阅读说明：本技术 一种金属-磷-碳多级孔催化剂及其制备方法与应用 (Metal-phosphorus-carbon hierarchical pore catalyst and preparation method and application thereof ) 是由 李福伟 高广 龙向东 聂超 孙鹏 赵泽伦 石利军 岳成涛 于 2019-12-02 设计创作，主要内容包括：本发明公开了一种金属-磷-碳多级孔催化剂及其制备方法与应用。所述制备方法包括：使包含碳源、模板剂、磷源、金属前驱体和溶剂的均匀混合体系于80-200℃进行碳化1-12h,之后在保护性气氛下于200-1200℃煅烧5-24h,最后除去模板剂即获得金属-磷-碳多级孔催化剂。本发明制备催化剂的方法,成本低、操作方法简易且普适性好；同时本发明提供了一种低成本且具有广发加氢能力的催化剂,其可以对多种有机化合物的不饱和键实现全加氢和选择性加氢,适用于进行工业化生产。(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.)

1. A preparation method of a metal-phosphorus-carbon hierarchical pore catalyst is characterized by comprising 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.

2. The method of claim 1, wherein: the carbon source comprises any one or the combination of more than two of glucose, fructose, sucrose, sorbitol, hemicellulose, chitobiose, xylobiose, rutinose and rutinose derivatives;

and/or the template agent comprises any one or the combination of more than two 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;

and/or the phosphorus source comprises any 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;

and/or, the metal precursor comprises a salt comprising a hydrogenation metal; wherein, the hydrogenation metal comprises any one or the combination of more than two of cobalt, ruthenium, nickel, iron, palladium, platinum, copper, iridium, silver, rhodium, zinc and gold;

and/or the solvent comprises any 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: 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;

preferably, the reagent used for removing the template agent comprises any one or a combination of more than two of sodium hydroxide, potassium hydroxide, hydrogen peroxide, ammonia water, hydrofluoric acid, nitric acid and hydrochloric acid.

4. A metal-phosphorus-carbon hierarchical pore catalyst prepared by the method of any one of claims 1-3.

5. A metal-phosphorus-carbon hierarchical pore catalyst is characterized by comprising 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。

6. The metal-phosphorus-carbon hierarchical pore catalyst according to claim 5, wherein a carbon source forming the hierarchical pore carbon support comprises any one or a combination of two or more of glucose, fructose, sucrose, sorbitol, hemicellulose, chitobiose, xylobiose, rutinose, and rutinose derivatives;

and/or the synergistic catalytic element contained in the synergistic catalytic component is phosphorus element; preferably, the content of the synergistic catalytic element in the metal-phosphorus-carbon hierarchical pore catalyst is 0.001-20 wt%;

and/or the hydrogenation metal comprises any one or the combination of more than two of cobalt, ruthenium, nickel, iron, palladium, platinum, copper, iridium, silver, rhodium, zinc and gold; preferably, the content of the hydrogenation metal in the metal-phosphorus-carbon hierarchical pore catalyst is 0.001-20 wt%.

7. Use of the metal-phosphorus-carbon hierarchical pore catalyst according to any one of claims 4 to 6 in hydrogenation reactions.

8. A process for hydrogenating an unsaturated compound, comprising:

providing the metal-phosphorus-carbon hierarchical pore catalyst of any one of claims 4-6;

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.

9. The method of claim 8, wherein the reaction conditions comprise: the pressure is 0.1-30MPa, and the temperature is 20-300 ℃.

10. The method according to claim 8, wherein the unsaturated compound contains a functional group including any one or a combination of two or more of an aldehyde group, a ketone group, a vinyl group, an acetylene group and an imine group; preferably, the unsaturated compound comprises an imine compound and a carbon-carbon triple bond-containing compound;

and/or the reducing atmosphere is formed by a reducing gas; preferably, the reducing gas comprises hydrogen and/or a mixed gas containing hydrogen;

and/or the solvent comprises one or the combination of more than two of water, alcohol solvent, ether solvent and hydrocarbon solvent;

preferably, the alcohol solvent comprises any one or a combination of two or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, ethylene glycol and glycerol;

preferably, the ether solvent comprises one or more of tetrahydrofuran, diethyl ether, 1, 4-dioxane, diphenyl ether and tert-butyl methyl ether;

preferably, the hydrocarbon solvent includes any one or a combination of two or more of pentane, hexane, benzene, toluene, petroleum ether, dichloromethane and chloroform.

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 metal-phosphorus-a carbon hierarchical pore catalyst comprising a hierarchical pore carbon support and a catalytically active component distributed on the hierarchical pore carbon support, the catalytically active component comprising 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。

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.