CN111468118A - Carbon-coated transition metal nanocomposite and preparation method and application thereof - Google Patents
Carbon-coated transition metal nanocomposite and preparation method and application thereof Download PDFInfo
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- CN111468118A CN111468118A CN201910063383.XA CN201910063383A CN111468118A CN 111468118 A CN111468118 A CN 111468118A CN 201910063383 A CN201910063383 A CN 201910063383A CN 111468118 A CN111468118 A CN 111468118A
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- nanocomposite
- transition metal
- hydrogenation
- carbon
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 70
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- 238000002360 preparation method Methods 0.000 title claims description 19
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- 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
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- 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
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- 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
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- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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Abstract
The invention provides a carbon-coated transition metal nanocomposite, which comprises a carrier and a core-shell structure loaded on the carrier, wherein a shell layer of the core-shell structure is a graphitized carbon layer containing oxygen, and an inner core of the core-shell structure is transition metal nanoparticles. The core-shell structure is constructed by taking the transition metal as the core, and the core-shell structure is loaded on the carrier to form the nano composite material, so that the mass transfer efficiency and the strength of the nano composite material are improved, the material has better particle morphology and less fine powder, and the nano composite material can be better applied to a fixed bed reactor. In addition, the nano composite material can also be a multi-level pore structure material with abundant mesopores or micropores and mesopores, and is favorable for better playing a role in more applications, particularly the applications in the field of catalysis.
Description
Technical Field
The invention relates to the field of carbon-coated metal composite materials, in particular to a carbon-coated transition metal nanocomposite material and a preparation method and application thereof.
Background
It has been found that nanocarbon catalysts, such as carbon fibers, nanodiamonds, carbon nanotubes, and (oxidized) graphene, are catalytically active for a series of reactions, such as catalytic direct dehydrogenation, oxidative dehydrogenation, halogenation, hydroxylation, alkylation of hydrocarbons, and liquid-phase oxidation and condensation reactions of aldehydes and ketones. The active sites of the nanocarbon catalyst are mainly structural defects and heteroatom functional groups of the carbon material, so in order to improve the catalytic activity of the nanocarbon catalyst, the number of the structural defects and the number of the heteroatom functional groups need to be increased, but the stability of the material is reduced.
Transition metal nano materials are widely concerned due to excellent optical, electrical, magnetic and catalytic properties, but because of high activity of transition metal nano particles, the transition metal nano particles are easy to agglomerate or be oxidized and even spontaneously combust in the air, and the properties and the application of the materials are greatly influenced. Transition metal nanomaterials have high catalytic activity but poor stability, while nanocarbon materials have good chemical stability but need further improvement in catalytic activity, and if the two are combined in a proper manner, a new synergistic effect may be generated, so that they exhibit new unique properties.
At present, relevant documents for coating transition metals by carbon materials are reported, but various problems still exist in the prior materials in practical application, such as harsh manufacturing conditions, complex process, low coating rate, and not tight coating, the prior materials need to be treated by nitric acid when oxygen-containing groups are introduced, the carbon coating layer is easy to damage, adverse effects are caused to metal cores, and the like, and the prior materials cannot be suitable for industrial production and application. For example, a method of pyrolyzing a metal-organic framework compound (MOF) as a precursor, which requires a crystalline solid Material (MOF) having a periodic structure to be prepared in a solvent at high temperature and high pressure, generally has strict conditions for preparing MOFs, requires expensive ligands, and is difficult to mass-produce; in addition, the composite material prepared by the method has an imprecise coating of the metal particles. Also, for example, CN 105032424a is a catalyst for selective hydrogenation of aromatic nitro compounds, the method for coating metal particles in this document is pechini method (sol-gel method), which also requires preparation of solid coordination polymers in solvents, similar to MOF method, and the method also produces composite materials with tight coating of metal particles.
The mesoporous material generally has a large specific surface area and a relatively regular pore channel structure, so that the mesoporous material can play a better role in separation, adsorption and catalytic reaction of macromolecules and can be a microreactor for limited-domain catalysis. Due to the characteristics of high hydrothermal stability, strong hydrophobicity, organophilic property and the like, the mesoporous carbon material has unique advantages in reactions such as hydrogenation, oxidation, decomposition and the like. If the mesoporous structure can be manufactured in the carbon-coated transition metal material, the mass transfer efficiency can be obviously improved, and the service performance can be improved. At present, the preparation methods of mesoporous carbon materials mainly comprise a catalytic activation method, an organogel carbonization method and a template method, but the preparation processes of the methods are still too complex.
In addition, the carbon-coated metal nanoparticles are smaller and have more fine powder, which can cause problems in special fields, such as fixed bed reactor applications. Therefore, there is an urgent need for carbon-coated metal nanoparticle composites having better particle morphology, strength, and less fines.
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 aims to provide a carbon-coated transition metal nano composite material, a preparation method and application thereof. In addition, the nano composite material can also have a rich mesoporous structure, particularly a hierarchical pore structure containing micropores and mesopores, can be used for various catalytic hydrogenation reactions to improve the catalytic efficiency, and can also be applied to the treatment of Volatile Organic Compounds (VOCs).
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a carbon-coated transition metal nanocomposite, which comprises a carrier and a core-shell structure loaded on the carrier, wherein a shell layer of the core-shell structure is a graphitized carbon layer containing oxygen, and an inner core of the core-shell structure is transition metal nanoparticles.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
According to an embodiment of the present invention, wherein the nanocomposite is a hierarchical pore structure material containing both micropores and mesopores.
According to one embodiment of the invention, the proportion of the mesopore volume in the nanocomposite material to the total pore volume is more than 50%, preferably more than 80%.
According to one embodiment of the invention, wherein the support is selected from one or more of activated carbon, silica, alumina and molecular sieves.
According to an embodiment of the present invention, wherein the oxygen content is less than 25.0 at%, preferably from 2.0 at% to 20.0 at%, more preferably from 5 at% to 15.0 at%, in terms of atomic percentage.
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 present invention, wherein the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
placing the carrier in the homogeneous solution, mixing, and drying to obtain a precursor;
and pyrolyzing the precursor in inert atmosphere or reducing atmosphere to obtain the nano composite material.
According to an embodiment of the present invention, wherein the transition metal salt is selected from one or more of organic acid salt, carbonate and basic carbonate of transition metal, the organic acid salt of transition metal is preferably organic carboxylate of transition metal without heteroatom, more preferably acetate of transition metal without heteroatom, wherein the heteroatom refers to metal atom other than the transition metal.
According to one embodiment of the invention, wherein the polybasic organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid and dipicolinic acid.
According to one embodiment of the present invention, the mass ratio of the transition metal salt to the polybasic organic carboxylic acid is 1: 0.1-10, preferably 1: 0.5-5, and more preferably 1: 0.8-3; the mass ratio of the carrier to the transition metal salt is 1: 1-20, preferably 1: 1-10.
According to one embodiment of the invention, wherein the solvent is water and/or ethanol.
According to an embodiment of the invention, wherein the 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 inert gas and hydrogen.
The invention also provides the application of the nano composite material as a catalyst in catalytic hydrogenation reaction.
According to an embodiment of the present invention, the catalytic hydrogenation reaction is hydrogenation of p-chloronitrobenzene to produce p-chloroaniline, hydrogenation of nitrobenzene to produce aniline, hydrogenation of nitrophenol to produce aminophenol, hydrogenation of p-nitroanisole to produce p-anisidine, hydrogenation of phenol to produce cyclohexanol, hydrogenation of olefin to produce saturated alkane, hydrogenation of aromatic hydrocarbon to produce cyclohexane or its derivative, hydrogenation of aldehyde to produce alcohol, or hydrogenation of ketone to produce alcohol.
The invention also provides the application of the nano composite material as a catalyst in treating volatile organic compounds, which comprises the following steps:
contacting the volatile organic compound with the nanocomposite to perform a catalytic oxidation reaction.
According to an embodiment of the present invention, wherein the volatile organic compound is a volatile organic compound contained in the industrial waste gas.
According to one embodiment of the present invention, the volatile organic compound comprises butane, and the content of the butane in the industrial waste gas is 0.01-2% by volume.
According to one embodiment of the present invention, wherein the catalytic oxidation reaction is carried out at a temperature of 200 ℃ to 500 ℃, preferably at a temperature of 300 ℃ to 400 ℃.
According to one embodiment of the invention, the reaction space velocity of the catalytic oxidation reaction is 2000-5000 ml industrial waste gas/(hour-g of the catalyst).
According to one embodiment of the present invention, the industrial waste gas is industrial waste gas generated by preparing maleic anhydride through n-butane oxidation.
The invention has the beneficial effects that:
according to the carbon-coated transition metal nanocomposite material, the oxygen-containing graphitized carbon layer is used as a shell layer, the transition metal is used as an inner core to construct a core-shell structure, and the core-shell structure is loaded on the carrier to form the nanocomposite material. The strength of the material can be further improved by loading the core-shell structure on the carrier, and the material has better particle morphology and less fine powder and can be better applied to a fixed bed reactor. In addition, the nano composite material also has rich mesoporous structure, and further has micropore and mesoporous hierarchical pore structure, which is beneficial to the diffusion efficiency of reaction molecules on pore channels, thereby improving the transfer efficiency of substances in the catalysis process.
The nano composite material, the graphitized carbon layer, the ferromagnetic metal inner core coated by the graphitized carbon layer and the abundant pore structure make the graphitized carbon layer better combine the magnetic separation function and the adsorption function, and the graphitized carbon layer is particularly suitable for the field of adsorption separation. The nano composite material can be used as a catalyst for various organic reactions, is favorable for improving the efficiency of catalytic reactions, particularly has excellent catalytic effect and selectivity for catalytic hydrogenation reactions, and has good industrial application prospect. In one illustrative application of the present invention, the nanocomposite of the present invention exhibits good low temperature activity when used as a catalytic oxidation catalyst, which is of great significance for the complete removal of volatile organic compounds from industrial waste gases by catalytic combustion.
The carbon-coated transition metal nano composite material disclosed by the invention is not self-ignited in the air, can be stored in the air for a long time like common commodities, and does not influence the service performance of the carbon-coated transition metal nano composite material in reactions such as catalytic oxidation, catalytic hydrogenation and the like.
Drawings
In order that the embodiments of the invention may be more readily understood, reference should now be made to the following detailed description taken in conjunction with the accompanying drawings. It should be noted that, in accordance with industry standard practice, various components are not necessarily drawn to scale and are provided for illustrative purposes only. In fact, the dimensions of the various elements may be arbitrarily expanded or reduced for clarity of discussion.
FIG. 1 is a TEM image of a carbon-coated transition metal nanocomposite prepared in example 1;
FIG. 2 is an XRD pattern of the carbon-coated transition metal nanocomposite prepared in example 1;
FIGS. 3a and 3b respectively show N of the carbon-coated transition metal nanocomposite prepared in example 12Adsorption-desorption isotherms and BJH mesoporous pore size distribution curves;
FIG. 4 is a TEM image of the carbon-coated transition metal nanocomposite prepared in example 2;
FIG. 5 is an XRD pattern of the carbon-coated transition metal nanocomposite prepared in example 2;
FIGS. 6a and 6b respectively show N of the carbon-coated transition metal nanocomposite prepared in example 22Adsorption-desorption isotherms and BJH mesoporous pore size distribution curves;
FIG. 7 is a TEM image of the carbon-coated transition metal nanocomposite prepared in example 3;
FIG. 8 is an XRD pattern of the carbon-coated transition metal nanocomposite prepared in example 3;
fig. 9 is a BJH mesoporous pore size distribution curve of the carbon-coated transition metal nanocomposite prepared in example 3;
FIG. 10 is a TEM image of the carbon-coated transition metal nanocomposite prepared in example 4;
FIG. 11 is an XRD pattern of a carbon-coated transition metal nanocomposite prepared in example 4;
FIGS. 12a and 12b respectively show the carbon pack prepared in example 4N of transition metal-coated nanocomposites2Adsorption-desorption isotherms and BJH mesoporous pore size distribution curves;
FIG. 13 is a TEM image of the carbon-coated transition metal nanocomposite prepared in example 5;
FIG. 14 is an XRD pattern of the carbon-coated transition metal nanocomposite prepared in example 5;
FIGS. 15a and 15b respectively show N of the carbon-coated transition metal nanocomposite prepared in example 52Adsorption-desorption isotherms and BJH mesoporous pore size distribution curves.
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 "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 transition metal nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a mesopore pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "hierarchical pore structure material" refers to a microporous-mesoporous material, a microporous-macroporous material, a macroporous-mesoporous material, a microporous-mesoporous-macroporous material, or a mesoporous-mesoporous material containing two or more different pore sizes.
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 × 1 during analysis and test0-9mbar. 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 desorption curve of a mesoporous distribution curve is calculated according to a Barrett-Joyner-Halenda (BJH) method.
The invention provides a carbon-coated transition metal nanocomposite, which comprises a carrier and a core-shell structure loaded on the carrier, wherein a shell layer of the core-shell structure is a graphitized carbon layer containing oxygen, and an inner core of the core-shell structure is transition metal nanoparticles.
The nano composite material comprises a carrier and a core-shell structure loaded on the carrier, wherein the core-shell structure consists of transition metal nano particles which are tightly coated (not contacted with the outside) by a graphitized carbon layer, transition metal nano particles which can be contacted with the outside and are limited and a carbon layer shell with a mesoporous structure, the surface of the graphitized carbon layer doped with oxygen has rich defect sites, and the carbon material has catalytic activity and can play a role in cooperation with the transition metal nano particles, so that the nano composite material has better catalytic performance; in addition, the core-shell structure with good catalytic performance is further loaded on the carrier, so that the strength of the nano composite material is increased, and the nano composite material has a better particle form, and can be better applied to a fixed bed reactor and the like.
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.
According to the nanocomposite material of the present invention, in some embodiments, a single batch of the composite material may contain both microporous and mesoporous hierarchical pore structures, which facilitate the diffusion efficiency of reactive molecules on the pore channels, thereby improving the transfer efficiency of substances during the catalytic process.
In the nanocomposite material of the invention, the proportion of the mesopore volume to the total pore volume is more than 50%. 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～0.70cm3/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。
According to the nanocomposite material of the present invention, the support is selected from one or more of activated carbon, silica, alumina and molecular sieves.
According to the invention, the activated carbon is an amorphous activated carbon having a large specific surface area, typically 100m2/g～800m2The particle morphology is spherical or other required particle morphologies, and the particle strength is higher.
According to the invention, the silica has the formula xSiO2·yH2O, a transparent or opalescent granular solid. It has open porous structure, strong adsorptivity and can adsorb various substances. Dilute sulfuric acid (or hydrochloric acid) is added to an aqueous solution of water glass and left to stand to form a hydrous silicic acid gel to be solidified. Washing with water to remove Na dissolved in electrolyte+And SO4 2-(Cl-) And (5) drying to obtain the carrier. The support has a large specific surface area, typically 100m2/g～800m2The particle morphology is spherical or other required particle morphologies, and the particle strength is higher. Microspheroidal amorphous supports of large specific surface area are preferred in the present invention. The morphology and particle size of the carrier may also be selected as appropriate for the particular application.
According to the invention, the alumina is also called alumina, has a molecular weight of 102 and is a white amorphous powder. The alumina described in the invention is preferably gamma-type alumina, which is made up by dewatering aluminium hydroxide at 140-150 deg.C, also called active alumina and aluminium gel in industry3+The gamma-type alumina is insoluble in water, can be dissolved in strong acid or strong alkali solution, and can be heated to 1200 deg.C, and can be completely converted into α type alumina, and the gamma-type alumina is a porous material, its internal surface area per gram is up to several hundred square meters, and its activity is high and adsorption capacity is strong.
According to the invention, the molecular sieveIs a synthetic hydrated aluminosilicate (zeolite) or natural zeolite with the function of screening molecules. The chemical general formula is (M' 2M) O.Al2O3·xSiO2·yH2O, wherein M', M independently represent a monovalent or divalent cation, e.g. K+、Na+And Ca2+、Ba2+And the like. It has many pore canals with uniform pore diameter and regularly arranged holes, and molecular sieves with different pore diameters separate molecules with different sizes and shapes. According to SiO2And Al2O3The molecular ratio of (A) is different, and molecular sieves with different pore diameters can be obtained. The types of the medicine are as follows: JSA, 3A (potassium a type), 4A (sodium a type), 5A (calcium a type), 10Z (calcium Z type), 13Z (sodium Z type), Y (sodium Y type), sodium mordenite type, and the like. The molecular sieve has the characteristics of high adsorption capacity, strong selectivity and high temperature resistance.
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
In some embodiments, the carbon layer of the composite contains oxygen and does not contain nitrogen.
According to the nanocomposite material of the invention, in some embodiments, the carbon layer of the composite material contains only oxygen and no other elements except hydrogen and oxygen.
According to the nanocomposite material of the present invention, oxygen is contained in the graphitized carbon layer. 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 surface is less than 25.0 at%, preferably from 2.0 at% to 20 at%, more preferably from 5.0 at% to 15.0 at%, as measured by XPS.
In some embodiments, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
In some embodiments, the core-shell structure has a particle size of 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
In some embodiments, the transition metal is selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn); preferably one or more of iron, cobalt, nickel and copper.
In some embodiments, the carbon-coated transition metal nanocomposite described above is prepared by:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
placing the carrier in the homogeneous solution, mixing, and drying to obtain a precursor;
and pyrolyzing the precursor in inert atmosphere or reducing atmosphere to obtain the nano composite material.
Specifically, the precursor is a water-soluble mixture, which means that a transition metal salt and a polybasic organic carboxylic acid are dissolved in a solvent such as water and/or ethanol to form a homogeneous solution, and then the solvent is directly removed to obtain the precursor containing the transition metal. 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.
In some embodiments, the transition metal salt is selected from one or more of organic acid salts, carbonates, and basic carbonates of transition metals, preferably organic acid salts of transition metals that do not contain heteroatoms, more preferably acetates of transition metals that do not contain heteroatoms, where the heteroatoms refer to metal atoms other than the transition metals.
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, the mass ratio of the transition metal 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 transition metal salt, the polybasic organic carboxylic acid and other organic compounds except the two in a solvent such as water, ethanol and the like to form a homogeneous solution, and removing the solvent to obtain the transition metal-containing water-soluble mixture. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the transition metal salt, the poly-organic carboxylic acid and the other organic compound is 1:0.5 to 10:0 to 10, preferably 1:1 to 3:0 to 3.
In some embodiments, the mass ratio of the carrier to the transition metal salt is 1:1 to 20, preferably 1:1 to 10. When the carrier quality is too high, the formation of the carbon-coated transition metal nano structure and the catalytic performance of the composite material are affected.
In some embodiments, wherein the solvent is water and/or ethanol.
In some embodiments, wherein the pyrolyzing 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 inert gas and hydrogen. For example, a small amount of hydrogen gas is doped in an inert atmosphere.
The invention also provides the application of the nano composite material as a catalyst in catalytic hydrogenation reaction. The catalytic hydrogenation reaction may be, but is not limited to, p-chloroaniline preparation by p-chloronitrobenzene hydrogenation, aniline preparation by nitrobenzene hydrogenation, aminophenol preparation by nitrophenol hydrogenation, p-anisidine preparation by p-nitroanisole hydrogenation, cyclohexanol preparation by phenol hydrogenation, saturated alkane preparation by olefin hydrogenation, cyclohexane or its derivative preparation by aromatic hydrocarbon hydrogenation, alcohol preparation by aldehyde hydrogenation or alcohol preparation by ketone hydrogenation. When the nano composite material is used for catalytic hydrogenation reaction, the reaction conversion rate and the target product selectivity can both reach over 95 percent, and partial reaction can reach 99.9 percent.
The invention also provides the application of the composite material as a catalyst in treating volatile organic compounds, wherein industrial waste gas often contains Volatile Organic Compounds (VOCs), the VOCs generally refer to organic compounds with saturated vapor pressure of more than 70Pa at normal temperature and boiling point of less than 250 ℃ at normal pressure, and the common organic compounds comprise alkanes, aromatic hydrocarbons, ether alcohols, halogenated hydrocarbons and the like. In chemical and petrochemical industries, the generation and emission of VOCs are the most important, and the VOCs are easy to be encountered in life (formaldehyde and the like are generated during decoration). For example, in the production of maleic anhydride from commercial n-butane, the above-mentioned VOCs are produced when the oxygen in the raw material and air is not converted to 100% into the product over the catalyst. VOCs are one of the main causes of photochemical smog, are used as important pollutants for controlling the air quality together with nitrogen oxides, inhalable particles and the like, and have high toxicity, carcinogenic hazards and the like, so that catalytic oxidation materials with excellent performance are urgently needed for treatment.
The method comprises the step of contacting the catalyst with gaseous volatile organic compounds to perform catalytic oxidation reaction, wherein the volatile organic compounds comprise butane, and the butane accounts for 0.01-2% of the industrial waste gas by volume.
In some embodiments, the temperature of the catalytic oxidation reaction is from 200 ℃ to 500 ℃, preferably from 300 ℃ to 400 ℃. The reaction space velocity is 2000-5000 ml industrial waste gas/(hour-g of the catalyst). The composite material of the invention is used as a catalyst to catalyze and oxidize butane components with the content of 0.01-2 volume percent in waste gas generated in a maleic anhydride production process into CO at 350 ℃ under the condition of reducing reaction severity, for example2The elimination rate can reach more than 90 percent by volume, and the butane component can be completely catalyzed and oxidized into CO at 400 DEG C2. Compared with the prior art, the method has the advantages of reducing the reaction temperature, increasing the airspeed and the like, and can obtain good reaction effect.
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.
Example 1
(1) 10g of nickel acetate and 20g of citric acid were weighed into 20m L of deionized water and stirred at 50 ℃ to obtain a homogeneous solution.
(2) And (2) adding 2g of silicon dioxide (Grace company, model 2485) into the homogeneous phase solution obtained in the step (1), continuously stirring for 2h, and heating and evaporating to dryness to obtain a solid microsphere precursor.
(3) And (3) placing the precursor obtained in the step (2) 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 600 ℃ 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 carbon-coated nickel nanocomposite containing the carrier.
The percentage contents of elements contained in the surface of the nano composite material obtained by XPS analysis are respectively as follows: 81.99 at% of carbon, 13.41 at% of oxygen, 1.36 at% of nickel and 3.24 at% of silicon.
The TEM image of the nanocomposite is shown in fig. 1, 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 this nanocomposite is shown in fig. 2, and it can be seen that there are diffraction peaks (2 θ angles of 44.46 °, 51.9 °, and 76.3 °) of fcc Ni in the diffraction pattern of this material. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 12.4nm by the scherrer equation.
BET test shows that the composite material is a hierarchical pore structure material containing micropores and mesopores, and the specific surface area of the material is 211m2Per g, micropore area 73m2(ii)/g; pore volume of 0.490cm3Per g, micropore volume of 0.031cm3The mesopore volume accounts for 93.7 percent of the total pore volume. FIG. 3a shows N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 3b, which is a BJH mesoporous size distribution curve of the nanocomposite, and it can be seen that a plurality of mesoporous distribution peaks exist at 3.83nm, 6.71nm, 13.37nm and 19.42nm of the nanocomposite respectively.
Example 2
(1) 10g of nickel acetate and 20g of citric acid were weighed into 60m L of deionized water and stirred at 70 ℃ to obtain a homogeneous solution.
(2) And (2) adding 4g of pseudo-boehmite into the homogeneous phase solution obtained in the step (1), continuing stirring for 2h, heating and evaporating to dryness, and then drying the solid microsphere precursor.
(3) And (3) placing the precursor obtained in the step (2) 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 1h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated transition metal nanocomposite containing the carrier.
The percentage content of the elements contained in the surface of the material obtained by XPS analysis is as follows: 80.48 at% carbon, 15.17 at% oxygen, 0.73 at% nickel, 3.62 at% aluminum.
The TEM image of the material is shown in fig. 4, and it can be seen that the composite material contains a carbon-coated nickel core-shell structure, and a carbon layer with a certain graphitization degree is coated on the outer layer of the metallic nickel nano-particles to form a complete core-shell structure. The X-ray diffraction pattern of the carbon-coated nickel nanocomposite is shown in fig. 5, and it can be seen that there are diffraction peaks (2 θ angle of 25.56 °) for graphitic carbon and diffraction peaks (2 θ angle of 44.38 °, 51.73 ° and 76.42 °) for fcc Ni in the diffraction pattern of the material. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 13.5nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 162m2Per g, pore volume 0.393cm3The mesoporous volume accounts for 100 percent of the total pore volume. FIG. 6a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 6b, which is a BJH mesoporous pore size distribution curve of the nanocomposite, and it can be seen that the nanocomposite has two mesoporous distribution peaks at 3.84nm and 19.19nm, respectively.
Example 3
(1) 10g of cobalt acetate and 10g of ethylenediamine tetraacetic acid were weighed, added to 150m L of deionized water, and stirred at 30 ℃ to obtain a homogeneous solution.
(2) And (2) adding 1g of silicon dioxide (Grace company, model 955) into the homogeneous phase solution obtained in the step (1), continuously stirring for 2h, and heating and evaporating to dryness to obtain a solid microsphere precursor.
(3) And (3) placing the precursor obtained in the step (2) 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 750 ℃ at a speed of 5 ℃/min, keeping the temperature for 1h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated cobalt nanocomposite containing the carrier.
The percentage contents of the elements contained in the surface of the composite material obtained by XPS analysis are respectively as follows: 85.84 at% of carbon, 6.94 at% of oxygen, 3.57 at% of cobalt, 2.31 at% of nitrogen and 1.34 at% of silicon.
The TEM image of the material is shown in FIG. 7, and it can be seen that the composite material contains a carbon-coated cobalt core-shell structure, and a carbon layer with a certain graphitization degree is coated on the outer layer of the metallic cobalt nanoparticles to form a complete core-shell structure. The X-ray diffraction pattern of the carbon-coated cobalt nanocomposite is shown in fig. 8, and it can be seen that the diffraction pattern of the material has diffraction peaks (2 θ angles of 44.36 °, 51.9 ° and 76.4 °) of fcc Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 24.6nm by the scherrer equation.
BET test shows that the material is a hierarchical pore structure material containing micropores and mesopores, and the specific surface area of the material is 114m2Per g, micropore area of 56m2(ii)/g; the pore volume is 0.387cm3Per g, micropore volume of 0.027cm3The mesopore volume accounts for 93 percent of the total pore volume. Fig. 9 is a BJH mesoporous pore size distribution curve of the nanocomposite, and it can be seen that the nanocomposite has two mesoporous distribution peaks at 3.84nm and 14.56nm, respectively.
Example 4
(1) 5g of nickel acetate, 5g of cobalt acetate, 10g of citric acid and 4g of maleic acid were weighed into 20m L of deionized water and stirred at 50 ℃ to give a homogeneous solution.
(2) And (2) adding 3g of activated carbon (40-100 meshes, manufactured by Beijing chemical reagent company) into the homogeneous phase solution obtained in the step (1), continuously stirring for 2h, and heating and evaporating to dryness to obtain a solid microsphere precursor.
(3) And (3) placing the precursor obtained in the step (2) 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 550 ℃ at a speed of 5 ℃/min, keeping the temperature for 1h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated transition metal nanocomposite containing the carrier.
The percentage contents of the elements contained in the surface of the material obtained by XPS analysis are respectively as follows: 87.98 at% carbon, 9.17 at% oxygen, 1.52 at% nickel, 1.33 at% cobalt.
The TEM image of the material is shown in fig. 10, and it can be seen that the composite material contains a core-shell structure of carbon-coated nickel and/or cobalt, and a carbon layer with a certain graphitization degree is coated on the outer layer of the metal nickel and/or cobalt nanoparticles to form a complete core-shell structure. The X-ray diffraction pattern of the carbon-coated nickel and/or cobalt nanocomposite material is shown in fig. 11, and it can be seen that there are diffraction peaks (2 θ angles of 44.38 °, 51.83 °, and 76.42 °) of fcc Ni in the diffraction pattern of the material. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 21.3nm by the scherrer equation.
BET test shows that the material is a hierarchical pore structure material containing micropores and mesopores, and the specific surface area of the material is 244m2Per g, pore area 160m2(ii)/g; pore volume of 0.293cm3Per g, micropore volume of 0.073cm3The mesopore volume accounts for 75 percent of the total pore volume. FIG. 12a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 12b, which is a BJH mesoporous size distribution curve of the nanocomposite, and it can be seen that the composite has two mesoporous distribution peaks at 3.84nm and 11.29nm, respectively.
Example 5
(1) 10g of nickel acetate, 10g of citric acid and 5g of neopentyl glycol were weighed into 150m L of deionized water and stirred at 30 ℃ to obtain a homogeneous solution.
(2) Adding 1g of JSA molecular sieve (JSA-1, model number, China petrochemical catalyst ChangLing division Co., Ltd.) into the homogeneous solution obtained in the step (1), continuously stirring for 2h, heating and evaporating to dryness, and then drying the solid microsphere precursor.
(3) And (3) placing the precursor obtained in the step (2) 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 500 ℃ at a speed of 5 ℃/min, keeping the temperature for 4h, stopping heating, and cooling to room temperature in a nitrogen atmosphere to obtain the carbon-coated transition metal nano material containing the carrier.
The percentage contents of the elements contained in the surface of the material obtained by XPS analysis are respectively as follows: 77.78 at% carbon, 1.06 at% silicon, 3.56 at% aluminum, 13.76 at% oxygen, and 3.84 at% nickel.
The TEM image of the material is shown in fig. 13, and it can be seen that the composite material contains a carbon-coated nickel core-shell structure, and a carbon layer with a certain graphitization degree is coated on the outer layer of the metallic nickel nanoparticles to form a complete core-shell structure. The X-ray diffraction pattern of the carbon-coated nickel nanocomposite is shown in fig. 14, and it can be seen that there are diffraction peaks corresponding to graphitic carbon (2 θ angle 25.66 °) and fcc Ni (2 θ angles 44.38 °, 51.8 ° and 76.5 °) in the diffraction pattern of the material. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 25.4nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 183m2Per g, pore volume 0.316cm3The mesoporous volume accounts for 100 percent of the total pore volume. FIG. 15a shows N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 15b, which is a BJH mesoporous size distribution curve of the nanocomposite, and it can be seen that the composite has two mesoporous distribution peaks at 3.8nm and 7.5nm, respectively.
Test example
Test example 1
The nanocomposites prepared in examples 1-5 and commercially available nickel oxide (NiO) (analytical purity, lot: 20160803, manufacturer: national drug group chemical reagent company) were used as catalysts for complete catalytic elimination experiments of butane in exhaust gas generated in the production process of maleic anhydride by oxidation of industrial n-butane, and butane elimination rate evaluation of the catalytic material was performed, and under the same conditions, the higher the butane elimination rate, the higher the catalyst activity. The specific evaluation method comprises the following steps:
sending the collected butane-containing maleic anhydride production process waste gas into a fixed bed reactor loaded with a composite material to contact with the composite material serving as a catalyst for catalytic oxidation reaction, carrying out gas chromatography analysis on the obtained reaction product, and calculating the butane elimination rate, wherein the butane elimination rate is 100 percent, and the butane volume in the reaction product/the butane volume in the maleic anhydride production process waste gas is × 100 percent.
The waste gas of the maleic anhydride production process contains about 1 volume percent of butane, the balance of air and a very small amount of carbon monoxide and carbon dioxide, the reaction space velocity is 5000 milliliters of industrial waste gas/(hour-gram catalyst), the evaluation time is 5 hours, and the specific reaction temperature and the butane elimination rate data are shown in Table 1.
TABLE 1
As can be seen from Table 1, the nanocomposite prepared by the method of the present invention can completely catalyze the oxidation of butane to CO at 400 ℃2. Wherein the nanocomposite of examples 3 and 4 can achieve 100% butane elimination in the off-gas of the maleic anhydride production process containing 1 vol% butane at 350 ℃. When the nano composite material is used as a catalytic oxidation catalyst, the nano composite material shows good low-temperature activity, and has important significance for thoroughly removing volatile organic compounds in industrial waste gas through catalytic combustion. The graphitized carbon layer plays a role in separating and stabilizing the active center of the metal under the reaction condition, and effectively prevents the aggregation and inactivation of the active center. When the catalytic material provided by the invention is applied to the treatment of the waste gas in the maleic anhydride production process, the reaction temperature can be greatly reduced, and the energy consumption is reduced.
Test example 2
The nanocomposite material of example 1 was used as a catalyst in a reaction for preparing aniline by hydrogenation of nitrobenzene, and the specific experimental steps were:
adding 0.1g of nano composite material, 2.7mmol of nitrobenzene and 30m of L anhydrous ethanol into a reaction kettle, introducing H2Replacing the reaction kettle for 3 times, and introducing H2And (3) controlling the pressure in the reaction kettle to be 1MPa, stirring and heating, heating to 80 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product 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
The conversion of nitrobenzene was 100% and the selectivity to aniline was 99.9%.
Test example 3
The nanocomposite material of example 1 is used as a catalyst for a reaction for preparing p-chloroaniline by hydrogenating p-chloronitrobenzene, and the specific experimental steps are as follows:
adding 0.1g of the nano composite material, 3.0mmol of p-chloronitrobenzene and 30m L of absolute ethyl alcohol into a reaction kettle, and introducing H2Replacing the reaction kettle for 3 times, and introducing H2And (3) controlling the pressure in the reaction kettle to be 1.0MPa, stirring and heating, heating to 80 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of p-chloronitrobenzene is 100 percent, and the selectivity of p-chloroaniline is 99.9 percent.
Test example 4
The nanocomposite material of example 2 was used as a catalyst for the reaction of phenol hydrogenation to cyclohexanol, and the specific experimental steps were:
adding 0.2g of composite material, 5.0mmol of phenol and 50m of L water 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 3MPa, stirring and heating, heating to 150 ℃, reacting for 8 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of phenol is 100%, and the selectivity of cyclohexanol is 99.7%.
Test example 5
The nanocomposite material of example 1 was used as a catalyst for a reaction for preparing isopropanol by acetone hydrogenation, and the specific experimental steps were:
adding 0.1g of composite material, 2.0mmol of acetone and 30m 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 3MPa, stirring and heating, heating to 150 ℃, reacting for 8 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion of acetone was 98.9% and the selectivity of isopropanol was 98.3%.
Test example 6
The nanocomposite material obtained in the embodiment 2 is used as a catalyst for a reaction for preparing isopropanol by acetone hydrogenation, and the specific experimental steps are as follows:
adding 0.2g of composite material, 4.0mmol of acetone and 50m 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 3MPa, stirring and heating, heating to 150 ℃, reacting for 8 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion of acetone was 96.4% and the selectivity to isopropanol was 97.9%.
Test example 7
The nanocomposite material of example 1 is used as a catalyst for a reaction for preparing p-aminophenol by hydrogenating p-nitrophenol, and the specific experimental steps are as follows:
adding 0.1g of composite material, 3.5mmol of p-nitrophenol and 50m of L ethanol into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 1.0MPa, stirring and heating, heating to 80 ℃, reacting for 1 hour, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of the p-nitrophenol is 100 percent, and the selectivity of the p-aminophenol is 99.8 percent.
Test example 8
The nanocomposite material in example 1 is used as a catalyst for a reaction for preparing p-anisidine by hydrogenation of p-nitroanisole, and the specific experimental steps are as follows:
adding 0.1g of composite material, 2.0mmol of p-nitrophenol and 30m of L ethanol into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 1.0MPa, stirring and heating, heating to 80 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of the paranitroanisole is 100 percent, and the selectivity of the paraanisidine is 99.9 percent.
Test example 9
The nano composite material of the embodiment 2 is used as a catalyst for the reaction of preparing p-anisidine by the hydrogenation of p-nitroanisole, and the specific experimental steps are as follows:
adding 0.2g of composite material, 4.0mmol of p-nitrophenol and 50m of L ethanol into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 1.0MPa, stirring and heating, heating to 80 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of the paranitroanisole is 100 percent, and the selectivity of the paraanisidine is 99.7 percent.
Test example 10
The nanocomposite material of example 1 was used as a catalyst for olefin hydrogenation saturation reactions, and the specific experimental steps were:
adding 0.2g of composite material, 4.0mmol of styrene and 50m 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 1.5MPa, stirring and heating, heating to 100 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of styrene is 100%, and the selectivity of ethylbenzene is 99.9%.
Test example 11
The nanocomposite material of example 2 was used as a catalyst in a reaction for producing cyclohexane derivatives by hydrogenation of aromatic hydrocarbons, and the specific experimental steps were:
0.2g of the composite material, 7.2mmol of toluene and 50m of L m of cyclohexane are added into a reaction kettle, H is introduced2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 3MPa, stirring and heating, heating to 200 ℃, reacting for 8 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion of toluene was 95.3% and the selectivity of methylcyclohexane was 99.6%.
Test example 12
The nanocomposite material of example 1 was used as a catalyst in the reaction of hydrogenation of aldehydes to alcohols, and the specific experimental steps were:
adding 0.1g of composite material, 2.0mmol of butyraldehyde and 30m of L m of cyclohexane into a reaction kettle, introducing H2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 3.0MPa, stirring and heating, heating to 150 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, and taking a product for chromatographic analysis. The conversion of the reactants and the selectivity to the desired product were calculated by the formula given in test example 2:
after analysis, the conversion rate of the butyraldehyde is 100 percent, and the selectivity of the n-butanol is 98.6 percent.
From the test examples 2-12, it can be seen that the catalytic hydrogenation reaction performed by using the nanocomposite material of the present invention can achieve a reaction conversion rate of substantially 95% or more and a product selectivity of 97% or more in a wide temperature range and pressure range, and exhibits good repeatability, high activity and high selectivity.
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 (21)
1. The carbon-coated transition metal nanocomposite comprises a carrier and a core-shell structure loaded on the carrier, wherein a shell layer of the core-shell structure is a graphitized carbon layer containing oxygen, and an inner core of the core-shell structure is transition metal nanoparticles.
2. The nanocomposite of claim 1, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
3. The nanocomposite as claimed in claim 1, wherein the nanocomposite is a hierarchical pore structure material containing both micropores and mesopores.
4. A nanocomposite as claimed in claim 2 or 3 wherein the proportion of the mesopore volume in the nanocomposite to the total pore volume is greater than 50%, preferably greater than 80%.
5. The nanocomposite of claim 1, wherein the support is selected from one or more of activated carbon, silica, alumina, and molecular sieves.
6. Nanocomposite according to claim 1, wherein the oxygen content is less than 25.0 at%, preferably from 2.0 at% to 20.0 at%, more preferably from 5 at% to 15.0 at%, in atomic percent.
7. The nanocomposite of claim 1, wherein the transition metal is selected from one or more of iron, cobalt, nickel, copper, and zinc.
8. A method of preparing a nanocomposite material as claimed in any one of claims 1 to 7, comprising:
putting transition metal salt and polybasic organic carboxylic acid into a solvent to be mixed to form a homogeneous solution;
placing the carrier in the homogeneous solution, mixing, and drying to obtain a precursor;
and pyrolyzing the precursor in inert atmosphere or reducing atmosphere to obtain the nano composite material.
9. The production method according to claim 8, wherein the transition metal salt is selected from one or more of organic acid salts, carbonates, and hydroxycarbonates of transition metals, preferably organic acid salts of transition metals containing no hetero atom, more preferably acetates of transition metals containing no hetero atom, wherein the hetero atom means a metal atom other than the transition metals.
10. The production method according to claim 8, wherein the polyvalent organic carboxylic acid is selected from one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid, and dipicolinic acid.
11. The preparation method according to claim 8, wherein the mass ratio of the transition metal salt to the polybasic organic carboxylic acid is 1: 0.1-10, preferably 1: 0.5-5, and more preferably 1: 0.8-3; the mass ratio of the carrier to the transition metal salt is 1: 1-20, preferably 1: 1-10.
12. The production method according to claim 8, wherein the solvent is water and/or ethanol.
13. The method of claim 8, wherein the pyrolyzing 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 inert gas and hydrogen.
14. Use of the nanocomposite according to any one of claims 1 to 7 as a catalyst in catalytic hydrogenation reactions.
15. The use of claim 14, wherein the catalytic hydrogenation reaction is the hydrogenation of p-chloronitrobenzene to produce p-chloroaniline, the hydrogenation of nitrobenzene to produce aniline, the hydrogenation of nitrophenol to produce aminophenol, the hydrogenation of p-nitroanisole to produce p-anisidine, the hydrogenation of phenol to produce cyclohexanol, the hydrogenation of olefin to produce saturated alkane, the hydrogenation of aromatic hydrocarbon to produce cyclohexane or its derivatives, the hydrogenation of aldehyde to produce alcohol, or the hydrogenation of ketone to produce alcohol.
16. Use of a nanocomposite according to any one of claims 1 to 7 as a catalyst in the treatment of volatile organic compounds, comprising:
contacting the volatile organic compound with the nanocomposite to perform a catalytic oxidation reaction.
17. Use according to claim 16, wherein the volatile organic compounds are volatile organic compounds contained in industrial waste gases.
18. The use according to claim 17, wherein the volatile organic compound comprises butane, and the butane is present in the industrial waste gas in an amount of 0.01 to 2% by volume.
19. Use according to claim 18, wherein the catalytic oxidation reaction is carried out at a temperature of from 200 ℃ to 500 ℃, preferably from 300 ℃ to 400 ℃.
20. The use according to claim 19, wherein the reaction space velocity of the catalytic oxidation reaction is 2000-5000 ml industrial waste gas/(hr-g of the catalyst).
21. The use according to any one of claims 17 to 20, wherein the industrial waste gas is industrial waste gas generated in preparation of maleic anhydride through n-butane oxidation.
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