CN111470944A - Synthetic method of alcohol compound - Google Patents

Synthetic method of alcohol compound Download PDF

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Publication number
CN111470944A
CN111470944A CN201910062954.8A CN201910062954A CN111470944A CN 111470944 A CN111470944 A CN 111470944A CN 201910062954 A CN201910062954 A CN 201910062954A CN 111470944 A CN111470944 A CN 111470944A
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alkaline earth
earth metal
nickel
carbon
ketone
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谢婧新
荣峻峰
宗明生
于鹏
吴耿煌
纪洪波
林伟国
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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

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  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a synthesis method of an alcohol compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze ketone compounds to carry out hydrogenation reduction reaction in a hydrogen atmosphere; the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles. The method adopts the carbon-coated nickel nanocomposite containing alkaline earth metal as the catalyst, the carbon material and the nickel nanoparticles act synergistically to produce a good catalytic effect, the alkaline earth metal of the shell layer further synergistically improves the catalytic performance of the material, and the catalyst is used for synthesizing alcohol compounds by hydrogenation reduction of ketone compounds and has excellent activity, selectivity and safety.

Description

Synthetic method of alcohol compound
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a synthesis method of an alcohol compound.
Background
The alcohol compound is a very important chemical intermediate, and has very wide application in the industries of organic solvents, fine chemicals, medicines, pesticides, household cosmetics and the like. For example, n-butanol is an important chemical raw material, can be used for preparing plasticizers such as butyl phthalate, aliphatic dibasic acid ester, butyl phosphate and the like, chemical raw materials such as butyric acid, butylamine, butyl acrylate and the like, and also can be used for solvents, dehydrating agents, anti-emulsifying agents, grease, spices, antibiotics, extracting agents such as vitamins and the like, additives of alkyd resin coatings, defoaming agents, mineral dressing agents and the like, and has wide application and wide market prospect.
The hydrogenation reaction has wide application in petrochemical production, wherein the method for obtaining the corresponding alcohol compound by the ketone compound through catalytic hydrogenation has very important significance. Most of the acetone is industrially obtained from cumene peroxidation and is co-produced with phenol. As the demand of phenol is increased, a large amount of acetone is produced, the acetone is excessive, and the preparation of isopropanol by acetone hydrogenation becomes a feasible route.
The isopropanol prepared by acetone hydrogenation can use nickel-based or copper-based catalysts, and can also use supported noble metal catalysts and transition metal-based catalysts, such as noble metal catalysts of platinum (Pt), palladium (Pd) and rhodium (Rh) and nickel (Ni) -based non-noble metal catalysts. The noble metal catalyst has the advantages of high catalytic activity, mild reaction conditions and the like, and plays an important role in generating corresponding alcohol compounds by catalytic hydrogenation of ketone compounds. Although noble metals have these advantages, noble metal catalysts are expensive and have severe requirements for raw material impurities. The supported nickel catalyst is easy to agglomerate in the preparation process, the catalytic efficiency is low, and side reactions are easy to occur.
From the above, it is an urgent problem in the art to develop a hydrogenation reduction catalyst which is stable in air and has excellent catalytic performance for the hydrogenation reduction of ketone compounds.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a synthesis method of alcohol compounds, which adopts a carbon-coated nickel-containing nanocomposite containing alkaline earth metal as a catalyst, wherein the nanocomposite is in a core-shell structure formed by coating nickel nanoparticles with a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, the carbon material and the nickel nanoparticles act synergistically to produce a good catalytic effect, the alkaline earth metal of the shell layer further synergistically improves the catalytic performance of the material, and the alcohol compounds are used for synthesizing the alcohol compounds by hydrogenation reduction of ketone compounds and have excellent activity, selectivity and safety.
The invention provides a synthesis method of an alcohol compound, which comprises the following steps:
the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze ketone compounds to carry out hydrogenation reduction reaction in a hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
According to one embodiment of the invention, the ketone compound is an aliphatic ketone, an alicyclic ketone or an aromatic ketone.
According to one embodiment of the invention, the ketone compound is selected from acetone or cyclohexanone.
According to one embodiment of the present invention, the catalyst is present in an amount of 1% to 50%, preferably 5% to 30%, based on the amount of the ketone compound.
According to one embodiment of the present invention, the temperature of the hydrogenation reduction reaction is generally 100 ℃ to 200 ℃.
According to one embodiment of the present invention, wherein the pressure of the hydrogen gas is generally 3MPa to 6 MPa.
According to an embodiment of the present invention, the hydrogenation reduction reaction is performed after the catalyst and the ketone compound are mixed in a solvent, wherein the solvent is one or more selected from the group consisting of alcohols, ethers, alkanes and water.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. Optionally, the nanocomposite is a mesoporous material having two or more mesopore distribution peaks. Optionally, the nanocomposite material has a mesopore distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively. Optionally, the mesoporous material has a mesopore volume fraction of greater than 50%, preferably greater than 80%, more preferably greater than 95% of the total pore volume.
According to an embodiment of the invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, the carbon content is 65 at% to 95 at%, the nickel content is 0.1 at% to 10 at%, the oxygen content is 1 at% to 20 at%, and the nitrogen content is 1 at% to 10 at%, in atomic percentage.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
The invention has the beneficial effects that:
the synthesis method of the alcohol compound provided by the invention takes the carbon-coated nickel nano composite material containing alkaline earth metal as the catalyst to carry out hydrogenation reduction on the ketone compound, and the catalyst material is very stable, does not spontaneously combust, is antioxidant, is resistant to acid corrosion and low in danger, and is suitable for storage and transportation, so that the safety of the synthesis process of the alcohol compound is ensured.
The carbon-coated nickel nanocomposite containing alkaline earth metal has good repeatability, high activity and high selectivity in the reaction of catalytically reducing ketone compounds into alcohol compounds, and the nickel coated in the graphitized carbon layer has a penetrating effect, so that the electronic state of the alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nanocomposite has good catalytic performance; in addition, the nano composite material has stronger magnetism, and can be conveniently used for separating a catalyst by utilizing the magnetism or used for processes such as a magnetic stabilization bed and the like.
Drawings
FIG. 1 is a photograph showing the magnetic properties of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 2 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 3 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIGS. 4a and 4b respectively show N of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 12Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 5 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIG. 6 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
fig. 7 is a BJH pore size distribution curve of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2.
Detailed Description
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Any terms not directly defined herein should be understood to have meanings associated with them as commonly understood in the art of the present invention. The following terms as used throughout this specification should be understood to have the following meanings unless otherwise indicated.
Term(s) for
The term "ketone compound" refers to a class of compounds that contain at least one carbonyl group in the molecule. The "ketone compound" of the present invention includes both monoketones and polyketones.
The term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is about 0.34 nm. The composite material formed after the graphitized carbon layer is coated with the nickel nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The terms "alkaline earth metal", "nitrogen" and "oxygen" in the "graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen" refer to alkaline earth metal elements, nitrogen elements and oxygen elements, wherein the "alkaline earth metal content" of the nanocomposite refers to the content of the alkaline earth metal elements, the "nitrogen content" refers to the content of the nitrogen elements, the "oxygen content" refers to the content of the oxygen elements, and specifically refers to the content of the alkaline earth metal elements, nitrogen elements and oxygen elements in various forms contained in the formed graphitized carbon layer during the preparation of the carbon-coated nanocomposite, the "alkaline earth metal content" is the total content of all forms of alkaline earth metal elements, the "nitrogen content" is the total content of all forms of nitrogen elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkaline earth metal content", "nitrogen content" and "oxygen content" were measured by XPS method.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "TOF" is defined herein as the amount of a reactant converted per unit time by a single active metal atom, and TOF measures the rate at which a catalyst catalyzes a reaction and indicates the intrinsic activity of the catalyst.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are Cu target, K α ray (the wavelength lambda is 0.154nm), tube voltage is 40kV, tube current is 200mA, and scanning speed is 10 degrees (2 theta)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: acceleration voltage of 200kV
The X-ray photoelectron spectrum analyzer (XPS) is an ESCA L ab220i-X L type electron spectrum analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromized A1K α X-rays, the power is 330W, and the basic vacuum is 3 × 10 during analysis and test-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6eV), and the late peak processing software was XPSPEAK.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
In the invention, after the average particle diameter of the metal nanoparticles is divided into peaks by an XRD (X-ray diffraction) pattern, the average particle diameter is calculated according to the Sherle formula: d ═ k γ/(B cos θ) was calculated. Wherein k is Scherrer constant, k is 0.89; b is half-height width; theta is the diffraction angle, unit radian; gamma is the x-ray wavelength, 0.154054 nm.
The invention provides a synthesis method of ketone compounds, which comprises the following steps: the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze ketone compounds to carry out hydrogenation reduction reaction in a hydrogen atmosphere; the chemical reaction equation is illustrated below:
Figure BDA0001954751840000061
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
In some embodiments, the ketone compound can be an aliphatic ketone, an aryl ketone, or an alicyclic ketone, i.e., R1And R2Can be alkyl, cycloalkyl, aryl and R1And R2The aliphatic ketone is a ketone with carbon atoms connected into a chain in a molecule and is in an open chain shape, the alicyclic ketone is a ketone with carbon atoms connected into a closed carbon ring in a molecule, and the carbonyl of the aromatic ketone is directly connected onto an aromatic ring. For example, the aliphatic ketone includes, but is not limited to, acetone, the alicyclic ketone includes, but is not limited to, cyclohexanone, and in some embodiments, the ketone compound is preferably acetone, cyclohexanone.
In some embodiments, the catalyst comprises 1% to 50%, preferably 5% to 30% of the mass of the ketone compound.
In some embodiments, the temperature of the hydrogenation reduction reaction is generally 100 ℃ to 200 ℃.
In some embodiments, the pressure of the hydrogen gas therein is generally from 3MPa to 6 MPa.
In some embodiments, the hydrogenation reduction reaction is performed after the catalyst and the ketone compound are mixed in a solvent, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water, such as ethanol, tetrahydrofuran, cyclohexane and the like.
According to one embodiment of the present invention, the nanocomposite of the present invention is a composite material composed of "a graphitized carbon layer containing an alkaline earth metal, nitrogen, and oxygen", "nickel nanoparticles tightly coated with (not in contact with) the graphitized carbon layer", and "nickel nanoparticles in a confined region in contact with the outside". The surface of the graphitized carbon layer containing nitrogen and oxygen of the nano composite material has rich defect sites, the carbon material has catalytic activity, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nano composite material has better catalytic performance.
In some embodiments, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. As known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play better roles in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the batch-produced composite has two distribution peaks in the mesoporous range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 5nm and 6nm to 15nm, respectively.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 7nm and 8nm to 20nm, respectively.
In some embodiments, the proportion of mesopore volume in the composite material to the total pore volume is greater than 50%, preferably greater than 80%, according to the nanocomposite material of the present invention. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous volume thereof may be 0.05cm3/g～1.25cm3Per g, also may be 0.10cm3/g～0.30cm3/g。
Nanocomposites according to the inventionThe composite material, in some embodiments, has a specific surface area generally greater than 140m2/g, may be greater than 200m2/g。
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
According to the nanocomposite material of the present invention, nitrogen and oxygen are doped in the carbon layer. The nitrogen and oxygen contents can be adjusted by additionally introducing oxygen-containing compounds and nitrogen-containing compounds, such as hexamethylenetetramine and polyhydric alcohols in the manufacturing process. The catalytic performance of the carbon layer can be adjusted by adjusting the contents of nitrogen and oxygen in the nano composite material, so that the carbon layer is suitable for catalyzing different reactions.
In some embodiments, the content of elements, in atomic percent, determined using XPS method: the content of the alkaline earth metal is 0.1at percent to 3at percent, preferably 0.2at percent to 2at percent; the carbon content is 65 at% to 95 at%, preferably 74 at% to 91 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 20 at%, preferably 5 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, preferably 0.1 at% to 10 at%. More preferably 1 at% to 5 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
In some embodiments, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
In some embodiments, the core-shell structure has a particle size of 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
In some embodiments, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with a solution containing alkaline earth metal, and then drying; and the contact mode comprises the step of immersing the product after the primary pyrolysis in the alkaline earth metal solution, or the step of placing the product after the primary pyrolysis in the alkaline earth metal solution for stirring. The time for dipping or stirring is not suitable to be too long or too short, preferably between 10min and 300min, the temperature is preferably between 0 ℃ and 100 ℃, and the contact reaction is preferably carried out under the condition of stirring. According to the invention, the product of the primary pyrolysis may or may not be filtered after being contacted with the alkaline earth metal-containing solution, and the obtained product is dried.
And putting the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated nickel nanocomposite containing the alkaline earth metal.
Specifically, the precursor is a water-soluble mixture, which means that nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound are dissolved into a homogeneous solution in water and/or ethanol and other solvents, and then the solvent is directly removed to obtain the nickel-containing precursor. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be by any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
It should be noted that the polyvalent organic carboxylic acid may be a nitrogen-containing polyvalent organic carboxylic acid or a nitrogen-free polyvalent organic carboxylic acid, and when the polyvalent organic carboxylic acid is a nitrogen-containing polyvalent organic carboxylic acid, the mass of the nitrogen-containing compound may be zero, that is, the nitrogen-containing compound may not be added, and the mass ratio of the mass of the nitrogen element to the mass of the nickel salt and the polyvalent organic carboxylic acid may be within a certain range. In some embodiments, the mass ratio of the nickel salt, the organic polycarboxylic acid and the nitrogen-containing compound is 1: 0.1-100: 0-100, preferably 1: 0.5-5, and more preferably 1: 0.8-2: 1-2.
In some embodiments, the method further comprises mixing the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds except the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds in a solvent such as water, ethanol and the like to form a homogeneous solution, and then removing the solvent to obtain the water-soluble mixture containing nickel. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and the other organic compound is preferably 1: 0.5-10: 0-10, more preferably 1: 1-3: 0-3, that is, the other organic compound may not be added at all.
In some embodiments, the nickel salt is selected from one or more of organic acid salts, carbonates, and basic carbonates of nickel, preferably organic acid salts of nickel without heteroatoms, more preferably acetates of the nickel without heteroatoms, wherein the heteroatoms refer to metal atoms other than the nickel. Nitrogen-containing compounds include, but are not limited to, hexamethylenetetramine.
In some embodiments, the poly-organic carboxylic acid includes, but is not limited to, one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid.
In some embodiments, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodiments, the alkaline earth metal solution is a solution containing a salt of an alkaline earth metal and/or a base, for example, magnesium chloride (MgCl)2) Solution, magnesium nitrate (Mg (NO)3)2) Solution, calcium chloride (CaCl)2) Solution, calcium nitrate (Ca (NO)3)2) Solution, barium chloride (BaCl)2) Solutions, and the like. The salt and/or base of the alkaline earth metal with the primaryThe mass ratio of the products after pyrolysis is 1: 1-100, preferably 1: 1.5 to 50, preferably 1: 1.5 to 20. When the amount of the alkaline earth metal-containing salt or base is too large, the catalytic performance of the finally formed nanocomposite is affected, and the activity is lowered.
In some embodiments, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-800 ℃, and preferably 300-600 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
The carbon-coated nickel nanocomposite is prepared by the method, a method of pyrolyzing a metal-organic framework compound (MOF) serving as a precursor is not adopted, the method needs to prepare a crystalline solid Material (MOF) with a periodic structure in a solvent at high temperature and high pressure, the condition for preparing MOFs is strict, the needed ligand is expensive, and the mass production is difficult; in addition, the composite material prepared by the method has imprecise cladding on the metal particles, and is remarkably different from the nano composite material in structure. The alkaline earth metal contained in the shell layer of the core-shell structure in the nano composite material can generate a synergistic effect with the core nickel nano particles, so that the catalytic performance is more excellent. The method for preparing the nano composite material is convenient for adjusting the nitrogen content and the oxygen content in the graphitized carbon layer in the preparation process, thereby conveniently adjusting the electronic characteristics of the nano composite material so as to be suitable for catalyzing different reactions.
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
Preparation example 1
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of L aqueous solution containing 0.5128g of magnesium nitrate, soaking for 24h, and drying the product at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 350 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 3h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: 88.68 at% carbon, 1.27 at% nickel, 5.67 at% oxygen, 3.56 at% nitrogen, and 0.82 at% magnesium.
As shown in fig. 1, the nanocomposite was placed in water as a suspension, a magnet was placed on the outside of the container, and after a period of time the nanocomposite was attracted to one side of the magnet, which was seen to be magnetic. The TEM image of the nanocomposite is shown in fig. 2, and it can be seen that a graphitized carbon layer is wrapped on the outer layer of the nickel nanoparticle to form a complete core-shell structure. As shown in fig. 3, the diffraction pattern of this material includes diffraction peaks (2 θ angle 25.9 °) of graphitic carbon and diffraction peaks (2 θ angles 44.37 °, 51.8 ° and 76.4 °) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 6.8nm by the scherrer equation.
The BET test showed that the specific surface area of the composite material was 173.4m2Per g, pore volume 0.296cm3Per g, wherein>2nm has a mesopore volume of 0.296cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 4a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 4b, which is a BJH pore size distribution curve of the nanocomposite, and it can be seen that the composite has two mesopore distribution peaks at 3.90nm and 15.03 nm.
Preparation example 2
(1) Weighing 10g of nickel acetate, 20g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker containing 100m L deionized water, stirring at 80 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of magnesium nitrate L containing 0.8589 into the carbon-coated nickel material, soaking the mixture for 24 hours, and then drying the mixture at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 70m L/min, heating to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 82.4 at%, the nickel content was 2.68 at%, the oxygen content was 9.26 at%, the nitrogen content was 4.09 at%, and the magnesium content was 1.57 at%.
From the TEM image (fig. 5) of this material it can be seen that: the outer layer of the nickel nano-particles is wrapped with a graphitized carbon layer to form a complete core-shell structure. Fig. 6 shows an X-ray diffraction pattern of the nanocomposite material in which diffraction peaks corresponding to carbon (25.9 ° 2 θ angle) and fcc Ni (44.5 °, 51.7 ° and 76.4 ° 2 θ angle) and nickel (hcp-Ni) of close-packed cubic structure (41.9 °, 44.4 °, 47.3 ° and 62.4 ° 2 θ angle) exist. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 13.4nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 142m2Per g, pore volume 0.221cm3Per g, wherein>Pore volume of 0.213cm at 2nm3In terms of/g, 96.3% of the total pore volume. Fig. 7 is a BJH pore size distribution curve of the nanocomposite, which has two mesopore distribution peaks at 3.65nm and 9.91 nm.
Comparative preparation example
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite.
The atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 90.47 at%, the nickel content was 1.38 at%, the oxygen content was 3.97 at%, and the nitrogen content was 4.18 at%.
Example 1
The composite material obtained in preparation example 1 is used as a catalyst for the reaction of preparing a target product alcohol compound by hydrogenation of a ketone compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.97g of acetone and 100m of L m of cyclohexane into a reaction kettle, and introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 6MPa, stirring and heating, heating to the preset reaction temperature of 100 ℃, stopping heating after the reaction is carried out for 12 hours, cooling to room temperature, discharging pressure, and opening the reaction kettle to take the product propanol for chromatographic analysis. The reactant conversion and mesh were calculated by the following formulaProduct selectivity of (a):
conversion-amount of reacted reaction mass/amount of added reaction × 100%
The selectivity is × 100% based on the mass of the target product/mass of the reaction product
After analysis, an acetone conversion of 100% and a propanol selectivity of 98.2% were obtained.
When the reaction proceeded for 300s, a sample was taken and subjected to chromatography to calculate the conversion of the reactant, and TOF of the catalyst was found to be 7.95 × 10 by the formula TOF (amount of reacted reactant substance)/(amount of catalytically active metal substance 300s)-3s-1。
Example 2
The nano composite material prepared in preparation example 1 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of the nano composite material, 0.34g of acetone and 30m of L m of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is controlled to be 3MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 150 ℃, the heating is stopped after the reaction is continued for 8 hours, the temperature is reduced to room temperature, the pressure is discharged, the reaction kettle is opened, the product propanol is taken out for chromatographic analysis, the conversion rate of reactants, the selectivity of the product and TOF are respectively calculated by the formula shown in example 1, the conversion rate of acetone is 99.4 percent, the selectivity of propanol is 99.5 percent, and the TOF is 8.1 × 10-3s-1。
Example 3
The nano composite material prepared in preparation example 1 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of the nano composite material, 0.52g of acetone and 50m of L m of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2And (3) controlling the pressure in the reaction kettle to be 3MPa, stirring and heating, heating to the preset reaction temperature of 200 ℃, stopping heating after continuously reacting for 2 hours, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out the product propanol for chromatographic analysis. The reactant conversion, product selectivity and TOF were calculated respectively by the formulas shown in example 1 to giveAcetone conversion 98.6%, propanol selectivity 99.1%, TOF 7.53 × 10-3s-1。
Example 4
The nano composite material prepared in preparation example 1 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of acetone and 50m of L g of water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 4MPa, stirring and heating, heating to the preset reaction temperature of 150 deg.C, continuously reacting for 6 hr, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle and taking out the product propanol, and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain acetone conversion rate of 96.9%, propanol selectivity of 98.9% and TOF of 8.56 × 10-3s-1。
Example 5
The nano composite material prepared in preparation example 1 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of the nano composite material, 0.34g of cyclohexanone and 30m of L m of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to preset reaction temperature of 200 deg.C, continuously reacting for 4 hr, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle and taking out cyclohexanol product to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using formula shown in example 1 to obtain cyclohexanone conversion rate of 100%, cyclohexanol selectivity of 99.1% and TOF of 8.24 × 10-3s-1。
Example 6
The nano composite material prepared in preparation example 2 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of the nano composite material, 0.34g of acetone and 30m of L m of cyclohexane into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Make contraryHeating the mixture to a predetermined reaction temperature of 150 ℃ under the condition that the pressure in the kettle is 3MPa, stirring and heating the mixture, keeping the reaction for 8 hours, stopping heating the mixture, cooling the mixture to room temperature, discharging the pressure, opening the reaction kettle, taking out the product propanol, and carrying out chromatographic analysis on the product propanol, wherein the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in example 1 to obtain the acetone conversion rate of 100 percent, the selectivity of the propanol of 99.4 percent and the TOF of 8.67 × 10-3s-1。
Comparative example
The nano composite material prepared by the comparative preparation example is used for the hydrogenation reduction reaction of the ketone compound as a catalyst, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 1.97g of acetone and 100m of L m of cyclohexane were added to a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 6MPa, stirring and heating, heating to 100 deg.C, continuously making reaction for 12 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product propanol, making chromatographic analysis, respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain acetone conversion rate of 100%, propanol selectivity of 97.7% and TOF of 4.51 × 10-3s-1。
It can be seen from the above examples and comparative examples that the nanocomposite of the present invention has a good catalytic effect when used as a catalyst for catalyzing a catalytic hydrogenation reaction of a ketone compound, and compared with a catalyst containing no alkaline earth metal, the nanocomposite containing carbon coated nickel containing alkaline earth metal not only enables the catalytic reaction to have a high conversion rate and a high product selectivity, but also has a higher catalytic reaction rate and a better catalytic performance.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims (12)

1. A method for synthesizing alcohol compounds comprises the following steps:
the carbon-coated nickel nano composite material containing alkaline earth metal is used as a catalyst to catalyze ketone compounds to carry out hydrogenation reduction reaction in a hydrogen atmosphere;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
2. The method of claim 1, wherein the ketone compound is an aliphatic ketone, an alicyclic ketone, or an aromatic ketone.
3. The synthesis process according to claim 2, the ketone compound being selected from acetone or cyclohexanone.
4. The synthesis process according to claim 1, wherein the catalyst represents from 1% to 50%, preferably from 5% to 30%, of the mass of the ketone compound.
5. The synthesis process of claim 1, wherein the hydrogenation reduction reaction temperature is from 100 ℃ to 200 ℃.
6. The synthesis process according to claim 1, wherein the pressure of the hydrogen is from 3MPa to 6 MPa.
7. The synthesis method according to claim 1, wherein the hydrogenation reduction reaction is carried out after the catalyst and the ketone compound are mixed in a solvent, and the solvent is selected from one or more of alcohols, ethers, alkanes and water.
8. The method of synthesizing according to any one of claims 1 to 7, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
9. The method of synthesizing as defined in claim 8 wherein the nanocomposite is a mesoporous material having two or more mesopore distribution peaks.
10. The method of synthesis according to claim 8, wherein the mesoporous material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
11. The method of claim 1, wherein the alkaline earth metal comprises 0.1 at% to 3 at%, carbon comprises 65 at% to 95 at%, nickel comprises 0.1 at% to 10 at%, oxygen comprises 1 at% to 20 at%, and nitrogen comprises 1 at% to 10 at%, in terms of atomic percentage.
12. The method of synthesis according to any one of claims 1 to 11, the alkaline earth metal being selected from one or more of beryllium, magnesium, calcium, strontium, barium and radium.
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CN105032424A (en) * 2015-06-05 2015-11-11 中国科学院化学研究所 Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst
CN105478755A (en) * 2016-01-13 2016-04-13 合肥工业大学 Method for preparing non-metallic element doped carbon coated metal nanoparticle magnetic composite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1346703A (en) * 2001-09-11 2002-05-01 中国石油天然气股份有限公司 Method for preparing sec-octanol by sec-octanone hydrogenation and nickel-containing catalyst thereof
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CN105032424A (en) * 2015-06-05 2015-11-11 中国科学院化学研究所 Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst
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