CN111470943A - Synthetic method of alcohol compound - Google Patents

Synthetic method of alcohol compound Download PDF

Info

Publication number
CN111470943A
CN111470943A CN201910063082.7A CN201910063082A CN111470943A CN 111470943 A CN111470943 A CN 111470943A CN 201910063082 A CN201910063082 A CN 201910063082A CN 111470943 A CN111470943 A CN 111470943A
Authority
CN
China
Prior art keywords
alkali metal
carbon
nickel
composite material
ketone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910063082.7A
Other languages
Chinese (zh)
Inventor
谢婧新
宗明生
荣峻峰
吴耿煌
于鹏
林伟国
纪洪波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201910063082.7A priority Critical patent/CN111470943A/en
Publication of CN111470943A publication Critical patent/CN111470943A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B01J35/33—
    • B01J35/40—
    • B01J35/50—
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • B01J35/69—
    • 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

Abstract

The invention provides a synthesis method of an alcohol compound, which comprises the following steps: the carbon-coated nickel nano composite material containing alkali 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 alkali metal and oxygen, and the inner core is nickel nano particles. The method adopts the carbon-coated nickel-containing nano composite material containing alkali metal as the catalyst, the carbon material and the nickel nano particles act synergistically to produce a good catalytic effect, the alkali 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, solvents, dehydrating agents, anti-emulsifying agents, extracting agents such as grease, spice, antibiotics, 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 corresponding alcohol compounds by the catalytic hydrogenation of ketone compounds has very important significance. Most of the acetone is industrially obtained by cumene peroxidation and is co-produced with phenol. As the demand of phenol is increased, a large amount of acetone is produced in a co-production manner, and the acetone is excessive, so that 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 occupies an important place in the catalytic hydrogenation of ketone compounds to generate corresponding alcohol 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 nanocomposite containing alkali metal as a catalyst, wherein the nanocomposite uses a graphitized carbon layer containing alkali metal and oxygen to coat nickel nanoparticles to form a core-shell structure, a carbon material and the nickel nanoparticles act synergistically to produce a good catalytic effect, and the alkali metal of a shell layer further synergistically improves the catalytic performance of the material, so that the alcohol compounds are synthesized by hydrogenation reduction of ketone compounds, and the alcohol compounds have excellent activity, selectivity and safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a synthesis method of an alcohol compound, which comprises the following steps:
the carbon-coated nickel nano composite material containing alkali 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 alkali metal 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 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 present invention, wherein the alkali metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 3 at%, in atomic percent; the carbon content is 80 at% to 95 at%, preferably 84 at% to 92 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
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 alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
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 alkali 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 aniline compound is ensured.
The carbon-coated nickel nanocomposite containing alkali 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 alkali metal loaded on the surface of the graphitized carbon layer is influenced, a synergistic effect is exerted, and 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 TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 2 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIGS. 3a and 3b show N of the alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1, respectively2Adsorption-desorption, etcTemperature line and BJH pore size distribution curve;
FIG. 4 is a TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIG. 5 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIGS. 6a and 6b respectively show N of the alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 22Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 7 is a TEM image of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3;
FIG. 8 is an XRD pattern of an alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3;
fig. 9 shows the BJH pore size distribution curve of the alkali metal-containing carbon-coated nickel nanocomposite prepared in preparation example 3.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments thereof, which are illustrated in the accompanying drawings, and it should be understood that the detailed description herein is merely illustrative and explanatory of the invention and is not restrictive thereof 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 the combination is considered by those skilled in the art 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 specified.
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" in 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 diameter of less than 2nm are defined as micropores and pores with a pore diameter 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 "alkali metal" and "oxygen" in the "graphitized carbon layer containing alkali metal and oxygen" refer to alkali metal elements and oxygen elements, wherein the "alkali metal content" of the nanocomposite refers to the content of the alkali metal elements, and the "oxygen content" refers to the content of the oxygen elements, and specifically means that the alkali metal elements and the oxygen elements exist in various forms in the graphitized carbon layer formed in the preparation process of the carbon-coated nanocomposite, wherein the "alkali metal content" is the total content of all forms of alkali metal elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkali metal content" and "oxygen content" were determined 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 reactant converted per active metal atom per unit time, 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 (Ribenseudu), 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, and the X-ray photoelectron spectrum analyzer is used under the condition that an excitation source is monochromized A1KαX-ray, power 330W, base vacuum 3 × 10 for analytical testing-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/(Bcos 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 alkali 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 BDA0001954805150000061
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 alkali metal 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 alkali metal and oxygen", a "nickel nanoparticle that is tightly coated with (not in contact with) the graphitized carbon layer", and a "nickel nanoparticle that can be in contact with and confined to the outside". The carbon material has catalytic activity, and the nickel coated in the graphitized carbon layer has penetration effect, so that the electronic state of the alkali metal loaded on the surface of the graphitized carbon layer is influenced, and the 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 the composite materials manufactured in multiple batches 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 0.05 cm3/g～1.25cm3Per g, also may be 0.10cm3/g～0.30cm3/g。
The nanocomposites according to the invention, in some embodiments, have specific surface areas 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 of the invention, in some embodiments, the carbon layer of the composite is doped with an oxygen element and not with a nitrogen element.
According to the nanocomposite material of the invention, in some embodiments, the carbon layer of the composite material is doped with only oxygen, and is not doped with other elements than hydrogen and oxygen.
In some embodiments, wherein the alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
In some embodiments, wherein the alkali metal content is from 0.1 at% to 3 at%, preferably from 0.2 at% to 3 at%, as measured by XPS; the carbon content is 80 at% to 95 at%, preferably 84 at% to 92 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 15 at%, preferably 5 at% to 12 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to the nanocomposite material of the present invention, the graphitized carbon layer is doped with oxygen. The oxygen content can be adjusted by additionally introducing an oxygen-containing compound, such as a polyol, during the manufacturing process. The catalytic performance of the graphitized carbon layer can be adjusted by adjusting the oxygen content in the nano composite material, so that the graphitized carbon layer is suitable for catalyzing different reactions. In some embodiments, the oxygen content in the nanocomposite is less than 15.0%, preferably 5% to 12%, by mass.
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 alkali metal is selected from one or more of lithium (L i), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting nickel salt and polybasic organic carboxylic acid 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 the solution containing alkali metal, and then drying;
and putting the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated nickel nanocomposite containing the alkali metal.
Specifically, the precursor is a water-soluble mixture, which means that nickel salt and polybasic organic carboxylic acid are dissolved into a homogeneous solution in a solvent such as water and/or ethanol, and then the solvent is directly removed to obtain the precursor containing nickel. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
In some embodiments, wherein the nickel salt is selected from one or more of an organic acid salt, a carbonate salt, and a basic carbonate salt of nickel, the organic acid salt of nickel is preferably an organic carboxylate salt of nickel that is free of heteroatoms, more preferably an acetate salt of the nickel that is free of heteroatoms, wherein the heteroatoms refer to metal atoms other than the nickel.
In some embodiments, wherein the poly-organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid. Wherein the mass ratio of the nickel salt to the polybasic organic carboxylic acid is 1: 0.1-10, preferably 1: 0.5-5, and more preferably 1: 0.8-3.
In some embodiments, the method further comprises mixing the nickel salt, the polybasic organic carboxylic acid and other organic compounds except the nickel salt, the polybasic organic carboxylic acid and the 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 poly-organic carboxylic acid and the other organic compound is 1: 0.5-10: 0-10, preferably 1: 1-3: 0-3.
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 30min to 300 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 alkali metal-containing solution is an alkali metal salt and/or base-containing solution, such as, for example, a potassium bicarbonate solution, a potassium hydroxide solution, a sodium carbonate solution, and the like. The mass ratio of the alkali metal salt and/or alkali to the product after primary pyrolysis is 1: 2-100, preferably 1: 2-50, and more preferably 1: 2-20. When the amount of alkali metal-containing salt or alkali is excessive, the core-shell structure of carbon-coated nickel is easily destroyed in the secondary pyrolysis process, and the nickel in the core is exposed to air and spontaneously ignited.
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 80-500 ℃, and preferably 100-400 ℃; 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 coating of the metal particles, and is remarkably different from the nano composite material in structure. The alkali 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 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 will be described in further detail below with reference to specific embodiments thereof, which are illustrated in the accompanying drawings, and it should be understood that the detailed description herein is merely illustrative and explanatory of the invention and is not restrictive thereof in any way.
Preparation example 1
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30m L of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution 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 zone 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) And (3) weighing 2g of the material obtained in the step (2), adding 4ml of aqueous solution containing 0.1538 potassium bicarbonate, stirring for 24 hours at room temperature, and drying to obtain the carbon-coated transition nickel material containing potassium.
(4) And (3) placing the 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 100m L/min, heating to 400 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature under the nitrogen atmosphere to obtain the carbon-coated nickel nano composite material containing potassium.
Characterization of the materials:
the atom percentage contents of the elements contained in the nano composite material are respectively as follows through X-ray photoelectron spectroscopy (XPS) determination: the carbon content was 84.9 at%, the nickel content was 6.34 at%, the oxygen content was 8.36 at%, and the potassium content was 0.4 at%.
A TEM image of the material is shown in fig. 1, and it can be seen that the material contains a carbon-coated nickel structured nanocomposite. The XRD pattern of this material is shown in fig. 2, and it can be seen that the diffraction pattern of this material includes diffraction peaks (2 θ angle 25.9 °) of graphite carbon and diffraction peaks (2 θ angles 44.5 °, 51.7 ° and 76.4 °) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 5.2nm by the scherrer equation.
The BET test shows that the specific surface area of the composite material is 151m2Per g, pore volume 0.365cm3Per g, wherein>The mesoporous volume of 2nm is 0.365cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 3a shows N of the composite material2An adsorption-desorption isotherm is shown in fig. 3b, which is a BJH pore size distribution curve of the composite material, and it can be seen that the composite material has two mesopore distribution peaks at 3.77nm and 12.19 nm.
Preparation example 2
(1) 10g of nickel acetate and 20g of citric acid were weighed into a beaker containing 50m L of deionized water, stirred at 80 ℃ to obtain a homogeneous solution, and continuously heated and evaporated 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 zone 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 material obtained in the step (2), adding 15M of L1M KOH aqueous solution, stirring at room temperature for 24h, filtering, and finally drying at 120 ℃ to obtain the potassium-containing carbon-coated nickel material.
(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 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite containing potassium.
Characterization of the materials:
the atom percentage contents of the elements contained in the nano composite material are respectively as follows through X-ray photoelectron spectroscopy (XPS) determination: 91.55 at% of carbon, 1.86 at% of nickel, 6.41 at% of oxygen and 0.18 at% of potassium.
The TEM image of the nanocomposite is shown in fig. 4, 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. The X-ray diffraction pattern of the nanocomposite is shown in fig. 5, in which diffraction peaks corresponding to carbon (2 θ angle of 25.9 °) and fcc Ni (2 θ angles of 44.5 °, 51.7 ° and 76.4 °) were present in the X-ray diffraction pattern of the material, and the average particle diameter of the carbon-coated nickel nanoparticles was calculated to be 31.3nm by scherrer's equation.
The BET test shows that the specific surface area of the material is 168m2Per g, pore volume 0.342cm3Per g, wherein>Pore volume of 0.32cm at 2nm3(ii) in terms of/g, 93.6% of the total pore volume. FIGS. 6a and 6b show N of the nanocomposite, respectively2According to the adsorption-desorption isotherm and the BJH pore size distribution curve, two mesoporous distribution peaks exist at 3.38nm and 8.94nm of the composite material.
Preparation example 3
(1) Weighing 10g of nickel acetate and 10g of terephthalic acid, adding the nickel acetate and the terephthalic acid into 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a precursor.
(2) And (2) placing the precursor in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen at a flow rate of 100m L/min, heating to 650 ℃ at a speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the material containing the carbon-coated nickel.
(3) 2g of the material from step (2) were weighed, 4m of L containing 0.2765g of aqueous sodium carbonate solution were added, and the mixture was soaked at room temperature for 24 hours, and then the product was dried at 120 ℃.
(4) And (3) placing the 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 200 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated nickel nano composite material containing sodium.
Characterization of the materials:
the atom percentage contents of the elements contained in the nano composite material are respectively as follows through X-ray photoelectron spectroscopy (XPS) determination: the carbon content was 82.27 at%, the nickel content was 4.34 at%, the oxygen content was 11.69 at%, and the sodium content was 1.7 at%.
The TEM image of the nanocomposite is shown in fig. 7, which shows that the outer layer of the nickel nanoparticle is coated with a graphitized carbon layer to form a complete core-shell structure. The X-ray diffraction pattern of this nanocomposite material is shown in FIG. 8, and there are diffraction peaks (2. theta. angle of 25.9 ℃) corresponding to carbon and fcc Ni (2. theta. angle of 44.5 °, 51.7 ° and 76.4 °) in the X-ray diffraction pattern of this material. The average particle size of the carbon-coated nickel nanoparticles was 27.6nm as calculated by the scherrer equation.
The BET test shows that the specific surface area of the material is 164m2Per g, pore volume 0.33cm3Per g, wherein>Pore volume of 0.33cm at 2nm3(ii) in terms of/g, representing 100% of the total pore volume. Fig. 9 shows the BJH pore size distribution curve of the material, and it can be seen that there are two mesopore distribution peaks at 4.01nm and 18.9nm in the material.
Comparative preparation example 1
(1) Weighing 10g of nickel acetate and 10g of citric acid, adding the nickel acetate and the citric acid into a beaker containing 30m L of deionized water, stirring the mixture at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating the homogeneous solution to dryness to obtain a solid precursor.
(2) And (2) placing the solid 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 nanocomposite.
Characterization of the materials:
the atom percentage contents of the elements contained in the nano composite material are respectively as follows through X-ray photoelectron spectroscopy (XPS) determination: the carbon content was 88.26 at%, the nickel content was 5.4 at%, and the oxygen content was 6.36 at%.
Comparative preparation example 2
The same as preparation example 1, except that 1.5g of potassium bicarbonate was added in step (3), impregnated, and baked at 400 ℃ to obtain a potassium-containing carbon-coated nickel composite material which was flammable in air.
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, 1.96g 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 the target product selectivity were calculated by the following formulas:
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 98.4% 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 8.12 × 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 hydrogenation reduction reaction of ketone compounds, 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 again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to the preset reaction temperature of 150 deg.C, continuously making reaction for 8 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product propanol to make chromatographic analysis so as to obtain the invented product with the conversion rate of reactant, selectivity of product and TOF, respectively, and the conversion rate of acetone is 99.2%, selectivity of propanol is 99.3% and TOF is 7.93 × 10-3s-1。
Example 3
The nano composite material prepared in preparation example 1 is used as a catalyst for hydrogenation reduction reaction of ketone compounds, 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 again2The pressure in the reaction kettle is controlled to be 3MPa, the temperature is raised to the preset reaction temperature of 200 ℃ by stirring, the heating is stopped after the reaction is continued for 2 hours, the pressure is discharged after the reaction is reduced to the room temperature, the reaction kettle is opened, the product propanol is taken out for chromatographic analysis, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, the conversion rate of the acetone is 98.4 percent, the selectivity of the propanol is 99.0 percent, and the TOF is 8.25 × 10-3s-1。
Example 4
The nano composite material prepared in preparation example 1 is used as a catalyst for hydrogenation reduction reaction of ketone compounds, 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 so as to obtain the invented product with acetone conversion rate of 97.1%, propanol selectivity of 98.9% and TOF of 7.14 × 10-3s-1。
Example 5
The nano composite material prepared in preparation example 1 is used as a catalyst for hydrogenation reduction reaction of ketone compounds, 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 making reaction for 4 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out cyclohexanol product to make chromatographic analysis so as to obtain the invented product with reactant conversion rate of 100%, cyclohexanol selectivity of 99.3% and TOF of 8.26 × 10-3s-1。
Example 6
The nano composite material prepared in preparation example 2 is used as a catalyst for hydrogenation reduction reaction of ketone compounds, 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 again2And (3) controlling the pressure in the reaction kettle to be 3MPa, stirring and heating, heating to the preset reaction temperature of 150 ℃, continuing to react for 8 hours, stopping heating, reducing the temperature to room temperature, discharging pressure, opening the reaction kettle, and taking out the product propanol for chromatographic analysis. The conversion of the reactant, the selectivity of the product and the TOF were calculated respectively by the formulas shown in example 1 to obtain a conversion of acetone of 100% and propanolSelectivity 99.6%, TOF 8.61 × 10-3s-1。
Example 7
The nano composite material prepared in preparation example 3 is used as a catalyst for hydrogenation reduction reaction of ketone compounds, 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 again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to predefined reaction temperature of 150 deg.C, continuously making reaction for 8 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product propanol to make chromatographic analysis so as to obtain the invented product with the conversion rate of reactant, selectivity of product and TOF, respectively, and obtaining acetone conversion rate of 100%, selectivity of propanol of 99.1% and TOF of 8.28 × 10-3s-1。
Comparative example
The nanocomposite prepared in comparative preparation example 1 is used as a catalyst for a ketone compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 1.96g 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 preset reaction temperature of 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, and respectively calculating conversion rate of reactant, product selectivity and TOF by using the formula shown in example 1 to obtain acetone conversion rate of 100%, propanol selectivity of 97.3% and TOF of 5.11 × 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 alkali metal, the nanocomposite containing carbon coated nickel containing alkali metal not only enables the catalytic reaction to have a high conversion rate and product selectivity, but also has a higher catalytic reaction rate and 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 alkali 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 alkali metal 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 alkali metal is present at 0.1 at% to 3 at%, the carbon is present at 80 at% to 95 at%, the nickel is present at 0.1 at% to 10 at%, and the oxygen is present at 1 at% to 15 at%, in terms of atomic percentage.
12. The synthesis method of any one of claims 1-11, wherein the alkali metal is selected from one or more of lithium, sodium, potassium, rubidium, cesium, and francium.
CN201910063082.7A 2019-01-23 2019-01-23 Synthetic method of alcohol compound Pending CN111470943A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910063082.7A CN111470943A (en) 2019-01-23 2019-01-23 Synthetic method of alcohol compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910063082.7A CN111470943A (en) 2019-01-23 2019-01-23 Synthetic method of alcohol compound

Publications (1)

Publication Number Publication Date
CN111470943A true CN111470943A (en) 2020-07-31

Family

ID=71743283

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910063082.7A Pending CN111470943A (en) 2019-01-23 2019-01-23 Synthetic method of alcohol compound

Country Status (1)

Country Link
CN (1) CN111470943A (en)

Citations (4)

* 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 Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni
CN103191746A (en) * 2013-03-20 2013-07-10 北京化工大学 Carbon supported core-shell structure nano metal catalyst as well as preparation method and application thereof
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

Patent Citations (4)

* 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 Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni
CN103191746A (en) * 2013-03-20 2013-07-10 北京化工大学 Carbon supported core-shell structure nano metal catalyst as well as preparation method and application thereof
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BO TANG等: "MOF-derived Ni-based nanocomposites as robust catalysts for chemoselective hydrogenation of functionalized nitro compounds", 《RSC ADV.》 *

Similar Documents

Publication Publication Date Title
CN109305881B (en) Synthetic method of alcohol compound
CN111468117A (en) Carbon-coated transition metal nanocomposite containing alkaline earth metal and preparation method and application thereof
CN111470985A (en) Synthetic method of aminoanisole compound
CN111470949A (en) Synthesis method of cyclohexanol compound
CN111468126A (en) Carbon-coated transition metal nanocomposite containing alkali metal, and preparation method and application thereof
CN111470947A (en) Synthesis method of cyclohexanol compound
CN111470950A (en) Synthesis method of cyclohexanol compound
CN111470948A (en) Synthesis method of cyclohexanol compound
CN111468157A (en) Synthesis method of aminophenol compound
CN111468155A (en) Synthetic method of alcohol compound
CN111470982A (en) Synthesis method of aniline compound
CN111470943A (en) Synthetic method of alcohol compound
CN111470978A (en) Synthesis method of halogenated aniline
CN111468119A (en) Carbon-coated transition metal nanocomposite containing alkaline earth metal and preparation method and application thereof
CN111470945A (en) Synthetic method of alcohol compound
CN111470989A (en) Synthesis method of aminophenol compound
CN111468125A (en) Synthetic method of alcohol compound
CN111470929A (en) Synthesis method of naphthenic compound
CN111470942A (en) Synthetic method of alcohol compound
CN111470986A (en) Synthetic method of aminoanisole compound
CN111468156A (en) Synthetic method of alcohol compound
CN111470979A (en) Synthesis method of aniline compound
CN111470975A (en) Synthesis method of aniline compound
CN111470944A (en) Synthetic method of alcohol compound
CN111470930A (en) Synthesis method of naphthenic compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200731

RJ01 Rejection of invention patent application after publication