CN110813337B - Metal-phosphorus-carbon hierarchical pore catalyst and preparation method and application thereof - Google Patents

Metal-phosphorus-carbon hierarchical pore catalyst and preparation method and application thereof Download PDF

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CN110813337B
CN110813337B CN201911211370.9A CN201911211370A CN110813337B CN 110813337 B CN110813337 B CN 110813337B CN 201911211370 A CN201911211370 A CN 201911211370A CN 110813337 B CN110813337 B CN 110813337B
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metal
phosphorus
carbon
catalyst
hierarchical pore
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CN110813337A (en
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龙向东
李福伟
高广
聂超
赵泽伦
石利军
岳成涛
其他发明人请求不公开姓名
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B01J35/617—
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B01J35/618—
    • B01J35/643—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a metal-phosphorus-carbon hierarchical pore catalyst and a preparation method and application thereof. The preparation method comprises the following steps: carbonizing a uniform mixed system containing a carbon source, a template agent, a phosphorus source, a metal precursor and a solvent at 80-200 ℃ for 1-12h, calcining at 200-1200 ℃ for 5-24h under a protective atmosphere, and finally removing the template agent to obtain the metal-phosphorus-carbon hierarchical pore catalyst. The method for preparing the catalyst has the advantages of low cost, simple operation method and good universality; meanwhile, the invention provides a catalyst with low cost and wide hydrogenation capability, which can realize full hydrogenation and selective hydrogenation on unsaturated bonds of various organic compounds and is suitable for industrial production.

Description

Metal-phosphorus-carbon hierarchical pore catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a metal-phosphorus-carbon hierarchical pore catalyst, and a preparation method and application thereof.
Background
The hierarchical porous carbon material has high specific surface area, high porosity, adjustable pore size and surface performance, excellent chemical stability and unique electronic conduction property, is an important and indispensable material in modern industry, and has wide application in the fields of catalysis, supercapacitors, biomedicine, gas separation, water purification and the like.
In recent years, with the rapid development of new technologies, the hierarchical porous carbon material shows very excellent performance in application research in a plurality of new fields such as fuel cells, supercapacitors, sensors and nano bioreactors. Meanwhile, in order to pursue higher and more excellent performance, higher requirements are also placed on the self-structure of the carbon material and its physicochemical properties, such as the kind and number of surface functional groups, and the pore structure and specific surface area of the material.
Because the hierarchical porous carbon material itself has high chemical stability and surface inertness (low reactivity), it is very difficult to functionalize it. According to literature reports, the functionalization of porous carbon materials is mainly divided into surface modification and preparation of composite carbon materials. At present, the effective method is to etch the carbon material by using acid or strong base with strong oxidizing property, thereby achieving the purpose of functionalizing the surface, improving the pore structure and increasing the specific surface area. However, this method is not easy to control the kind, amount and distribution of the surface functional groups, and also causes the destruction and collapse of the structure, so that the concentration, amount and treatment time of the acid and alkali are strictly controlled.
Disclosure of Invention
The invention mainly aims to provide a metal-phosphorus-carbon hierarchical pore catalyst, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a metal-phosphorus-carbon hierarchical pore catalyst, which comprises the following steps:
carbonizing a uniform mixed system containing a carbon source, a template agent, a phosphorus source, a metal precursor and a solvent at 80-200 ℃ for 1-12h, calcining at 200-1200 ℃ for 5-24h under a protective atmosphere, and finally removing the template agent to obtain the metal-phosphorus-carbon hierarchical pore catalyst.
The embodiment of the invention also provides the metal-phosphorus-carbon hierarchical pore catalyst prepared by the method.
The embodiment of the invention also provides a metal-phosphorus-carbon hierarchical pore catalyst, which comprises a hierarchical pore carbon carrier and a catalytic active component, wherein the catalytic active component is distributed on the hierarchical pore carbon carrier and comprises a hydrogenation metal and a synergistic catalytic component; the metal-phosphorus-carbon hierarchical pore catalyst is provided with a plurality of pore channel structures, the pore channel structures comprise macropores with the pore diameters of 50-60nm, mesopores with the pore diameters of 10-20nm and micropore structures with the pore diameters of less than 1nm, the pore channels are mutually connected in series, and the specific surface area is 500-1500m2/g。
The embodiment of the invention also provides the application of the metal-phosphorus-carbon hierarchical pore catalyst in hydrogenation reaction.
Embodiments of the present invention also provide a method for hydrogenating an unsaturated compound, which includes:
providing the foregoing metal-phosphorus-carbon hierarchical pore catalyst;
and in a reducing atmosphere, continuously inputting an unsaturated compound solution into a continuous tubular reactor provided with the metal-phosphorus-carbon hierarchical pore catalyst, or adding the unsaturated compound, the metal-phosphorus-carbon hierarchical pore catalyst and a solvent into a batch type reaction kettle to react to prepare a hydrogenation product of the unsaturated compound.
Compared with the prior art, the invention has the beneficial effects that: the method for preparing the catalyst has the advantages of low cost, simple operation method and good universality; meanwhile, the invention provides a catalyst with low cost and wide hydrogenation capability, which can realize full hydrogenation and selective hydrogenation on unsaturated bonds of various organic compounds and is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image of a catalyst prepared in example 1 of the present invention;
FIG. 2 is a TEM image of a catalyst prepared in example 4 of the present invention;
FIG. 3 is a graph showing the results of chromatography in example 18 of the present invention;
FIG. 4 is a graph showing the results of recycling the catalyst obtained in example 7 in example 19 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a large amount of practice, wherein a hard template method is mainly adopted, a saccharide compound is used as a carbon source, a phosphorus compound is used as a phosphorus source, and a metal salt is used as a metal source, a uniformly dispersed precursor is obtained through preliminary carbonization treatment, then the high temperature carbonization is directly carried out, and finally a template agent is removed to obtain the metal-phosphorus-carbon hierarchical pore catalyst.
An aspect of an embodiment of the present invention provides a method for preparing a metal-phosphorus-carbon hierarchical pore catalyst, including:
carbonizing a uniform mixed system containing a carbon source, a template agent, a phosphorus source, a metal precursor and a solvent at 80-200 ℃ for 1-12h, calcining at 200-1200 ℃ for 5-24h under a protective atmosphere, and finally removing the template agent to obtain the metal-phosphorus-carbon hierarchical pore catalyst.
In some more specific embodiments, the carbon source includes any one or a combination of two or more of glucose, fructose, sucrose, sorbitol, hemicellulose, chitobiose, xylobiose, rutinose, and rutinose derivatives, and is not limited thereto.
Further, the template agent includes any one or a combination of two or more of liquid silica sol, gaseous silica sol, nano silica, amorphous silica, molecular sieve, nano magnesia, nano alumina, nano zirconia, nano iron oxide, nano cobalt oxide, nano copper oxide, nano titanium oxide, nano zinc oxide, and nano cerium oxide, but is not limited thereto.
Further, the phosphorus source includes any one or a combination of two or more of phosphoric acid, ammonium salt of phosphoric acid, glucose phosphoric acid, ammonium salt of gluconic acid, phytic acid, ammonium salt of phytic acid, triphenylphosphine, and triphenylphosphine derivatives, and is not limited thereto.
Further, the metal precursor comprises a salt containing a hydrogenation metal; the hydrogenation metal includes any one or a combination of two or more of cobalt, ruthenium, nickel, iron, palladium, platinum, copper, iridium, silver, rhodium, zinc, and gold, but is not limited thereto.
Further, the solvent includes any one or a combination of two or more of water, methanol, ethanol, propanol, 1, 4-dioxane, tetrahydrofuran, ethyl acetate methyl tert-butyl ether, and acetone, and is not limited thereto.
In some more specific embodiments, the method further comprises: and after the calcination is finished, removing the template agent in the obtained solid, and filtering and drying to obtain the metal-phosphorus-carbon hierarchical pore catalyst.
Further, the reagent used for removing the template agent includes any one or a combination of two or more of sodium hydroxide, potassium hydroxide, hydrogen peroxide, ammonia water, hydrofluoric acid, nitric acid, and hydrochloric acid, but is not limited thereto.
Another aspect of an embodiment of the invention also provides a metal-phosphorus-carbon hierarchical pore catalyst prepared by the foregoing method.
Another aspect of an embodiment of the present invention also provides a metal-phosphorus-carbon hierarchical pore catalyst, which includes a hierarchical pore carbon support and a catalytically active component, wherein the catalytically active component is distributed on the hierarchical pore carbon support, and the catalytically active component includes a hydrogenation metal and a co-catalytic component; the metal-phosphorus-carbon hierarchical pore catalyst is provided with a plurality of pore channel structures, the pore channel structures comprise macropores with the pore diameters of 50-60nm, mesopores with the pore diameters of 10-20nm and micropore structures with the pore diameters of less than 1nm, the pore channels are mutually connected in series, and the specific surface area is 500-1500m2/g。
Further, the carbon source forming the hierarchical porous carbon support includes any one or a combination of two or more of glucose, fructose, sucrose, sorbitol, hemicellulose, chitobiose, xylobiose, rutinose, and rutinose derivatives, and is not limited thereto.
Further, the synergistic catalytic component contains a synergistic catalytic element which is phosphorus.
Further, the content of the synergistic catalytic element in the metal-phosphorus-carbon hierarchical pore catalyst is 0.001-20 wt%.
Further, the hydrogenation metal includes any one or a combination of two or more of cobalt, ruthenium, nickel, iron, palladium, platinum, copper, iridium, silver, rhodium, zinc, and gold, and is not limited thereto.
Further, the content of the hydrogenation metal in the metal-phosphorus-carbon hierarchical pore catalyst is 0.001-20 wt%.
In another aspect of the embodiments of the present invention, there is also provided an application of the aforementioned metal-phosphorus-carbon hierarchical pore catalyst in hydrogenation reaction.
Yet another aspect of an embodiment of the present invention provides a method of hydrogenating an unsaturated compound, comprising:
providing the foregoing metal-phosphorus-carbon hierarchical pore catalyst;
and in a reducing atmosphere, continuously inputting an unsaturated compound solution into a continuous tubular reactor provided with the metal-phosphorus-carbon hierarchical pore catalyst, or adding the unsaturated compound, the metal-phosphorus-carbon hierarchical pore catalyst and a solvent into a batch type reaction kettle to react to prepare a hydrogenation product of the unsaturated compound.
In some more specific embodiments, the reaction conditions include: the pressure is 0.1-30MPa, and the temperature is 20-300 ℃.
Further, the functional group contained in the unsaturated compound includes any one or a combination of two or more of an aldehyde group, a ketone group, a vinyl group, an ethynyl group, and an imine group, and is not limited thereto.
Further, the unsaturated compound includes an imine-based compound, a carbon-carbon triple bond-containing compound, and is not limited thereto.
Further, the reducing atmosphere is formed of a reducing gas.
Further, the reducing gas includes hydrogen gas, a mixed gas containing hydrogen gas, and is not limited thereto.
Further, the solvent includes any one or a combination of two or more of water, an alcohol solvent, an ether solvent, and a hydrocarbon solvent, and is not limited thereto.
Further, the alcohol solvent includes any one or a combination of two or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, ethylene glycol and glycerol, and is not limited thereto.
Further, the ether solvent includes any one or a combination of two or more of tetrahydrofuran, diethyl ether, 1, 4-dioxane, diphenyl ether and t-butyl methyl ether, and is not limited thereto.
Further, the hydrocarbon solvent includes any one or a combination of two or more of pentane, hexane, benzene, toluene, petroleum ether, dichloromethane, and chloroform, and is not limited thereto.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Preparation of Fe/P/C catalyst: adding 2g of nano silicon dioxide powder and 10g of fructose into a mixed solution of 0.005 mol/iron nitrate and 0.01mol/L phytic acid, fully stirring for 24 hours, drying, calcining at 80 ℃ for 12 hours in air, then carrying out carbon calcination at 200 ℃ for 24 hours in nitrogen to obtain a template-containing catalyst, adding the template-containing catalyst into 4mol/L sodium hydroxide solution, stirring and reacting for 10 hours at 80 ℃, cooling to room temperature, washing with water to pH 7 to obtain the target catalyst, and carrying out electron microscope photography on the obtained catalyst as shown in figure 1.
Example 2
Preparation of Ru/P/C catalyst: adding 2g of nano silica sol and 10g of glucose into a mixed solution of 0.005 mol/L ruthenium chloride and 0.01mol/L phosphoric acid, fully stirring for 20h, drying, calcining at 200 ℃ in air for 1h, then calcining at 1200 ℃ in nitrogen for 5h to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L sodium hydroxide solution, stirring and reacting at 80 ℃ for 10h, cooling to room temperature, and washing with water until the pH value is 7 to obtain the target catalyst.
Example 3
Preparation of Pt/P/C catalyst: adding 2g of nano titanium dioxide powder and 10g of cane sugar into a mixed solution of 0.004 mol/L chloroplatinic acid and 0.01mol/L phytic acid, fully stirring for 20h, drying, calcining at 160 ℃ for 10h in the air, then calcining at 800 ℃ for 10h in nitrogen to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrogen fluoride solution, stirring and reacting at 80 ℃ for 10h, cooling to room temperature, and washing with water until the pH value is 7 to obtain the target catalyst.
Example 4
Preparation of Co/P/C catalyst: adding 2g of nano zinc dioxide powder and 10g of rutinose into a mixed solution of 0.005 mol/cobalt nitrate and 0.01mol/L ammonium hydrogen phosphate, fully stirring for 20h, drying, calcining at 160 ℃ for 10h in air, then calcining at 800 ℃ for 12h in nitrogen to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrochloric acid solution, stirring to room temperature at 80 ℃, washing with water to pH 7 to obtain the target catalyst, and obtaining the electron microscope photo of the catalyst as shown in FIG. 2.
Example 5
Preparation of Ni/P/C catalyst: adding 2g of nano iron oxide powder and 10g of xylobiose into a mixed solution of 0.005 mol/L nickel nitrate and 0.01mol/L glucose and phosphoric acid, fully stirring for 20h, drying, calcining at 160 ℃ for 10h in air, then calcining at 800 ℃ for 12h in nitrogen to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrochloric acid solution, stirring and reacting at 80 ℃ for 24h, cooling to room temperature, and washing with water until the pH value is 7 to obtain the target catalyst.
Example 6
Preparation of Ru-Co/P/C catalyst: adding 2g of nano silica sol, 5g of glucose and 5g of sucrose into a mixed solution of 0.025 mol/L ruthenium chloride, 0.04 mol/cobalt chloride and 0.01mol/L glucose phosphate, fully stirring for 20h, drying, calcining at 160 ℃ in the air for 10h, then carrying out carbon calcination at 800 ℃ in nitrogen for 12h to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrochloric acid solution, stirring and reacting at 80 ℃ for 24h, cooling to room temperature, washing with water until the pH is 7, and obtaining the target catalyst.
Example 7
Ir/P/C catalyst preparation: adding 2g of nano silica sol, 5g of glucose and 5g of fructose into a mixed solution of 0.005 mol/L iridium chloride and 0.01mol/L phytic acid, fully stirring for 20h, drying, calcining at 160 ℃ in air for 10h, then calcining at 800 ℃ in nitrogen for 12h to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrochloric acid solution, stirring and reacting at 80 ℃ for 24h, cooling to room temperature, and washing with water until the pH is 7 to obtain the target catalyst.
Example 8
Preparation of Pt-Ni/P/C catalyst: adding 2g of nano silica sol and 10g of cane sugar into a mixed solution of 0.005 mol/chloroplatinic acid, 0.03 mol/nickel nitrate and 0.01mol/L triphenylphosphine, fully stirring for 20h, drying, calcining at 160 ℃ for 10h in the air, then calcining at 700 ℃ for 12h in nitrogen to obtain a catalyst containing a template, adding the catalyst containing the template into 4mol/L hydrochloric acid solution, stirring and reacting at 80 ℃ for 24h, cooling to room temperature, and washing with water until the pH value is 7 to obtain the target catalyst.
Example 9
Weighing 0.5g of the catalyst prepared in the example 1, 5g of p-aldehyde benzoic acid, 15ml of ammonia water and 20ml of water, adding the materials into a high-pressure reaction kettle, introducing high-purity hydrogen to replace gas for 6 times, filling hydrogen to 3.0MPa, heating to 100 ℃, reacting for 5 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, and taking supernatant to carry out quantitative calculation on a reaction system. The yield of 4- (aminomethyl) benzoic acid was 95% as characterized by HPLC detection.
Example 10
0.5g of the catalyst prepared in the embodiment 3, 5g of p-tert-butyl benzaldehyde, 20g of 1- (4-chloro-benzhydryl) piperazine and 40ml of ethanol are weighed and added into a high-pressure reaction kettle, high-purity hydrogen is introduced to replace gas for 6 times, the hydrogen is charged to 0.1MPa, the temperature is increased to 300 ℃, the reaction is carried out for 10 hours, after the reaction is finished, the reaction solution is rapidly cooled to room temperature, then the reaction solution is centrifugally separated, the solution is taken to carry out recrystallization quantitative calculation on the reaction system, and the yield of the buclizine is 85%.
Example 11
Weighing 0.5g of the catalyst prepared in the example 6, 4g of benzaldehyde, (R) - (+) -1-phenylethylamine 5g and 40ml of 1, 4-dioxane, adding into a high-pressure reaction kettle, introducing high-purity hydrogen to replace gas for 6 times, charging hydrogen to 30.0MPa, heating to 20 ℃, reacting for 10 hours, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, taking the solution to carry out recrystallization quantitative calculation on the reaction system, wherein the yield of (S) - (-) -N-benzyl-alpha-methylbenzylamine is 90%.
Example 12
0.5g of the catalyst prepared in the embodiment 6, 5.0g of phenylacetylene, 15ml of ethanol and 15ml of water are weighed and added into a high-pressure reaction kettle, high-purity hydrogen is introduced to replace gas for 6 times, then the hydrogen is charged to 5.0MPa, the temperature is raised to 120 ℃, the reaction is carried out for 10 hours, after the reaction is finished, the reaction solution is rapidly cooled to room temperature, then the reaction solution is subjected to centrifugal separation, the solution is taken to carry out GC analysis on the reaction system, and the yield of the styrene is 98%.
Example 13
Weighing 0.5g of the catalyst prepared in the example 2 and 30ml of hexane, adding the catalyst and the hexane into a high-pressure reaction kettle, introducing a mixed gas of acetylene 30% and 70% hydrogen to replace gas for 6 times, then filling the mixed gas to 3.0MPa, heating to 100 ℃, reacting for 10 hours, after the reaction is finished, rapidly cooling to room temperature, collecting gas components for GC analysis, then carrying out centrifugal separation on the reaction liquid, taking the solution for GC analysis, wherein the yield of ethylene is 94%.
Example 14
2.0g (20-60 meshes) of the catalyst prepared in example 4 was weighed, placed in a reaction tube of a fixed bed, mixed gas of 20% acetylene and 80% hydrogen was introduced to 2.0MPa, the temperature was raised to 110 ℃, mixed gas was introduced at 50ml/min, and the yield of ethylene was 95% by GC analysis of the tail gas.
Example 15
2.0g (20-60 meshes) of the catalyst prepared in example 4 was weighed, placed in a reaction tube of a fixed bed, a mixed gas of acetylene 50% and 50% hydrogen was introduced to 4.0MPa, the temperature was raised to 80 ℃, a mixed gas was introduced at 40ml/min, and the tail gas was subjected to GC analysis, whereby the yield of ethylene was 91%.
Example 16
0.5g of the catalyst prepared in the embodiment 6, 5.0g of 1-hexyne and 30ml of tetrahydrofuran are weighed and added into a high-pressure reaction kettle, high-purity hydrogen is introduced to replace gas for 6 times, then the gas is charged to 3.0MPa, the temperature is raised to 80 ℃, the reaction is carried out for 10 hours, after the reaction is finished, the reaction solution is rapidly cooled to room temperature, then the reaction solution is subjected to centrifugal separation, the solution is taken to carry out recrystallization quantitative calculation on the reaction system, and the yield of the 1-hexene is 95%.
Example 17
0.5g of the catalyst prepared in the embodiment 6, 5.0g of tolane and 30ml of toluene are weighed and added into a high-pressure reaction kettle, high-purity hydrogen is introduced to replace gas for 6 times, then the gas is charged to 3.0MPa, the temperature is raised to 140 ℃, the reaction is carried out for 10 hours, after the reaction is finished, the reaction solution is rapidly cooled to room temperature, then the reaction solution is subjected to centrifugal separation, the solution is taken to carry out recrystallization quantitative calculation on the reaction system, and the yield of the stilbene is 98%.
Example 18
Weighing 1.0g of the catalyst prepared in the example 6 and 1.0g of silicon dioxide, uniformly mixing, tabletting to prepare 40-60-mesh catalyst particles, filling the catalyst particles into a fixed bed reaction tube, filling 3.0MPa of hydrogen at the hydrogen flow rate of 50ml/min, heating to 110 ℃, dissolving 200g of p-chloronitrobenzene into 1000ml of toluene solvent, continuously filling the p-chloronitrobenzene into a reactor by using a high-pressure injection pump at the air speed of 30g/g.h, collecting reaction liquid in a liquid storage tank of the device, carrying out chromatographic analysis on the reaction liquid, and preparing the reaction liquid by using an agilent6980 gas chromatography with an SE-54 capillary column, wherein the result is shown in figure 3.
Example 19
The catalyst of example 7 was recycled (the reaction conditions for the reaction of p-aldehyde benzoic acid and ammonia to produce 4- (aminomethyl) benzoic acid were the same as those of example 10), and the yield of the product of the recycled catalyst is shown in fig. 4, which shows that the catalyst prepared by the present invention still maintains a high catalytic effect after seven times of use.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (14)

1. A preparation method of a metal-phosphorus-carbon hierarchical pore catalyst is characterized by comprising the following steps:
uniformly mixing a carbon source, a template agent, a phosphorus source, a metal precursor and a solvent, drying, calcining for 1-12h at 80-200 ℃ in air, calcining for 24h at 200 ℃ in a nitrogen atmosphere, and finally removing the template agent to obtain the metal-phosphorus-carbon hierarchical pore catalyst; the metal-phosphorus-carbon hierarchical pore catalyst comprises a hierarchical pore carbon carrier and a catalytic active component, wherein the catalytic active component is distributed on the hierarchical pore carbon carrier and comprises a hydrogenation metal and a synergistic catalytic component, and the synergistic catalytic element contained in the synergistic catalytic component is a phosphorus element; the metal-phosphorus-carbon hierarchical pore catalyst is provided with a plurality of pore channel structures, wherein the pore channel structures comprise macropores with the pore diameters of 50-60nm, mesopores with the pore diameters of 10-20nm and micropore structures with the pore diameters of less than 1nm, and the pore channels are mutually communicatedIn series, the specific surface area is 500-1500m2The content of the synergistic catalytic element in the metal-phosphorus-carbon hierarchical pore catalyst is 0.001-20wt%, and the content of the hydrogenation metal is 0.001-20 wt%; wherein the carbon source is selected from any one or the combination of more than two of glucose, fructose, sucrose, sorbitol, hemicellulose, chitobiose, xylobiose, rutinose and rutinose derivatives; the template agent is selected from any one or the combination of more than two of liquid silica sol, gaseous silica sol, nano silicon dioxide, amorphous silicon dioxide, molecular sieve, nano magnesium oxide, nano aluminum oxide, nano zirconium oxide, nano iron oxide, nano cobalt oxide, nano copper oxide, nano titanium oxide, nano zinc oxide and nano cerium oxide; the phosphorus source is selected from one or the combination of more than two of phosphoric acid, ammonium salt of phosphoric acid, glucose phosphoric acid, ammonium salt of gluconic acid, phytic acid, ammonium salt of phytic acid, triphenylphosphine and triphenylphosphine derivatives; the metal precursor is selected from a salt containing a hydrogenation metal; the hydrogenation metal is selected from any one or combination of more than two of cobalt, ruthenium, nickel, iron, palladium, platinum, copper, iridium, silver, rhodium, zinc and gold.
2. The method of claim 1, wherein: the solvent is selected from one or the combination of more than two of water, methanol, ethanol, propanol, 1, 4-dioxane, tetrahydrofuran, ethyl acetate methyl tert-butyl ether and acetone.
3. The production method according to claim 1, characterized by comprising: and after the calcination is finished, removing the template agent in the obtained solid, and filtering and drying to obtain the metal-phosphorus-carbon hierarchical pore catalyst.
4. The production method according to claim 3, characterized in that: the reagent adopted when removing the template agent is selected from any one or the combination of more than two of sodium hydroxide, potassium hydroxide, hydrogen peroxide, ammonia water, hydrofluoric acid, nitric acid and hydrochloric acid.
5. A process for hydrogenating an unsaturated compound, comprising:
preparing a metal-phosphorus-carbon hierarchical pore catalyst using the method of any one of claims 1-4;
and in a reducing atmosphere, continuously inputting an unsaturated compound solution into a continuous tubular reactor provided with the metal-phosphorus-carbon hierarchical pore catalyst, or adding the unsaturated compound, the metal-phosphorus-carbon hierarchical pore catalyst and a solvent into a batch type reaction kettle to react to prepare a hydrogenation product of the unsaturated compound.
6. The method of claim 5, wherein the reaction conditions comprise: the pressure is 0.1-30MPa, and the temperature is 20-300 ℃.
7. The method according to claim 5, wherein the unsaturated compound contains a functional group selected from the group consisting of an aldehyde group, a ketone group, a vinyl group, an acetylene group and an imine group.
8. The method according to claim 5, wherein the unsaturated compound is selected from the group consisting of an imine compound and a carbon-carbon triple bond-containing compound.
9. The method of claim 5, wherein the reducing atmosphere is formed from a reducing gas.
10. The method according to claim 9, wherein the reducing gas is selected from hydrogen gas or a mixed gas containing hydrogen gas.
11. The method according to claim 5, wherein the solvent is selected from the group consisting of water, alcohol solvents, ether solvents, and hydrocarbon solvents.
12. The method according to claim 11, wherein the alcohol solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, ethylene glycol and glycerol.
13. The method according to claim 11, wherein the ethereal solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, 1, 4-dioxane, diphenyl ether and t-butyl methyl ether.
14. The method according to claim 11, wherein the hydrocarbon solvent is selected from any one or a combination of two or more of pentane, hexane, benzene, toluene and petroleum ether.
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