CN111470990A - Synthesis method of aminophenol compound - Google Patents

Synthesis method of aminophenol compound Download PDF

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Publication number
CN111470990A
CN111470990A CN201910063256.XA CN201910063256A CN111470990A CN 111470990 A CN111470990 A CN 111470990A CN 201910063256 A CN201910063256 A CN 201910063256A CN 111470990 A CN111470990 A CN 111470990A
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nitrophenol
alkaline earth
earth metal
nickel
catalyst
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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
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • B01J35/23—
    • B01J35/33—
    • B01J35/398—
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • B01J35/69—

Abstract

The invention provides a synthesis method of an aminophenol compound, which comprises the following steps: the method comprises the following steps of (1) catalyzing a nitrophenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst; 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 aminophenol compounds by hydrogenation reduction of the nitrophenol compounds and has excellent activity, selectivity and safety.

Description

Synthesis method of aminophenol compound
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a synthesis method of an aminophenol compound.
Background
The aminophenol compounds can be widely applied to the dye industry, the medicine industry and the perfume intermediates. For example, p-aminophenol is an organic chemical intermediate with wide application, is mainly used for producing medicines, dyes, antioxidants, developers and the like, is also an alcohol compound which is an intermediate of disperse dyes, acid dyes, direct dyes, sulfur dyes and fur dyes, 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.
Currently, there are three main methods for industrially producing p-aminophenol: nitrobenzene hydrogenation reduction method, p-nitrophenol iron powder reduction method and p-nitrophenol hydrogenation reduction method. Among them, the p-nitrophenol hydrogenation reduction method is a widely applied process. The catalyst for catalytic hydrogenation reaction is mainly noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh) and non-noble metal catalysts such as copper (Cu), nickel (Ni), lead (Zn) and molybdenum (Mo). However, in practical application, the noble metal catalyst has too high cost, and the loss of noble metal has great harm to the environment, so the application in industrial production is limited; non-noble metal supported catalysts also have a series of problems, such as easy agglomeration in the preparation process, easy elution in the catalytic hydrogenation process, poor stability, greater potential safety hazard and the like.
Therefore, it is desirable to provide a new method for synthesizing aminophenol compounds, which overcomes the above problems.
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 aminophenol compounds, which adopts a carbon-coated nickel 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, a 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 the aminophenol compounds by hydrogenation reduction of the nitrophenol compounds and has excellent activity, selectivity and safety.
The invention provides a synthesis method of an aminophenol compound, which comprises the following steps:
the method comprises the following steps of (1) catalyzing a nitrophenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst;
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 an embodiment of the present invention, the benzene ring of the nitrophenol compound further comprises a substituent selected from the group consisting of C1-20One or more of alkyl, cycloalkyl and aryl.
According to an embodiment of the present invention, wherein the nitrophenol compound is selected from one or more of o-nitrophenol, p-nitrophenol, m-nitrophenol and 4, 5-dimethyl-2-nitrophenol.
According to one embodiment of the invention, the catalyst is present in an amount of 1% to 50%, preferably 5% to 30%, by weight of the nitrophenol compounds.
According to one embodiment of the present invention, wherein the temperature of the hydrogenation reduction reaction is 50 ℃ to 120 ℃.
According to one embodiment of the present invention, wherein the pressure of the hydrogen gas is 0.5 to 2 MPa.
According to one embodiment of the present invention, the hydrogenation reduction reaction is performed after the catalyst and the nitrophenol 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.
According to an embodiment of the present invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 2 at%, in terms of atomic percentage; 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 4 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, 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%.
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 aminophenol compound provided by the invention uses the carbon-coated nickel nano composite material containing alkaline earth metal as the catalyst to carry out hydrogenation reduction on the nitrophenol compound, and because the catalyst material contains a graphitized carbon layer/metal core-shell structure, no pore channel or defect which can enable reactants to approach the center of nickel exists, so that the nickel material of the inner core is very stable, free from spontaneous combustion, resistant to acid corrosion and low in danger, and is suitable for storage and transportation, thereby ensuring the use safety of the composite material. The catalyst material disclosed by the invention is very stable, free of spontaneous combustion, resistant to oxidation and acid corrosion, low in risk and suitable for storage and transportation, so that the safety of the aminophenol synthesis process is ensured.
The carbon-coated nickel nanocomposite containing alkaline earth metal shows good repeatability, high activity and high selectivity in the reaction of catalytically reducing nitrophenol compounds into aminophenol compounds, and the nickel coated in the graphitized carbon layer has a penetration 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 technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The numerical ranges of the invention include the numbers defining the range. The phrase "comprising" is used herein as an open-ended term substantially equivalent to the word "including, but not limited to," and the phrase "comprising" has a corresponding meaning. As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a thing" includes more than one such thing, including all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings. 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.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Term(s) for
The term "alkyl" is defined herein as a straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and the like.
The term "cycloalkyl" is defined herein as an alkyl group connected by single bonds and constituting a ring, such as cyclohexyl.
The term "aryl" is defined herein as a functional group or substituent derived from a simple aromatic ring, such as benzyl.
The term "nitrophenol-type compound" refers to a compound in which at least one hydrogen atom on the benzene ring is substituted with a nitro group and at least another hydrogen atom is substituted with a hydroxyl group, and includes nitrophenols having no substituent other than hydroxyl and nitro groups on the benzene ring and nitrophenols having at least one hydrogen atom other than hydroxyl and nitro groups on the benzene ring substituted with a substituent other than hydroxyl and nitro groups.
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 size in the range of 2nm 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: the acceleration voltage was 200 kV.
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, the composition of the gas is obtained by on-line gas chromatography analysis, and the chromatographic type is as follows: an Agilent GC7890B was used,accuracy of 10-6. And introducing test gas into the chromatogram from the sample inlet, separating by using a chromatographic column, and calculating the percentage of each gas component by integrating each chromatographic peak.
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 an aminophenol compound, which comprises the following steps:
the method comprises the following steps of (1) catalyzing a nitrophenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst; the chemical reaction equation is exemplified as follows,
Figure BDA0001954857070000061
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 nitrobenzene compound further comprises a substituent R on the benzene ring, wherein the substituent R is selected from C1-20The above-mentioned substitution may be mono-or poly-substituted, such as o-nitrophenol, p-nitrophenol, m-nitrophenol or 4, 5-dimethyl-2-nitrophenol.
In some embodiments, the catalyst accounts for 1% to 50%, preferably 5% to 30% of the mass of the nitrophenol compounds.
In some embodiments, the temperature of the hydrogenation reduction reaction is generally 50 ℃ to 120 ℃.
In some embodiments, the pressure of the hydrogen gas therein is generally in the range of 0.5MPa to 2 MPa.
In some embodiments, the hydrogenation reduction reaction is performed after the catalyst and the nitrophenol 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.
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 (not in contact with the outside) with the graphitized carbon layer ", and" nickel nanoparticles in contact with the outside and confined regions ". The surface of the graphitized carbon layer doped with 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 of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in a pore size range of 2nm to 7nm and a pore size range of 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 0.30cm3/g～0.50cm3/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 an embodiment of the present invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, preferably 0.2 at% to 2 at%, in terms of atomic percentage; 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 4 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, 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%.
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), 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 the alkaline earth metal, and then carrying out drying treatment; 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.
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-containing solution is an alkaline earth metal-containing salt and/or base solution, e.g., 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 mass ratio of the alkaline earth metal salt and/or alkali to the product after primary 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 method for preparing the carbon-coated nickel 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>The mesoporous volume of 2nm is 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 rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite material, wherein the atomic percentage content of elements in the nanocomposite material is respectively 90.47at percent of carbon, 1.38at percent of nickel, 3.97at percent of oxygen and 4.18at percent of nitrogen, which are determined by X-ray photoelectron spectroscopy (XPS).
Example 1
The composite material obtained in the preparation example 1 is used as a catalyst for the reaction of preparing a target product aminophenol compound by hydrogenation of a nitrophenol compound reactant, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.95g of p-nitrophenol and 100m of L ethanol into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2The pressure in the reaction kettle is made to be 2MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 50 ℃, the heating is stopped after the preset reaction time of 3 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product p-aminophenol is taken out for color developmentAnd (4) performing spectrum 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, the conversion rate of the p-nitrophenol is 100 percent, and the selectivity of the p-aminophenol is 99.2 percent.
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 9.11 × 10, which was obtained by the formula TOF (amount of reacted reactant substance)/(amount of catalytically active metal substance 300s)-3s-1。
Example 2
The nanocomposite prepared in preparation example 1 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of p-nitrophenol and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 1MPa, stirring and heating, heating to 60 deg.C, continuously making reaction for 2 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product p-aminophenol and making chromatographic analysis, and respectively calculating conversion rate of reactant, product selectivity and TOF by using formula shown in example 1 to obtain p-nitrophenol conversion rate of 100%, p-aminophenol selectivity of 99.4% and TOF of 8.62 × 10-3s-1。
Example 3
The nanocomposite prepared in preparation example 1 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of p-nitrophenol and 50m of L ethanol 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 0.5MPa, the temperature is raised by stirring, the temperature is raised to 120 ℃ of the preset reaction temperature, the heating is stopped after the reaction is continued for 1 hour, the pressure is discharged after the temperature is reduced to the room temperature, and the reaction is openedThe product, p-aminophenol, was taken out from the autoclave and subjected to chromatographic analysis by calculating the conversion of the reactant, the selectivity of the product and TOF, respectively, using the formulas shown in example 1, to obtain p-nitrophenol at 100%, p-aminophenol at 99.2% and TOF at 8.56 × 10-3s-1。
Example 4
The nanocomposite prepared in preparation example 1 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.49g of p-nitrophenol and 50m 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 2MPa, stirring and heating, heating to preset reaction temperature of 100 deg.C, continuously making reaction for 1 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product p-aminophenol and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitrophenol conversion rate of 100%, p-aminophenol selectivity of 99.0% and TOF of 9.68 × 10-3s-1。
Example 5
The nanocomposite prepared in preparation example 1 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of o-nitrophenol and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is enabled to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 60 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product o-aminophenol 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 o-nitrophenol is 100 percent, the selectivity of the o-aminophenol is 99.4 percent, and the TOF is 9.-3s-1。
Example 6
The nanocomposite prepared in preparation example 1 is used as a catalyst for olefin hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of m-nitrophenol and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 1MPa, stirring and heating, heating to 60 deg.C, continuously making reaction for 2 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product m-aminophenol to make chromatographic analysis, and respectively calculating conversion rate of reactant, product selectivity and TOF by using formula shown in example 1 to obtain m-nitrophenol conversion rate of 100%, m-aminophenol selectivity of 99.3% and TOF of 8.70 × 10-3s-1。
Example 7
The nanocomposite prepared in preparation example 1 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of 4, 5-dimethyl-2-nitrophenol and 30m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is made to be 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 60 ℃, the heating is stopped after the reaction is continued for 2 hours, the temperature is reduced to the room temperature, the pressure is discharged, the reaction kettle is opened, the product 4, 5-dimethyl-2-aminophenol is taken out for chromatographic analysis, the conversion rate of a 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 4, 5-dimethyl-2-nitrophenol is 100 percent, the selectivity of the 4, 5-dimethyl-2-aminophenol is 99.5 percent, and the TOF is 9.11 × 10-3s-1。
Example 8
The nano composite material prepared in preparation example 2 is used as a catalyst for a nitrophenol compound hydrogenation reduction reaction, and the specific experimental steps are as follows:
adding 0.2g of nano composite material, 0.67g of p-nitrophenol and 50m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is 1MPa, the temperature is raised by stirring, the temperature is raised to the preset reaction temperature of 60 ℃, the heating is stopped after the reaction is continued for 2 hours, and the temperature is reduced to the room temperatureThe reaction vessel was vented and the product p-aminophenol was taken out for chromatographic analysis by calculating the conversion of the reactant, the selectivity of the product and TOF by the formulas shown in example 1, respectively, to obtain a conversion of p-nitrophenol of 100%, a selectivity of p-aminophenol of 99.3% and a TOF of 8.83 × 10-3s-1。
Comparative example
The nano composite material prepared by the comparative preparation example is used for hydrogenation reduction reaction of nitrophenol compounds as a catalyst, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 1.95g of p-nitrophenol and 100m of L ethanol into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 2MPa, stirring and heating, heating to 50 deg.C, continuously making reaction for 3 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out product p-aminophenol and making chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain p-nitrophenol conversion rate of 100%, p-aminophenol selectivity of 99.1% and TOF of 5.62 × 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 nitrophenol 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 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 aminophenol compounds, comprising:
the method comprises the following steps of (1) catalyzing a nitrophenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst;
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 synthesis method according to claim 1, wherein the benzene ring of the nitrophenol compound further comprises a substituent selected from C1-20One or more of alkyl, cycloalkyl and aryl.
3. The method of synthesis of claim 1, wherein the nitrophenol compounds are selected from one or more of o-nitrophenol, p-nitrophenol, m-nitrophenol and 4, 5-dimethyl-2-nitrophenol.
4. The synthesis process according to claim 1, wherein the catalyst represents from 1% to 50%, preferably from 5% to 30%, by mass of the nitrophenol compounds.
5. The synthesis process of claim 1, wherein the hydrogenation reduction reaction temperature is from 50 ℃ to 120 ℃.
6. The synthesis process according to claim 1, wherein the pressure of the hydrogen is between 0.5MPa and 2 MPa.
7. The synthesis method according to claim 1, wherein the catalyst and the nitrophenol compound are mixed in a solvent and then subjected to hydrogenation reduction reaction, wherein 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 is present at 0.1 at% to 3 at%, the carbon is present at 65 at% to 95 at%, the nickel is present at 0.1 at% to 10 at%, the oxygen is present at 1 at% to 20 at%, and the nitrogen is present at 1 at% to 10 at%, in 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.
CN201910063256.XA 2019-01-23 2019-01-23 Synthesis method of aminophenol compound Pending CN111470990A (en)

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