4
0.5 86.7 68.4 28.3 92.0
1 91.4 29.0 24.1 96.8
Example 10
The reaction raw materials and the steps are the same as those in example 3, and the used solvent is methanol, which is different from the mass ratio of the furfural and the cyclic alcohol which are added as the raw materials. This example is useful to the skilled person in understanding the effect of the ratio of the feed to be hydrogenated and the dehydrogenation feed on the present invention. The conversion rates of furfural and cyclic alcohol and the selectivity of furfuryl alcohol and cyclic ketone in the reaction solution were determined by gas chromatography as shown in Table 8.
TABLE 8 Furfural and cyclic alcohol Properties for furfuryl alcohol, cyclic ketone preparation from furfural and cyclic alcohol at different mass ratios of furfural to cyclic alcohol
And (3) furfural: cyclic alcohols Furfural conversion (%) Furfuryl alcohol selectivity (%) Cyclohexanol conversion (%) Cyclohexanone Selectivity (%)
1:6 (cyclohexanol) 98.5 54.1 17.1 88.3
1:4 (cyclohexanol) 95.4 76.9 30.2 92.6
1:3 (cyclohexanol) 86.7 68.4 28.3 92.0
1:2 (cyclohexanol) 59.4 42.2 25.5 91.3
1:1.5 (cyclohexanol) 40.3 50.5 23.9 92.0
1:6 (cyclopentanol) 83.1 54.2 25.4 96.1
1:3 (cyclopentanol) 79.3 60.1 27.1 90.9
1:2 (cyclopentanol) 49.3 58.5 19.2 98.2
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (8)

1. A double transition metal hierarchical pore catalyst is characterized in that: the high specific surface area hierarchical pore catalyst is a hierarchical pore SiO2Is a carrier, comprising: 0.1-2wt% of a noble metal component and 10-20wt% of a transition metal component; wherein the noble metal component is one or a mixture of two of Rh, Ru, Pt, Pd, Au, Ir and Os, and the transition metal component is one or a mixture of two of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, In, W and Re.
2. The method of claim 1, wherein the catalyst comprises: the method comprises the following steps:
mixing the transition metal soluble salt, organosilane, water and organic acid pore-forming agent according to the mass ratio of 1 (15-20) to (25-35) to (5-15), reacting at 60-90 ℃ to generate silicon gel, roasting at 550 ℃ and reducing to obtain the silicon gel.
3. The method of claim 2, wherein the catalyst comprises: the transition metal soluble salt is nitrate, chloride or organic acid salt, the organosilane is one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate and tetrabutyl orthosilicate, and the organic acid pore-forming agent is one or a mixture of more of oxalic acid, glycolic acid, citric acid, malonic acid, succinic acid, 1,2,3, 4-butanetetracarboxylic acid, tartaric acid, malic acid, gluconic acid, mucic acid, terephthalic acid, 1,3, 5-benzenetricarboxylic acid, 1,2,4, 5-benzenetetracarboxylic acid and 2, 2-bis (hydroxymethyl) propionic acid.
4. The method of claim 1, wherein the catalyst comprises: the specific surface area of the high specific surface area hierarchical pore catalyst is in the range of 300-800 m2The pore diameter of the micropores is 0.7-1.6 nm, the pore diameter of the mesopores is 3-14 nm, and the catalyst contains a large number of micropores and mesopores.
5. The use of a double transition metal multiwell catalyst according to claim 1, wherein: can be used for hydrogenation-dehydrogenation coupling reaction.
6. The use of claim 5, wherein: the method comprises the following steps: mixing biomass furfural, a solvent and cyclic alcohol, adding a double-transition metal hierarchical pore catalyst, wherein the weight ratio of the double-transition metal hierarchical pore catalyst to aldehyde to cyclic alcohol is (1), (1.5-6): (3-12), carrying out a hydrogenation-dehydrogenation coupling process of biomass aldehyde-cyclic alcohol under the condition of liquid phase heating, wherein the reaction temperature is 165-210 ℃, and the reaction time is 4-24 hours; the resulting mixture was then centrifuged in a high speed centrifuge to separate the catalyst from the filtrate.
7. The use of claim 6, wherein: the biomass furfural is furfural (α-furfural), 5-hydroxymethylfurfural or a mixture of two thereof; the cyclic alcohol subjected to dehydrogenation reaction is taken as a hydrogen source and is one of cyclooctanol, cycloheptane pure, cyclohexanol, cyclopentanol, cyclobutanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol and 1, 3-cyclopentanediol.
8. The use of claim 6, wherein: the solvent is one of methanol, ethanol, N-butanol, tetrahydrofuran, isopropanol, benzene, alkylbenzene, cyclohexane, dioxane, N-N Dimethylformamide (DMF), ethyl acetate, gama-valerolactone, etc.
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