CN107661763B - Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method - Google Patents

Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method Download PDF

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CN107661763B
CN107661763B CN201610602659.3A CN201610602659A CN107661763B CN 107661763 B CN107661763 B CN 107661763B CN 201610602659 A CN201610602659 A CN 201610602659A CN 107661763 B CN107661763 B CN 107661763B
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nanocarbon material
shaped body
weight
body according
organic base
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CN107661763A (en
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史春风
荣峻峰
于鹏
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/40—
    • B01J35/615—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

Abstract

A nano carbon material forming body, a preparation method and application thereof, a forming method of the nano carbon material and a hydrocarbon dehydrogenation reaction method. The invention discloses a nano carbon material forming body, a preparation method and application thereof, and a hydrocarbon dehydrogenation reaction method using the forming body as a catalyst. The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.

Description

Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method
Technical Field
The invention relates to the technical field of nano carbon material forming, in particular to a nano carbon material forming body and a preparation method thereof, and also relates to application of the nano carbon material forming body as a catalyst for hydrocarbon dehydrogenation reaction.
Background
Dehydrogenation of hydrocarbons is an important type of reaction, for example, most lower alkenes are obtained by dehydrogenation of lower alkanes. Dehydrogenation reactions can be classified into two types, direct dehydrogenation reactions (i.e., oxygen does not participate) and oxidative dehydrogenation reactions (i.e., oxygen does participate), depending on whether oxygen participates.
Various types of nanocarbon materials have been demonstrated to have catalytic effects on both direct dehydrogenation reactions and oxidative dehydrogenation reactions of hydrocarbon materials.
In the hydrocarbon oxidative dehydrogenation process using the nano-carbon material as the catalyst, for example, a fixed bed reaction process is adopted, the nano-carbon material needs to be molded, and the molded body needs to meet the following two requirements: (1) the catalyst has certain strength to avoid the molded body from being crushed in the reaction process, and on one hand, the pressure drop of a catalyst bed layer is increased due to fine particles or powder formed by crushing, so that the production and operation cost is increased, and the production danger is increased; on the other hand, the fine particles or powder formed by crushing can cause catalyst loss and product separation complication if the fine particles or powder is carried out by reaction products; (2) the nano carbon material has certain porosity to improve the specific surface area of the formed body, so that the nano carbon material in the formed body can be more fully contacted with reaction materials.
As an example of shaping nanocarbon materials, researchers have attempted to load Carbon Nanotubes (CNTs) on the surface of SiC foams to form CNT/SiC foams. Although CNTs anchor well to the surface of the SiC foam, the loading of CNTs is low, typically reaching only 0.5-4 wt%.
Therefore, how to form the nanocarbon material into a formed body with high strength in a wide nanocarbon material content range still remains a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a nano carbon material forming body and a preparation method thereof, wherein the nano carbon material forming body not only has higher strength, but also can adjust the content of a nano carbon material in a wider range.
According to one aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material containing an O element and an N element, and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material.
According to a second aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material, at least one nitrogen-containing compound selected from NH and at least one organic base are dispersed in a closed vessel3Hydrazine and urea, the organic base being selected from the group consisting of amines and quaternary ammonium bases, the temperature of the aqueous dispersion being maintained in the range of 80-250 ℃ during the reaction.
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material molded body, comprising mixing a nanocarbon material with a binder source, molding the obtained mixture to obtain a molded body, drying and optionally firing the molded body, the binder source being selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nanocarbon material being a nanocarbon material which has not been surface-treated and/or a surface-treated nanocarbon material which has been determined by X-ray photoelectron spectroscopy, the surface-treated nanocarbon material containing an O element and an N element.
According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.
According to a fifth aspect of the present invention, there is provided a method for forming a nanocarbon material, comprising subjecting a nanocarbon material to hydrothermal treatment in an aqueous dispersion, forming a slurry obtained by the hydrothermal treatment to obtain a formed product, and drying and optionally calcining the formed product, wherein the aqueous dispersion contains a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, and the nanocarbon material is an unpretreated nanocarbon material and/or a surface-treated nanocarbon material, as determined by X-ray photoelectron spectroscopy, and the surface-treated nanocarbon material contains an O element and an N element.
According to a sixth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the fifth aspect of the present invention.
According to a seventh aspect of the present invention, the present invention provides a use of the nanocarbon material shaped body according to the present invention as a catalyst for dehydrogenation reaction of hydrocarbons.
According to an eighth aspect of the present invention, there is provided a hydrocarbon dehydrogenation reaction method comprising contacting a hydrocarbon with the nanocarbon material shaped body according to the first, second, fourth or sixth aspect of the present invention under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the invention, the nano carbon material refers to a carbon material with at least one dimension of a disperse phase dimension less than 100 nm. In the present invention, "at least one" means one or two or more. In the present invention, "in the range of x to x" includes two boundary values when a numerical range is expressed.
According to a first aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material.
According to the nanocarbon material molded body of the present invention, the nanocarbon material may be a pure nanocarbon material or a nanocarbon material containing an oxygen atom and a nitrogen atom.
The nanocarbon material preferably contains an O element and an N element (hereinafter sometimes also referred to as a heteroatom-containing nanocarbon material) from the viewpoint of further improving the nanocarbon material molded body as a catalyst for a dehydrogenation reaction of hydrocarbons. More preferably, the content of the element O may be 1 to 8% by weight, preferably 2.5 to 7.5% by weight, more preferably 3 to 7% by weight, and still more preferably 4.5 to 7% by weight, in terms of element, based on the total amount of the nanocarbon material; the content of the N element may be 1 to 8% by weight, preferably 2 to 6% by weight, more preferably 3 to 5% by weight, and further preferably 3.5 to 4.5% by weight; the content of the element C may be 84 to 98% by weight, preferably 86.5 to 95.5% by weight, more preferably 88 to 94% by weight, and still more preferably 88.5 to 92% by weight.
the content of each element in the nano carbon material is measured by adopting an X-ray photoelectron spectroscopy method, a sample is dried for 3 hours in a helium atmosphere at the temperature of 150 ℃ before the test, wherein, the X-ray photoelectron spectroscopy is tested on an ESCALab250 type X-ray photoelectron spectrometer which is provided with Thermo Avantage V5.926 software and is manufactured by Thermoscientific company, the excitation source is monochromatized Al K α X-ray, the energy is 1486.6eV, the power is 150W, the penetrating energy used by narrow scanning is 30eV, and the basic vacuum during the analysis test is 6.5 multiplied by 10-10mbar, electron binding energy was corrected for the C1s peak (284.0eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method.
In the nanocarbon material, the amount of an O element (i.e., C ═ O) determined by a peak in the range of 531.0 to 532.5eV in an X-ray photoelectron spectrum is IO cThe amount of O element (i.e., C-O) determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eMay be in the range of 0.2 to 2.5, preferably in the range of 1.2 to 2.5, more preferably in the range of 1.3 to 2.2, and further preferably in the range of 1.4 to 2Within the range of (1). In the present invention, the area A of the peak of O1s spectrum in the X-ray photoelectron spectrumO 1Determining the total amount of O element, dividing the peak of O1s in X-ray photoelectron spectrum into two groups, namely the peak in 531.0-532.5eV (corresponding to C ═ O species) and the peak in 532.6-533.5eV (corresponding to C-O species), and recording the area of the peak in 531.0-532.5eV as AO 2The area of the peak in the range of 532.6 to 533.5eV is designated as AO 3，IO c/IO e＝AO 2/AO 3。
In the nanocarbon material, the content of the C element determined from a peak in the range of 284.7 to 284.9eV in the X-ray photoelectron spectrum may be 60 to 98% by weight, preferably 65 to 95% by weight, more preferably 70 to 90% by weight, based on the total amount of the C element in the nanocarbon material determined by the X-ray photoelectron spectrum; the total content of the C element determined from a peak in the range of 286.0 to 288.8eV in the X-ray photoelectron spectrum may be 2 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight. In the present invention, the area A of the peak of C1s spectrum in the X-ray photoelectron spectrumC 1Determining the total amount of C element, dividing the peak of C1s in X-ray photoelectron spectrum into two groups, i.e. peak in 284.7-284.9eV (corresponding to graphite type carbon species) and peak in 286.0-288.8eV (corresponding to non-graphite type carbon species), and recording the area of peak in 284.7-284.9eV as AC 2The area of a peak in the range of 286.0-288.8eV is designated as AC 3The content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum (A)C 2/AC 1Total content of C element determined from peak in range of 286.0-288.8eV in X-ray photoelectron spectrumC 3/AC 1。
In the nanocarbon material, the amount of C element determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum is IC cAmount of C element determined from a peak in the range of 286.0-286.2eV in X-ray photoelectron spectrumIs IC e，IC c/IC eMay be in the range of 0.3 to 4, preferably 1.5 to 4, more preferably 1.5 to 3.5, and further preferably 1.55 to 3. In the present invention, peaks in the X-ray photoelectron spectrum in the range of 286.0-288.8eV (corresponding to non-graphitic carbon species) are further divided into two groups of peaks, i.e., peaks in the range of 286.0-286.2eV (corresponding to hydroxyl and ether-type carbon species) and peaks in the range of 288.6-288.8eV (corresponding to carboxyl, anhydride and ester-type carbon species), and the area of the peaks in the range of 286.0-286.2eV is designated as AC 4The area of a peak in the range of 288.6-288.8eV is designated as AC 5，IC c/IC e＝AC 5/AC 4。
In the nano carbon material, the total amount of N elements in the nano carbon material is determined to be I through X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is IN c，IN c/IN tMay be in the range of 0.7 to 1, preferably in the range of 0.75 to 0.98, more preferably in the range of 0.8 to 0.95.
The nano carbon material has low or no N element content determined by the peak in the range of 400.6-401.5eV in an X-ray photoelectron spectrum. Generally, the amount of N element determined by a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is IN g，IN g/IN tIs not higher than 0.3, and is generally in the range of 0.02 to 0.25, preferably in the range of 0.05 to 0.2.
In the present invention, the total amount A of N element is determined from the area of the peak of N1s in the X-ray photoelectron spectrumN 1The peaks in the X-ray photoelectron spectrum of N1s were divided into two groups, i.e., a peak in the range of 400.6 to 401.5eV (corresponding to a graphite-type nitrogen species) and a peak in the range of 398.5 to 400.1eV (a nitrogen species other than graphite-type nitrogen), the respective areas of the two groups were determined, and the area of the peak in the range of 400.6 to 401.5eV was designated as AN 2The area of the peak in the range of 398.5-400.1eV is designated as AN 3，IN c/IN t＝AN 3/AN 1，IN g/IN t＝AN 2/AN 1When the obtained ratio is 0.01 or less, the species is considered to be absent, and the content of the species is noted as 0.
In the present invention, the position of each peak is determined by the binding energy corresponding to the peak top of the peak, and the peak determined by the above-mentioned range refers to a peak having the binding energy corresponding to the peak top within the range, and may include one peak or two or more peaks within the range. For example: the peak in the range of 398.5-400.1eV means all peaks having a binding energy in the range of 398.5-400.1eV corresponding to the peak top.
The nanocarbon material may exist in various forms, and specifically, may be, but not limited to, one or a combination of two or more of carbon nanotubes, graphene, thin-layer graphite, nanocarbon particles, nanocarbon fibers, nanodiamonds, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube, and is preferably a multi-walled carbon nanotube.
Preferably, the specific surface area of the multi-walled carbon nanotube is 50 to 500m2The catalyst performance of the nanocarbon material shaped body, particularly the catalyst for dehydrogenation reaction of hydrocarbon substance, can be further improved. The specific surface area of the multi-wall carbon nano-tube is more preferably 80-300m2Per g, more preferably 90 to 150m2Per g, more preferably 95 to 140m2(ii) in terms of/g. In the present invention, the specific surface area is measured by the nitrogen adsorption BET method.
The weight loss rate of the multi-walled carbon nano-tube in a temperature range of 400-800 ℃ is w800The weight loss rate in the temperature interval of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01 to 0.5, which enables better catalytic performance, in particular as a catalyst for dehydrogenation reactions of hydrocarbonsWhen the catalyst is used, a better catalytic effect can be obtained. w is a500/w800More preferably in the range of 0.02 to 0.2. In the present invention, w800＝W800－W400，w500＝W500－W400，W400The mass loss rate, W, measured at a temperature of 400 deg.C800The mass loss rate, W, measured at a temperature of 800 deg.C500Is the mass loss rate determined at a temperature of 500 ℃; the weight loss rate is measured in an air atmosphere by adopting a thermogravimetric analyzer, the test starting temperature is 25 ℃, and the heating rate is 10 ℃/min; the samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
According to the nanocarbon material molded body of the present invention, the content of other non-metallic hetero atoms such as sulfur atom and phosphorus atom may be a conventional content. Generally, the total amount of non-metallic heteroatoms (such as sulfur atoms and phosphorus atoms) other than oxygen atoms and nitrogen atoms in the nanocarbon material may be 0.5% by weight or less, preferably 0.2% by weight or less. The nanocarbon material may also contain a small amount of metal atoms, which are generally derived from the catalyst used in the preparation of the nanocarbon material, the content of the metal atoms being generally 0.5% by weight or less, preferably 0.2% by weight or less.
The nanocarbon material molded body according to the present invention further contains a heat-resistant inorganic oxide for binding and molding the nanocarbon material. In the present invention, the term "heat-resistant inorganic oxide" means an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ in oxygen or an oxygen-containing atmosphere (for example, a decomposition temperature of 300 to 1000 ℃).
According to the nanocarbon material molded body of the present invention, the heat-resistant inorganic oxide is preferably one or two or more of alumina, silica and titania. In one example, the heat-resistant inorganic oxide is alumina, and the nanocarbon material molding according to this example can achieve a higher conversion rate of raw materials.
In a preferred embodiment, at least a portion of the refractory inorganic oxide is silica, and the nanocarbon material shaped body according to this preferred embodiment can achieve a better balance between feedstock conversion and product selectivity when used as a catalyst for a hydrocarbon dehydrogenation reaction. In the preferred embodiment, the content of the silicon oxide may be 10 to 100% by weight, preferably 20 to 99% by weight, and more preferably 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxides, and the content of the heat-resistant inorganic oxides other than silicon oxide may be 0 to 90% by weight, preferably 1 to 80% by weight, and more preferably 1 to 50% by weight. In the preferred embodiment, specific examples of the heat-resistant inorganic oxide other than silicon oxide may include, but are not limited to, aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide other than silicon oxide is titanium oxide.
According to the nanocarbon material molded body of the present invention, the content of the nanocarbon material can be varied in a wide range, and still the nanocarbon material molded body has high strength. In general, the content of the nanocarbon material may be 6 to 94% by weight, preferably 8 to 92% by weight, more preferably 10 to 90% by weight, still more preferably 20 to 90% by weight, still more preferably 40 to 90% by weight, and particularly preferably 70 to 90% by weight, and the content of the heat-resistant inorganic oxide may be 6 to 94% by weight, preferably 8 to 92% by weight, more preferably 10 to 90% by weight, still more preferably 10 to 80% by weight, still more preferably 10 to 60% by weight, and particularly preferably 10 to 30% by weight, based on the total amount of the nanocarbon material molded body. The composition of the shaped bodies can be determined by X-ray fluorescence spectroscopy. In the examples disclosed in the present invention, the composition of the molded article calculated from the charged amount was substantially the same as the composition of the molded article measured by X-ray fluorescence spectrometry with an error of within 5%.
According to a second aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material.
According to the molded body of the second aspect of the present invention, the nanocarbon material is produced by a method comprising: reacting an aqueous dispersion in which a raw material nanocarbon material, at least one nitrogen-containing compound and at least one organic base are dispersed in a closed vessel.
The nitrogen-containing compound is selected from NH3Hydrazine and urea.
The organic base is selected from amines and quaternary ammonium bases.
The quaternary ammonium base may specifically be a compound of formula I:
Figure BDA0001061592100000051
in the formula I, R1、R2、R3And R4Each may be C1-C20Alkyl (including C)1-C20Straight chain alkyl of (2) and C3-C20Branched alkyl of) or C6-C12Aryl group of (1). Said C is1-C20Specific examples of the alkyl group of (a) may include, but are not limited to: one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Said C is6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, 4-methylphenyl and 4-ethylphenyl. R1、R2、R3And R4Preferably each is C1-C10Alkyl (including C)1-C10Straight chain alkyl of (2) and C3-C10Branched alkyl groups of) more preferably each C1-C6Alkyl (including C)1-C6Straight chain alkyl of (2) and C3-C6Branched alkyl groups of (a).
The amine refers to a substance in which one, two or three hydrogens in an ammonia molecule are replaced with an organic group, which may be bonded to a nitrogen atom to form a cyclic structure. The organic group may be a substituted (e.g., hydroxyl-substituted) or unsubstituted aliphatic hydrocarbon group and/or a substituted (e.g., hydroxyl-substituted) or unsubstituted aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic hydrocarbon group, and a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic hydrocarbon group. Specifically, the amine may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted heterocyclic amine, and a substituted (e.g., hydroxyl-substituted) or unsubstituted arylamine.
The saturated aliphatic amine is preferably a compound represented by formula II, a compound represented by formula III, or a compound represented by general formula R12(NH2)2One or more of the substances shown,
Figure BDA0001061592100000052
in the formula II, R5、R6And R7Each is H or C1-C6And R is alkyl of5、R6And R7Not H at the same time. In the present invention, C1-C6Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.
In the formula III, R8、R9And R10Each is-R11OH or hydrogen, and R8、R9And R10At least one of which is-R11OH，R11Is C1-C4An alkylene group of (a). In the present invention, C1-C4Alkylene of (A) includes C1-C4Linear alkylene of (A) and (C)3-C4A branched alkylene group ofSpecific examples may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and tert-butylene.
General formula R12(NH2)2In, R12Can be C1-C6An alkylene group of (a). In the present invention, C1-C6Alkylene of (A) includes C1-C6Linear alkylene of (A) and (C)3-C6Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, and n-hexylene.
The unsaturated aliphatic amine refers to an aliphatic chain amine having an unsaturated group in a molecular structure, and the unsaturated group is preferably an alkenyl group (i.e., -C ═ C —). The number of the unsaturated group and the amino group may be one or two or more, and is not particularly limited.
Specific examples of the organic base may include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, sec-butylamine, di-isobutylamine, triisobutylamine, tert-butylamine, n-pentylamine, di-n-pentylamine, tri-n-pentylamine, neopentylamine, isopentylamine, diisopentylamine, triisopentylamine, tert-pentylamine, hexylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, monoethanolamine, triethanolamine, triisopropanolamine, diethanolamine, dipropanolamine, tripropanolamine, dibutanolamine, tributanolamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, Ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, substituted or unsubstituted pyrrole, substituted or unsubstituted tetrahydropyrrole, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline, substituted or unsubstituted pyrimidine, aniline, diphenylamine, benzidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-toluidine, m-toluidine, p-toluidine, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, o-ethylaniline, N-butylaniline, 2, 6-diethylaniline, cyclohexylamine, cyclopentylamine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including its various isomers, such as tetra-N-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including its various isomers, such as tetra-N-butylammonium hydroxide, tetra-sec-butylammonium hydroxide, tetra-isobutyl ammonium hydroxide and tetra-tert-butylammonium hydroxide), and tetrapentylammonium hydroxide (including its various isomers).
Raw material nano carbon material: nitrogen-containing compounds: the weight ratio of the organic base is preferably 1: 0.01-20: 0.01 to 20, which can further improve the catalytic effect of the nanocarbon material shaped body when used as a catalyst for dehydrogenation reaction of hydrocarbon. More preferably, the raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-10: 0.02-15.
The molar ratio of the nitrogen-containing compound to the organic base is preferably 1: 0.05-100. The molar ratio of the nitrogen-containing compound to the organic base is more preferably 1: 0.1 to 90, more preferably 1: 0.4-80.
Preferably, the raw material nanocarbon material: h2The weight ratio of O is 1: 2-1000, and when the amount of water is within the range, the structural morphology of the nanocarbon material is better maintained during the treatment, such as: when the raw material nanocarbon material is a carbon nanotube, it is hardly cut off in the process of treatment. Raw material nano carbon material: h2The weight ratio of O is more preferably 1: 5 to 500, more preferably 1: 10-300, more preferably 1: 20-200. In addition, the amount of water used may be adjusted depending on the types of the nitrogen-containing compound and the organic base,so that the nitrogen-containing compound can be uniformly dispersed in water.
From the viewpoint of further improving the catalytic activity of the nanocarbon material in the dehydrogenation reaction of hydrocarbons, in a preferred embodiment, the nitrogen-containing compound is ammonia, and the organic base is selected from the group consisting of compounds represented by formula III, preferably ethanolamine, diethanolamine and triethanolamine, which can further improve the catalytic reaction effect of the nanocarbon material molded body when used as a catalyst for the dehydrogenation reaction of hydrocarbons. In this preferred embodiment, the raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is preferably in the range of 1: 0.02-10: in the range of 0.05 to 8, more preferably in the range of 1: 0.03-5: in the range of 0.1 to 6, further preferably in the range of 1: 0.05-2: in the range of 0.2-5. In this preferred embodiment, the nitrogen-containing compound: the molar ratio of the organic base is preferably in the range of 1: in the range of 0.05 to 5, more preferably in the range of 1: in the range of 0.1 to 2.5, further preferably in the range of 1: 0.4-0.8. In this preferred embodiment, the raw material nanocarbon material: h2The weight ratio of O is preferably in the range of 1: in the range of 5 to 100, more preferably in the range of 1: 10 to 90, more preferably in the range of 1: 40-80.
In another preferred embodiment, the nitrogen-containing compound is hydrazine, and the organic base is selected from quaternary ammonium bases represented by formula I, which can further improve the catalytic reaction effect of the nanocarbon material shaped body when used as a catalyst for a hydrocarbon dehydrogenation reaction. In this preferred embodiment, the raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.01-5: in the range of 0.02 to 10, preferably in the range of 1: 0.02-2.5: 1-9, more preferably in the range of 1: 0.02-1.5: 4.5-8. In this preferred embodiment, the nitrogen-containing compound: the molar ratio of the organic base is preferably 1: 0.5 to 100, more preferably 1: 1 to 90, more preferably 1: 1.1-80. In this preferred embodiment, the raw material nanocarbon material: h2The weight ratio of O is preferably 1: 10-400, more preferably 1: 20-250.
In yet another preferred embodiment, the nitrogen-containing compound is urea and the organic base is selected from the group consisting of compounds of formula II and compounds of formula R12(NH2)2The substance represented by (1) is preferably selected from ethylenediamine, n-butylamine, and hexamethylenediamine, and the catalytic reaction effect of the nanocarbon material molded body when used as a catalyst for a hydrocarbon dehydrogenation reaction can be further improved. In this preferred embodiment, the raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-10: 0.05 to 20, preferably 1: 0.1-8: 0.5 to 15, more preferably 1: 1-5: 1-10. In this preferred embodiment, the nitrogen-containing compound: the molar ratio of the organic base is preferably 1: 0.1 to 5, more preferably 1: 0.5-2. In this preferred embodiment, the raw material nanocarbon material: h2The weight ratio of O is preferably 1: 5-200, more preferably 1: 20-150.
Preferably, the temperature of the aqueous dispersion during the reaction is in the range of 80-250 ℃. When the temperature of the aqueous dispersion is within the above range, the content of oxygen atoms and/or nitrogen atoms in the raw material nanocarbon material can be effectively increased, and the structural morphology of the raw material nanocarbon material is not significantly affected. More preferably, the temperature of the aqueous dispersion during the reaction is in the range of 100-180 ℃. The duration of the reaction may be selected according to the temperature of the reaction, based on the ability to introduce a sufficient amount of oxygen and nitrogen atoms into the raw nanocarbon material. In general, the duration of the reaction may be in the range of 0.5 to 96 hours, preferably in the range of 2 to 72 hours, more preferably in the range of 10 to 40 hours.
The aqueous dispersion may be formed by various methods commonly used, and for example, the raw nanocarbon material may be dispersed in water (preferably deionized water) and then mixed with the nitrogen-containing compound and the organic base to obtain the aqueous dispersion. In order to further improve the dispersion effect of the raw material nano carbon material and shorten the dispersion time, the raw material nano carbon material can be dispersed in water by adopting an ultrasonic oscillation method. The conditions of the ultrasonic oscillation may be conventionally selected, and in general, the frequency of the ultrasonic oscillation may be 10 to 100kHz, and the duration of the ultrasonic oscillation may be 0.1 to 6 hours, preferably 0.5 to 2 hours. The nitrogen-containing compound and the organic base may be each provided in the form of a solution (preferably an aqueous solution) or may be provided in the form of a pure substance, and are not particularly limited.
According to the molded body of the second aspect of the present invention, the content of the oxygen element and the nitrogen element in the raw material nanocarbon material is not particularly limited and may be selected conventionally. Generally, the content of the oxygen element in the raw material nanocarbon material is not more than 1.5% by weight, preferably not more than 0.5% by weight, more preferably not more than 0.3% by weight; the content of nitrogen element is not more than 0.2% by weight, preferably not more than 0.1% by weight, more preferably not more than 0.05% by weight, and further preferably not more than 0.02% by weight. The total amount (in terms of elements) of the non-metallic hetero atoms (such as phosphorus atoms and sulfur atoms) other than oxygen atoms and nitrogen atoms in the raw material nanocarbon material may be a conventional amount. Generally, the total amount (in terms of elements) of the non-metallic hetero atoms other than oxygen and nitrogen in the raw material nanocarbon material is not more than 0.5% by weight, preferably not more than 0.2% by weight, more preferably not more than 0.1% by weight, and further preferably not more than 0.05% by weight. The raw nanocarbon material may contain some metal elements depending on the source, for example, metal atoms derived from the catalyst used in the preparation of the raw nanocarbon material. The content (in terms of element) of the metal atom in the raw nanocarbon material is generally 2.5 wt% or less, preferably 1.8 wt% or less, and more preferably 0.5 wt% or less.
According to the molded body of the second aspect of the present invention, the raw material nanocarbon material may be pretreated (e.g., washed) by a method commonly used in the art before use to remove some impurities on the surface of the raw material nanocarbon material; or may be used without pretreatment. In the preparation examples disclosed in the present invention, the raw material nanocarbon material was not pretreated before use.
According to the molded body of the second aspect of the present invention, the raw material nanocarbon material may be, but is not limited to, one or a combination of two or more of carbon nanotubes, graphene, nanodiamonds, thin-layer graphites, nanocarbon particles, nanocarbon fibers, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. Preferably, the raw material nanocarbon material is a carbon nanotube, more preferably a multiwall carbon nanotube.
In a preferred embodiment of the molded body according to the second aspect of the present invention, the raw nanocarbon material is multi-walled carbon nanotubes, and the specific surface area of the multi-walled carbon nanotubes may be 50 to 500m2A/g, preferably from 80 to 300m2A/g, more preferably 100 to 260m2Per g, more preferably 120 to 190m2/g。
When the raw material nano carbon material is a multi-wall carbon nano tube, the weight loss rate of the multi-wall carbon nano tube in a temperature range of 400-800 ℃ is w800The weight loss rate in the temperature interval of 400-500 ℃ is w500，w500/w800May be in the range of 0.01 to 0.5, preferably in the range of 0.02 to 0.4.
According to the molded article of the second aspect of the present invention, the reaction is carried out in a closed vessel. The reaction may be carried out under autogenous pressure (i.e., without additional application of pressure) or under pressurized conditions. Preferably, the reaction is carried out under autogenous pressure. The closed container can be a common reactor capable of realizing sealing and heating, such as a high-pressure reaction kettle.
The molded body according to the second aspect of the present invention may further comprise separating solid matter from the mixture obtained by the reaction and drying the separated solid matter to obtain a nanocarbon material. The solid matter can be separated from the mixture obtained by the reaction by a conventional solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The drying conditions may be chosen conventionally, so as to be able to remove volatile substances from the separated solid material. In general, the drying may be carried out at a temperature of from 50 to 400 ℃, preferably from 80 to 180 ℃. The duration of the drying may be selected according to the temperature and manner of drying. Generally, the duration of the drying may be no more than 48 hours, preferably 4 to 24 hours, more preferably 6 to 12 hours. The drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure. From the viewpoint of further improving the efficiency of drying, the drying is preferably performed under reduced pressure. Spray drying or the like can also be employed without a step of separating solid substances from the mixture, and the drying may be carried out at a temperature of 120 to 400 ℃, preferably at a temperature of 150 to 350 ℃, more preferably at a temperature of 180 to 300 ℃, and the duration of the drying may be selected depending on the degree of drying, such as not more than 0.5 hour, preferably not more than 0.2 hour, more preferably not more than 0.1 hour.
The molded article according to the second aspect of the present invention further contains a heat-resistant inorganic oxide for binding and molding the nanocarbon material. The kind and content of the refractory inorganic oxide are the same as those of the refractory inorganic oxide described in the first aspect of the present invention, and are not described in detail herein.
The nanocarbon material molded body according to the first and second aspects of the present invention may have various shapes such as a spherical shape and a strip shape as needed.
The nanocarbon material molded body according to the first and second aspects of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm. In the present invention, the radial crush strength was measured by a method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (first edition, 1990, ed., Yankee edition, and edited by Yankee corporation).
The nanocarbon material molded body according to the first and second aspects of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the invention may be 5% or more, even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, more preferably in the range of 12 to 25%. In the present invention, the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (see document "research on porosity of graphite porous material", "lubrication and sealing", "2010, 35 (10): 99-101) in percentage).
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material shaped body, comprising mixing a nanocarbon material with a binder source, shaping the obtained mixture to obtain a shaped body, drying and optionally firing the shaped body.
According to the method of the third aspect of the invention, the binder source is selected from the group consisting of refractory inorganic oxides and/or precursors of refractory inorganic oxides. The heat-resistant inorganic oxide is preferably one or more of alumina, silica and titania. In one example, the heat-resistant inorganic oxide is alumina, and the nanocarbon material molding according to this example can achieve a higher conversion rate of raw materials.
In a preferred embodiment, at least a portion of the refractory inorganic oxide is silica, and the nanocarbon material shaped body prepared according to this preferred embodiment can achieve a better balance between feedstock conversion and product selectivity when used as a catalyst for a hydrocarbon dehydrogenation reaction. In the preferred embodiment, the content of the silicon oxide may be 10 to 100% by weight, preferably 20 to 99% by weight, and more preferably 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxides, and the content of the heat-resistant inorganic oxides other than silicon oxide may be 0 to 90% by weight, preferably 1 to 80% by weight, and more preferably 1 to 50% by weight. In the preferred embodiment, specific examples of the heat-resistant inorganic oxide other than silicon oxide may include, but are not limited to, aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide other than silicon oxide is titanium oxide.
The refractory inorganic oxide may be provided in various forms as is common, for example, in the form of a sol (e.g., silica sol, titanium sol, aluminum sol). The precursor of the heat-resistant inorganic oxide may be selected according to the kind of the intended heat-resistant inorganic oxide.
For example, when the refractory inorganic oxide is alumina, the precursor of the refractory inorganic oxide may be a substance capable of being converted into alumina, such as a substance capable of forming alumina by hydrolytic condensation reaction and/or calcination, for example, organic aluminum salts and inorganic aluminum salts, specific examples of which may include, but are not limited to, hydrated alumina (such as pseudo-boehmite), aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and C1-C10And one or more of organic aluminum salts (e.g., aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate) of (a).
For another example, when the heat-resistant inorganic oxide is silicon oxide, the precursor of the heat-resistant inorganic oxide may be a substance that can be converted into silicon oxide, such as a substance that can form silicon oxide by a hydrolytic condensation reaction and/or firing, and specific examples thereof may include, but are not limited to, organosilicon compounds that can undergo a hydrolytic condensation reaction. The organosilicon compound capable of undergoing a hydrolytic condensation reaction may be any of various conventional substances capable of forming silicon oxide by a hydrolytic condensation reaction. As an example, the organosilicon compound capable of undergoing hydrolytic condensation reaction may be one or more than two of the compounds represented by formula IV:
Figure BDA0001061592100000091
in the formula IV, R13、R14、R15And R16Each is C1-C4Alkyl group of (1). Said C is1-C4Alkyl of (2) includes C1-C4Straight chain alkyl of (2) and C3-C4Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Preferably, the organic silicon source is selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, and n-butyl orthosilicate.
For another example, when the heat-resistant inorganic oxide is titanium oxide, the precursor of the heat-resistant inorganic oxide may be an organic titanate and/or an inorganic titanium salt, and specific examples thereof may include, but are not limited to, TiCl4、Ti(SO4)2、TiOCl2One or more of titanium hydroxide, titanium nitrate, titanium phosphate, titanium alkoxide, and organic titanate (e.g., one or more of tetraisopropyl titanate, tetra-n-propyl titanate, tetrabutyl titanate, and tetraethyl titanate).
In an embodiment of the method according to the third aspect of the invention, the binder source is selected from refractory inorganic oxides, such as refractory inorganic oxides provided in the form of a sol. In this embodiment, the nanocarbon material and the binder source may be uniformly mixed and then molded. In another embodiment, at least a portion of the binder source is a precursor to a refractory inorganic oxide. In this embodiment, after mixing the nanocarbon material with the binder source, treatment is performed according to the kind of the binder source to convert the precursor of the heat-resistant inorganic oxide in the binder source into the heat-resistant inorganic oxide.
According to the method of the third aspect of the present invention, the mixture preferably further contains at least one base, which can further improve the catalytic activity of the finally prepared nanocarbon material shaped body when used as a catalyst for a dehydrogenation reaction of hydrocarbons. The base may be an organic base and/or an inorganic base. The inorganic base may be one or more of ammonia, an alkali whose cation is an alkali metal, and an alkali whose cation is an alkaline earth metal. The organic base can be one or more than two of hydrazine, urea, amine and quaternary ammonium base. The amines and quaternary ammonium bases are described in detail in the shaped bodies according to the second aspect of the invention and are not described in detail here.
Preferably, the base is an organic base (such as formula I, formula II, formula III and general formula R)12(NH2)2Represented by formula I), more preferably quaternary ammonium base (the quaternary ammonium base is represented by formula I), more preferably template agent for synthesizing titanium silicalite molecular sieve, and the nano carbon material formed body prepared by the method has higher anti-crushing strengthAnd further exhibit improved catalytic activity when used as a catalyst for hydrocarbon dehydrogenation reactions.
The amount of the base may be selected according to the amount of the binder source. Generally, the molar ratio of the base to the binder source may be from 0.05 to 15: 1, preferably 0.1 to 12: 1, the binder source is calculated by oxide.
According to the method of the third aspect of the present invention, the nanocarbon material may be uniformly mixed with the binder source and optionally the alkali using various dispersion media. Preferably, the dispersion medium is water. The amount of the dispersion medium is such that the nanocarbon material, the binder source and optionally the alkali can be mixed uniformly. As an example, where the dispersing medium is water, the molar ratio of water to the binder source may be from 1 to 150: 1, preferably 4 to 120: 1, the binder source is calculated by oxide.
The inventor of the present invention finds in the research process that the molecular sieve preparation solution generated in the molecular sieve preparation process usually contains the binder source and the alkali required in the present invention, and also contains water, and after the molecular sieve preparation solution is mixed with the nanocarbon material, one, two or three of the water, the binder source and the alkali are optionally supplemented, so that not only can the nanocarbon material be molded, but also the prepared nanocarbon material shows higher crushing resistance strength, and simultaneously still shows better catalytic activity, and in addition, the reuse of the waste liquid in the molecular sieve preparation process is realized.
The molecular sieve preparation solution can be any common molecular sieve preparation solution capable of providing the binder source and optional base required by the invention. Preferably, the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid of a silicon-containing molecular sieve and a rearrangement modified mother liquid of the silicon-containing molecular sieve. The silicon-containing molecular sieve can be one or more than two of an all-silicon molecular sieve, a heteroatom-containing molecular sieve (such as a titanium-silicon molecular sieve) and a silicon-aluminum molecular sieve. The crystallization mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained by hydrothermal crystallization when a molecular sieve is prepared by hydrothermal crystallization, namely a liquid mixture remaining after a formed molecular sieve is separated from the mixture obtained by hydrothermal crystallization, and is also called as synthesis mother liquor, filtered waste liquor or filtered stock liquor. The rearrangement modified mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained after hydrothermal modification rearrangement when the modified molecular sieve is prepared by hydrothermal modification rearrangement, namely a liquid mixture remaining after the molecular sieve is separated from the mixture obtained by hydrothermal modification rearrangement, and is also called as rearrangement mother liquor, modified mother liquor, rearrangement filtration waste liquor, modified filtration raw liquor or rearrangement filtration raw liquor. The crystallization mother liquor and the rearrangement liquor can be directly mixed with the nano-carbon material, and can also be mixed with the nano-carbon material after being concentrated or diluted according to the needs, so that the dosage of the binder source, the alkali and the water can meet the requirements, for example, the proportion requirements are met.
More preferably, the solution for preparing the silicon-containing molecular sieve is one or more of a crystallization mother liquor of the silicon molecular sieve (e.g. a crystallization mother liquor of the all-silicon molecular sieve), a crystallization mother liquor of the heteroatom-containing molecular sieve (e.g. a crystallization mother liquor of the titanium-silicon molecular sieve), a crystallization mother liquor of the silicon-aluminum molecular sieve, and a modified heavy liquid discharge of the silicon-containing molecular sieve (e.g. a heavy liquid discharge of the all-silicon molecular sieve and the titanium-silicon molecular sieve).
The specific composition of the crystallization mother liquor and the heavy liquor is not particularly limited, so long as a binder source and, optionally, a base are provided. As an example, in the crystallization mother liquor of the silicon-containing molecular sieve, SiO is used2The content of elemental silicon is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 4% by weight; the content of the base is generally 0.05 to 15% by weight, preferably 0.1 to 15% by weight, more preferably 1.5 to 14% by weight. As another example, in heavy liquid discharge of titanium silicalite, SiO is used2The content of elemental silicon is generally 0.01 to 10% by weight, preferably 0.02 to 5% by weight, more preferably 0.5 to 2% by weight; with TiO2The content of titanium element is generally 0.0001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, more preferably 0.01 to 0.08% by weight; the content of the base is generally 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 1 to 4% by weight. As an example, in the crystallization mother liquor of the silicon-aluminum molecular sieve, SiO is used2The content of elemental silicon is generally 0.05 to 10% by weight,preferably 0.1 to 8 wt%, more preferably 1 to 4 wt%; with Al2O3The content of the aluminum element is generally 0.01 to 5% by weight, preferably 0.05 to 2% by weight, and more preferably 0.1 to 0.5% by weight, and the content of the alkali is generally 0.05 to 15% by weight, preferably 0.1 to 14% by weight, and more preferably 8 to 13% by weight.
According to the method of the third aspect of the present invention, in a preferred embodiment, the mixture is subjected to hydrothermal treatment (i.e., the mixture obtained by the hydrothermal treatment is subjected to molding) before the mixture is subjected to molding, which can further improve the catalytic activity of the finally produced nanocarbon material molded body when used as a catalyst for a dehydrogenation reaction of hydrocarbons. In this preferred embodiment, the nanocarbon material, the binder source and optionally the base may be dispersed in water and the aqueous dispersion subjected to a hydrothermal treatment.
In this preferred embodiment, the conditions of the hydrothermal treatment are not particularly limited, and the hydrothermal treatment may be performed at a high temperature in a closed environment. Specifically, the temperature of the hydrothermal treatment may be 100 to 200 ℃, preferably 120 to 180 ℃. The time for the hydrothermal treatment may be selected depending on the temperature at which the hydrothermal treatment is carried out, and may be generally 0.5 to 24 hours, preferably 6 to 12 hours. The hydrothermal treatment may be performed under autogenous pressure (i.e., no additional pressure is applied during the hydrothermal treatment), or may be performed under additional applied pressure. Preferably, the hydrothermal treatment is carried out under autogenous pressure.
According to the method of the third aspect of the present invention, the amount of the binder source may be selected according to the content of the binder in the desired nanocarbon material shaped body. Generally, the binder source is used in an amount such that the nanocarbon material content in the finally produced molded article may be 5 wt% or more (e.g., 6 wt% or more), preferably 10 wt% or more, more preferably 50 wt% or more, further preferably 60 wt% or more, further preferably 70 wt% or more, further preferably 75 wt% or more, and particularly preferably 80 wt% or more, and the nanocarbon material content is generally 95 wt% or less, preferably 94 wt% or less, and more preferably 90 wt% or less. In one example, the nanocarbon material may be contained in an amount of 5 to 95% by weight, preferably 6 to 94% by weight, more preferably 8 to 92% by weight, still more preferably 10 to 90% by weight, still more preferably 20 to 90% by weight, particularly preferably 40 to 90% by weight, and still more preferably 70 to 90% by weight, based on the total amount of the nanocarbon material molded body, and the heat-resistant inorganic oxide may be contained in an amount of 5 to 95% by weight, preferably 6 to 94% by weight, more preferably 8 to 92% by weight, still more preferably 10 to 90% by weight, still more preferably 10 to 80% by weight, particularly preferably 10 to 60% by weight, and still more preferably 10 to 30% by weight. When subjected to hydrothermal treatment prior to molding, higher strength can be obtained even at a lower binder content. Generally, when the hydrothermal treatment is performed before the molding, the content of the nanocarbon material is preferably 75 to 95% by weight, more preferably 85 to 95% by weight, and the content of the heat-resistant inorganic oxide is preferably 5 to 25% by weight, more preferably 5 to 15% by weight, based on the total amount of the molded body.
According to the method of the third aspect of the present invention, the mixture containing the nanocarbon material and the binder source may be shaped by a conventional method to obtain a shaped article. As an example, the mixture may be shaped by kneading and/or extrusion. The molding may have various shapes such as a spherical shape and a strip shape.
According to the method of the third aspect of the present invention, the shaped product may be dried under conventional conditions to remove volatile substances from the shaped product. Generally, the drying may be carried out at a temperature of 50 to 200 ℃, preferably at a temperature of 80 to 180 ℃, more preferably at a temperature of 120 to 180 ℃. The duration of the drying may be selected depending on the temperature of the drying, and may be generally not more than 48 hours, preferably 3 to 24 hours, more preferably 5 to 15 hours.
The dried shaped product may be calcined or not. The conditions for the calcination in the present invention are not particularly limited, and the calcination may be carried out under conventional conditions. Generally, the calcination may be carried out at a temperature of 300 to 800 ℃, preferably not higher than 650 ℃. The calcination may be performed in an oxygen-containing atmosphere (e.g., air, oxygen) or in an oxygen-free atmosphere (e.g., nitrogen, a group zero gas). When the calcination is carried out in an oxygen-containing atmosphere, the calcination is preferably carried out at a temperature of 300 to 500 ℃, more preferably at a temperature of not higher than 450 ℃. When the calcination is carried out in an oxygen-free atmosphere, the calcination is preferably carried out at a temperature of 400 to 800 ℃, more preferably at a temperature of not higher than 750 ℃. The duration of the calcination may be from 1 to 12 hours, preferably from 2 to 4 hours.
According to the method of the third aspect of the present invention, nanocarbon materials of various sources can be treated, and the nanocarbon materials can be non-surface-treated nanocarbon materials or surface-treated nanocarbon materials. In the present invention, the surface of the nanocarbon material is detected by X-ray photoelectron spectroscopy, and if the total content of elements other than C in the surface elements of the nanocarbon material detected is 2 wt% or less, the nanocarbon material is regarded as a nanocarbon material without surface treatment, whereas the nanocarbon material is regarded as a nanocarbon material with surface treatment.
In one embodiment, the nanocarbon material is a nanocarbon material that has not been surface treated. In this embodiment, the mixture is preferably subjected to a hydrothermal treatment before the mixture is shaped, which not only significantly improves the strength of the finally produced shaped body, but also significantly improves the catalytic properties of the finally produced shaped body. More preferably, the binder source and the optional alkali source are from a molecular sieve preparation solution, and the catalytic performance of the finally prepared formed body in the hydrocarbon dehydrogenation reaction can be further improved by carrying out hydrothermal treatment on the nano carbon material without modified surface treatment in the molecular sieve preparation solution. In this embodiment, the nanocarbon material may exist in various forms, and specifically, may be, but not limited to, one or a combination of two or more of carbon nanotubes, graphene, thin graphite, nanocarbon particles, nanocarbon fibers, nanodiamonds, and fullerenes. The carbon nanotube can be single-walled carbon nanotube, double-walled carbon nanotube and multi-walled carbon nanotubePreferably, it is a multiwalled carbon nanotube. The specific surface area of the multi-walled carbon nanotube can be 50-500m2A/g, preferably from 80 to 300m2A/g, more preferably 100 to 250m2(ii) g, more preferably 120 to 180m2(ii) in terms of/g. The weight loss rate of the multi-walled carbon nano-tube in a temperature range of 400-800 ℃ is w800The weight loss rate in the temperature interval of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01 to 0.5, more preferably in the range of 0.02 to 0.3, and further preferably in the range of 0.05 to 0.15. As an example, the nanocarbon material without surface treatment may be a raw nanocarbon material in the molded body according to the second aspect of the invention.
In another embodiment, the nanocarbon material is a surface treated nanocarbon material selected from the group consisting of elements O and elements N as determined by X-ray photoelectron spectroscopy. Preferably, the content of the element O is 1 to 8 wt%, preferably 2.5 to 7.5 wt%, more preferably 3 to 7 wt%, and further preferably 4.5 to 7 wt%, based on the total amount of the nanocarbon material and calculated as the element; the content of the N element is 2 to 8% by weight, preferably 2 to 6% by weight, more preferably 3 to 5% by weight, and still more preferably 3.5 to 4.5% by weight.
Specifically, the surface-treated nanocarbon material may be a nanocarbon material in the molded body according to the first aspect of the present invention and/or a nanocarbon material in the molded body according to the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.
The nanocarbon material molded body according to the fourth aspect of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm.
The nanocarbon material molded body according to the fourth aspect of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the fourth aspect of the present invention may be 5% or more, or even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, and more preferably in the range of 12 to 25%.
According to a fifth aspect of the present invention, there is provided a method of forming a nanocarbon material, comprising subjecting a nanocarbon material to hydrothermal treatment in an aqueous dispersion containing a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide in a closed container, forming a slurry obtained by the hydrothermal treatment to obtain a formed product, and drying and optionally firing the formed product. The binder source is of the same kind as the binder source of the third aspect of the invention and will not be described in detail here.
According to the method of the fifth aspect of the present invention, nanocarbon materials of various sources can be treated, and the nanocarbon materials can be non-surface-treated nanocarbon materials or surface-treated nanocarbon materials. The nano carbon material may be specifically the nano carbon material described in the method according to the third aspect of the present invention, and will not be described in detail herein.
According to the method of the fifth aspect of the present invention, the aqueous dispersion preferably further contains at least one treating agent which is an organic base and/or a nitrogen-containing compound. This can further improve the crushing strength of the finally produced nanocarbon material shaped body and can further improve the catalytic activity of the finally produced nanocarbon material shaped body when used as a catalyst for dehydrogenation reaction of hydrocarbons. Particularly, when the nano carbon material is a nano carbon material without surface treatment, the crushing resistance and the catalytic performance of the finally prepared nano carbon material forming body can be obviously improved.
The organic base can be one or more of amine and quaternary ammonium base (such as formula I, formula II, formula III and general formula R)12(NH2)2Of the representationSubstances) which have been described in detail in the shaped bodies according to the second aspect of the invention and which are not described in detail here. The organic base is preferably quaternary ammonium base (a compound shown as a formula I), and is particularly preferably a template agent for synthesizing the titanium silicalite molecular sieve. The nitrogen-containing compound may be selected from NH3Hydrazine and urea.
According to the method of the fifth aspect of the present invention, in one embodiment, the treating agent is an organic base or a nitrogen-containing compound.
In a more preferred embodiment, the treating agent is an organic base and/or a nitrogen-containing compound. In this more preferred embodiment, the organic base may be present in an amount of 20 to 100 wt%, preferably 35 to 92 wt%, based on the total amount of the treating agent. More preferably, the treating agent is an organic base and a nitrogen-containing compound, and the nanocarbon material molded body prepared by hydrothermally treating a nanocarbon material (particularly, a nanocarbon material which is not surface-treated) with the organic base and the nitrogen-containing compound as the treating agents has higher crushing strength than the nanocarbon material molded body prepared by using the organic base and the nitrogen-containing compound as the treating agents alone, and shows higher catalytic activity even when used as a catalyst for a dehydrogenation reaction of hydrocarbons. Compared with the method that the nano carbon material without surface treatment is subjected to hydrothermal treatment by adopting a nitrogen-containing compound, and then is subjected to hydrothermal treatment with a binder source in the presence of an organic base and then is formed, the nano carbon material without surface treatment is mixed with the binder source and the organic base in the presence of the nitrogen-containing compound and then is formed after the hydrothermal treatment, so that the use amount of the nitrogen-containing compound can be obviously reduced, and the prepared nano carbon material forming body shows the strength and the catalytic activity which are equivalent to or even higher than those of the forming body prepared by modifying and then forming. The content of the organic base is preferably 50 to 95% by weight, more preferably 65 to 92% by weight, based on the total amount of the treating agent. Still more preferably, at least a portion of the organic base is a quaternary ammonium base (compound of formula I), preferably in an amount of 50 to 95 wt.%, more preferably 65 to 92 wt.%, based on the total amount of the treating agent, and preferably in an amount of 40 to 100 wt.%, more preferably 45 to 92 wt.%, based on the total amount of the organic base. When part of the organic base is a quaternary ammonium base, the remaining part of the organic base may be an alcohol amine and/or an amine (specific examples thereof may be referred to the alcohol amine and the amine described in the molded article according to the second aspect of the present invention, and will not be described in detail here).
From the viewpoint of further improving the strength and catalytic performance of the finally produced nanocarbon material shaped body, in a preferred embodiment, the nitrogen-containing compound is ammonia, a part of the organic base is selected from compounds represented by formula III, preferably from ethanolamine, diethanolamine and triethanolamine, and the remaining part of the organic base is preferably a quaternary ammonium base (the quaternary ammonium base is preferably 50 to 85% by weight); in another preferred embodiment, the nitrogen-containing compound is hydrazine, and at least a portion of the organic base is selected from quaternary ammonium bases of formula I (the quaternary ammonium base is preferably present in an amount of 45 wt% or more); in yet another preferred embodiment, the nitrogen-containing compound is urea and the portion of the organic base is selected from the group consisting of compounds of formula II and compounds of formula R12(NH2)2The substance(s) represented, are preferably chosen from ethylenediamine, n-butylamine and hexamethylenediamine, the remaining part of the organic base preferably being a quaternary ammonium base (said quaternary ammonium base preferably being from 75 to 95% by weight).
The amount of the treating agent to be used may be appropriately selected depending on the amount of the binder source. Preferably, the molar ratio of the treating agent to the binder source may be from 0.05 to 15: 1, preferably 0.1 to 12: 1, more preferably 0.5 to 3.5: 1, the binder source is calculated by oxide.
According to the method of the fifth aspect of the present invention, the amount of water is such that the nanocarbon material and the binder source, and optionally the base, can be mixed homogeneously. Generally, the molar ratio of water to the binder source may be from 1 to 150: 1, preferably 4 to 120: 1, the binder source is calculated by oxide.
According to the method of the fifth aspect of the invention, the amount of the binder source may be selected according to the desired composition of the shaped body. Generally, the binder source is used in an amount such that the nanocarbon material content in the finally produced molded article may be 5 wt% or more (e.g., 6 wt% or more), preferably 10 wt% or more, more preferably 50 wt% or more, further preferably 60 wt% or more, further preferably 70 wt% or more, further preferably 75 wt% or more, and particularly preferably 80 wt% or more, and the nanocarbon material content is generally 95 wt% or less, preferably 94 wt% or less, and more preferably 90 wt% or less. In one example, the nanocarbon material may be contained in an amount of 5 to 95 wt% (e.g., 6 to 94 wt%), preferably 8 to 92 wt%, more preferably 10 to 90 wt%, further preferably 20 to 90 wt%, further preferably 40 to 90 wt%, and particularly preferably 70 to 90 wt%, and the heat-resistant inorganic oxide may be contained in an amount of 5 to 95 wt% (e.g., 6 to 94 wt%), preferably 8 to 92 wt%, more preferably 10 to 90 wt%, further preferably 10 to 80 wt%, further preferably 10 to 60 wt%, and particularly preferably 10 to 30 wt%, based on the total amount of the nanocarbon material molded body. The nanocarbon material molded body produced by the method according to the fifth aspect of the present invention can obtain a high strength even at a low binder content. Generally, the content of the nanocarbon material is preferably 75 to 95 wt%, more preferably 85 to 95 wt%, and the content of the heat-resistant inorganic oxide is preferably 5 to 25 wt%, more preferably 5 to 15 wt%, based on the total amount of the molded body.
According to the method of the fifth aspect of the present invention, the conditions of the hydrothermal treatment are not particularly limited as long as the treatment is performed at a high temperature in a closed environment. Specifically, the temperature of the hydrothermal treatment may be 100 to 200 ℃, preferably 120 to 180 ℃. The time for the hydrothermal treatment may be selected depending on the temperature at which the hydrothermal treatment is carried out, and may be generally 0.5 to 24 hours, preferably 6 to 12 hours. The hydrothermal treatment may be performed under autogenous pressure (i.e., no additional pressure is applied during the hydrothermal treatment), or may be performed under additional applied pressure. Preferably, the hydrothermal treatment is carried out under autogenous pressure.
The methods and conditions for the forming, drying of the formed article and optional firing according to the method of the fifth aspect of the present invention are the same as those described in the method of the third aspect of the present invention and will not be described in detail herein.
In a sixth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the fifth aspect of the present invention.
The nanocarbon material molded body according to the sixth aspect of the present invention has high crushing strength. In general, the nanocarbon material molded body according to the sixth aspect of the present invention may have a radial crush strength of 7N/mm or more, preferably 10N/mm or more, and generally in the range of 12 to 25N/mm. The nanocarbon material molded body according to the sixth aspect of the invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the sixth aspect of the present invention may be 5% or more, or even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, and more preferably in the range of 12 to 25%.
According to a seventh aspect of the present invention, there is provided a use of the nanocarbon material shaped body according to the first, second, fourth and sixth aspects of the present invention as a catalyst for dehydrogenation reaction of hydrocarbon. The dehydrogenation reaction may be carried out in the presence or absence of oxygen. Preferably, the dehydrogenation reaction is carried out in the presence of oxygen, which results in a better catalytic effect. The type of hydrocarbon and the specific conditions of the dehydrogenation reaction will be described in detail below and will not be described in detail here.
According to an eighth aspect of the present invention, there is provided a hydrocarbon dehydrogenation reaction method comprising contacting a hydrocarbon with the nanocarbon material shaped bodies according to the first, second, fourth and sixth aspects of the present invention under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen. The nanocarbon material molded body according to the present invention can be used as it is as a catalyst, or can be used as a catalyst after being crushed as needed.
The hydrocarbon dehydrogenation reaction process according to the present invention can dehydrogenate various types of hydrocarbons to obtain unsaturated hydrocarbons such as olefins. The method according to the invention is particularly suitable forThe alkane is dehydrogenated to obtain the alkene. The hydrocarbon is preferably an alkane, such as C2-C12Of (a) an alkane. Specifically, the hydrocarbon may be, but not limited to, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2, 3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2-ethylpentane, 3-ethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2, 3-dimethylhexane, 2, 4-dimethylhexane, 2, 5-dimethylhexane, 3-ethylhexane, 2, 3-trimethylpentane, 2,3, 3-trimethylpentane, 2,4, 4-trimethylpentane, 2-methyl-3-ethylpentane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2, 3-dimethylheptane, 2, 4-dimethylheptane, 3-ethylheptane, 4-ethylheptane, 2,3, 4-trimethylhexane, 2,3, 5-trimethylhexane, 2,4, 5-trimethylhexane, 2, 3-trimethylhexane, 2, 4-trimethylhexane, 2, 5-trimethylhexane, 2,3, 3-trimethylhexane, 2,4, 4-trimethylhexane, 2-methyl-3-ethylhexane, 2-methyl-4-ethylhexane, 3-methyl-3-ethylhexane, 3-methyl-4-ethylhexane, 3-diethylpentane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, n-propylcyclohexane, isopropylcyclohexane, trimethylcyclohexane (including various isomers of trimethylcyclohexane, such as 1,2, 3-trimethylcyclohexane, 1,2, 4-trimethylcyclohexane, 1,2, 5-trimethylcyclohexane, 1,3, 5-trimethylcyclohexane), n-decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 2, 3-dimethyloctane, 2, 4-dimethyloctane, 3-ethyloctane, 1-methyl-2-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-4-ethylcyclohexane, 1-methyl-3-ethylcyclohexane, 1-methyl-, 4-ethyloctane, 2,3, 4-trimethylheptane, 2,3, 5-trimethylheptane, 2,3, 6-trimethylheptane, 2,4, 5-trimethylheptane, 2,4, 6-trimethylheptane, 2, 3-trimethylheptane, 2, 4-trimethylheptane, 2, 5-trimethylheptane, 2,2, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane.One or a combination of two or more of an alkane, 4-methyl-4-ethylheptane, 4-propylheptane, 3-diethylhexane, 3, 4-diethylhexane, 2-methyl-3, 3-diethylpentane, phenylethane, 1-phenylpropane, 2-phenylpropane, 1-phenylbutane, 2-phenylbutane, 1-phenylpentane, 2-phenylpentane and 3-phenylpentane.
The hydrocarbon is more preferably one or two or more of propane, n-butane, isobutane and phenylethane, and further preferably n-butane.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the reaction may be carried out in the presence or absence of oxygen. Preferably in the presence of oxygen. When carried out in the presence of oxygen, the amount of oxygen may be conventionally selected. Generally, the molar ratio of hydrocarbon to oxygen may be from 0.01 to 100: 1, preferably 0.1 to 10: 1, more preferably 0.2 to 5: 1, most preferably 0.5-2: 1.
according to the hydrocarbon dehydrogenation reaction method, the hydrocarbon and optional oxygen can be fed into the reactor by the carrier gas to contact and react with the heteroatom-containing nano carbon material. The carrier gas may be a commonly used gas that does not chemically interact with the reactants and the reaction product under the reaction conditions and does not undergo decomposition, such as one or a combination of two or more of nitrogen, carbon dioxide, a noble gas, and water vapor. The amount of carrier gas may be conventionally selected. Generally, the carrier gas may be present in an amount of 30 to 99.5% by volume, preferably 50 to 99% by volume, more preferably 70 to 98% by volume.
In the process for the dehydrogenation of hydrocarbons according to the present invention, the temperature of the contacting may be conventionally selected to be sufficient for the dehydrogenation of hydrocarbons to take place. Generally, the contacting may be carried out at a temperature of from 200 to 650 ℃, preferably at a temperature of from 300 to 600 ℃, more preferably at a temperature of from 350 to 550 ℃, even more preferably at a temperature of from 400 to 450 ℃ when the hydrocarbon is butane.
According to the process for the dehydrogenation of hydrocarbons according to the present invention, the contacting is preferably carried out in a fixed bed reactor.
According to the invention, the dehydrogenation reaction of hydrocarbons is carried outThe duration of the contacting can be selected based on the temperature of the contacting, and can be expressed in terms of the weight hourly space velocity of the feed as the contacting is conducted in a fixed bed reactor. In general, the weight hourly space velocity of the feed gas may be in the range of from 1 to 50000h-1Preferably 10 to 20000h-1More preferably 50 to 10000h-1More preferably 100 to 8000h-1E.g. 1000-3000h-1。
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
in the following preparations, X-ray photoelectron spectroscopy was carried out on an ESCALab model 250X-ray photoelectron spectrometer equipped with ThermoAvantage V5.926 software, manufactured by Thermo Scientific, with an excitation source of monochromated AlK α X-rays, an energy of 1486.6eV, a power of 150W, a transmission energy for narrow scanning of 30eV, and a base vacuum of 6.5X 10 for analytical tests-10mbar, electron binding energy was corrected for the C1s peak (284.0eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
In the following preparation examples, thermogravimetric analysis was carried out on a TA5000 thermal analyzer under air atmosphere at a temperature rise rate of 10 ℃/min and at a temperature range of room temperature (25 ℃) to 1000 ℃. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing. The method adopts ASAP2000 type N of Micromertrics corporation in America2The physical adsorption apparatus measures the specific surface area.
The properties of the multi-walled carbon nanotubes as the raw nanocarbon material in the following preparation examples are listed in table 1 below.
TABLE 1
Figure BDA0001061592100000151
In the following examples and comparative examples, the contents of silicon, titanium and aluminum elements and the alkali content in the crystallization mother liquor and the heavy liquid were measured by a Perkin-Elmer 3300DV type Inductively Coupled Plasma (ICP) spectrometer.
In the following examples and comparative examples, the radial crush strength was measured according to the method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (edited by scientific Press, first edition 1990, Yankee, et al); the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (refer to "research on porosity of graphite porous material", lubrication and sealing ", 2010, 35 (10): 99-101) in percentage).
Preparation examples 1 to 40 were used to prepare heteroatom-containing nanocarbon materials.
Preparation example 1
(1) 20g of multiwall carbon nanotube A (purchased from Chengdu organic chemistry, Inc., of Chinese academy of sciences) as a raw nanocarbon material was dispersed in deionized water under ultrasonic oscillation conditions including: the frequency was 14kHz and the time was 0.5 hour. Then, NH is added3And triethanolamine to obtain an aqueous dispersion, wherein the weight ratio of the raw materials of the nano carbon material: NH (NH)3: triethanolamine: h2The weight ratio of O is 1: 0.05: 0.25: 50 parts of the raw materials.
(2) The resulting aqueous dispersion was reacted in a high-pressure autoclave with a polytetrafluoroethylene liner at a temperature of 140 ℃ under autogenous pressure for 36 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid substance at normal pressure (1 atm, the same below) and 120 deg.C for 12 hr to obtain heteroatom-containing nano carbon material with composition, specific surface area and w500/w800Listed in table 2.
Preparation example 2
The same aqueous dispersion as in preparation example 1 was placed in a three-necked flask equipped with a condenser tube, and the three-necked flask was placed in an oil bath at a temperature of 140 ℃ and subjected to reflux reaction under normal pressure for 36 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at the temperature of 120 ℃ for 12 hours under normal pressure to obtain the heteroatom-containing nano carbon material.
Preparation example 3
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that in step (1), the nanocarbon material was a multiwall carbon nanotube B.
Preparation example 4
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 1, except that, in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 90 ℃ under autogenous pressure for 36 hours.
Preparation example 5
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that, in step (1), NH was used3And triethanolamine in the same total molar amount as in preparation example 13The molar ratio of the triethanolamine to the triethanolamine is 1: 1.
preparation example 6
(1) 20g of multiwall carbon nanotube C (purchased from Chengdu organic chemistry, Inc., of Chinese academy of sciences) as a raw nanocarbon material was dispersed in deionized water under ultrasonic oscillation conditions including: the frequency was 90kHz and the time was 2 hours. Then, NH is added3And diethanolamine to obtain an aqueous dispersion, wherein the carbon nano-material is prepared from the following raw materials: NH (NH)3: diethanolamine: h2The weight ratio of O is 1: 2: 5: 80 in proportion.
(2) The resulting aqueous dispersion was reacted in a high-pressure autoclave with a polytetrafluoroethylene liner at a temperature of 180 ℃ under autogenous pressure for 24 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. The collected solid matter was dried at 150 ℃ for 6 hours under normal pressure to obtain a heteroatom-containing nanocarbon material, the structural parameters of which are listed in table 2.
Preparation example 7
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), the nanocarbon material was a multiwall carbon nanotube D.
Preparation example 8
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 6, except that, in step (2), the resulting aqueous dispersion was reacted in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner at a temperature of 230 ℃ under autogenous pressure for 24 hours.
Preparation example 9
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), NH was used3And diethanolamine under the same conditions as in preparation example 53: the mol ratio of the diethanol amine is 1: 0.1.
preparation example 10
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with an equimolar amount of n-propylamine.
Preparation example 11
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with an equimolar amount of pyridine.
Preparation example 12
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with an equimolar amount of cyclohexylamine.
Preparation example 13
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with ethylenediamine in a molar amount of 0.5 times that of diethanolamine in preparation example 6.
Preparation example 14
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with an equimolar amount of tetraethylammonium hydroxide.
Preparation example 15
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 6, except that, in step (1), diethanolamine was replaced with hexamethylenetetramine in a molar amount of 0.25 times that of diethanolamine in production example 6.
Preparation example 16
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that, in step (1), diethanolamine was replaced with diethylenetriamine having a molar amount of 0.3 times that of the diethanolamine in preparation example 6.
Preparation example 17
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that:
in the step (1), dispersing a raw material nano carbon material in deionized water, adding hydrazine and tetramethylammonium hydroxide, and uniformly mixing, wherein the raw material nano carbon material comprises the following components in percentage by weight: hydrazine: tetramethyl ammonium hydroxide: h2The weight ratio of O is 1: 0.02: 4.5: feeding at a ratio of 40; in the step (2), the obtained aqueous dispersion is reacted for 48 hours in a high-pressure reaction kettle with a polytetrafluoroethylene lining at the temperature of 120 ℃ under autogenous pressure to obtain the heteroatom-containing nano carbon material, and the structural parameters of the heteroatom-containing nano carbon material are listed in a table 3.
Preparation example 18
The same aqueous dispersion as in preparation example 17 was placed in a three-necked flask equipped with a condenser, and the three-necked flask was placed in an oil bath at a temperature of 120 ℃ and subjected to reflux reaction under normal pressure for 48 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at the temperature of 120 ℃ for 12 hours under normal pressure to obtain the heteroatom-containing nano carbon material.
Preparation example 19
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 17, except that, in step (2), the resulting aqueous dispersion was reacted in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner at a temperature of 80 ℃ under autogenous pressure for 48 hours.
Preparation example 20
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 17, except that the nanocarbon material used in the preparation example was a multiwall carbon nanotube B.
Preparation example 21
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 17, except that, in step (1), the total molar amount of hydrazine and tetramethylammonium hydroxide was changed under the same conditions as in production example 17 such that hydrazine: the molar ratio of the tetramethylammonium hydroxide is 1: 85.
preparation example 22
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that:
in the step (1), dispersing a raw material nano carbon material in deionized water, adding hydrazine and tetrapropyl ammonium hydroxide, and uniformly mixing to obtain an aqueous dispersion, wherein the raw material nano carbon material comprises the following components in percentage by weight: hydrazine: tetrapropylammonium hydroxide: h2The weight ratio of O is 1: 1: 8: 200 of a carrier; in the step (2), the obtained aqueous dispersion is placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 24 hours at the temperature of 170 ℃ under the autogenous pressure.
Preparation example 23
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 22, except that in step (1), the nanocarbon material used was a multiwall carbon nanotube D preparation example.
Preparation example 24
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 22, except that, in step (1), the total molar amount of hydrazine and tetrapropylammonium hydroxide was changed under the same conditions as in production example 22 such that hydrazine: the molar ratio of tetrapropylammonium hydroxide is 1: 1.
preparation example 25
A nanocarbon material containing hetero atoms was prepared in the same manner as in preparation example 22, except that, in step (2), the resulting aqueous dispersion was reacted in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner at a temperature of 200 ℃ under autogenous pressure for 24 hours.
Preparation example 26
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 22, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of diethanolamine.
Preparation example 27
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 22, except that in step (1), tetrapropylammonium hydroxide was replaced with an equimolar amount of n-propylamine.
Preparation example 28
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 22, except that in step (1), tetrapropylammonium hydroxide was replaced with hexamethylenediamine, which was present in an amount of 0.5 times the molar amount of tetrapropylammonium hydroxide in production example 22.
Preparation example 29
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 1, except that: in the step (1), dispersing a raw material nano carbon material in deionized water, adding urea and hexamethylenediamine, and uniformly mixing to obtain a water dispersion, wherein the raw material nano carbon material comprises the following components in percentage by weight: urea: hexamethylene diamine: h2The weight ratio of O is 1: 1: 1: 20; in the step (2), the obtained aqueous dispersion is placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 36 hours at the temperature of 110 ℃ under autogenous pressure.
Preparation example 30
The same aqueous dispersion as in preparation example 29 was placed in a three-necked flask equipped with a condenser, and the three-necked flask was placed in an oil bath at a temperature of 110 ℃ and subjected to reflux reaction under normal pressure for 36 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the heteroatom-containing nano carbon material.
Preparation example 31
A nanocarbon material containing hetero atoms was produced in the same manner as in production example 29, except that in step (2), the resulting aqueous dispersion was reacted at a temperature of 80 ℃ under autogenous pressure for 36 hours in a high-pressure reaction vessel with a polytetrafluoroethylene liner.
Preparation example 32
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 29, except that the nanocarbon material used in the preparation example was a multiwall carbon nanotube B.
Preparation example 33
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 29, except that, in step (1), the total molar amount of urea and hexamethylenediamine was changed in the same manner as in production example 29 such that urea: the molar ratio of hexamethylene diamine is 1: 0.1.
preparation example 34
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 6, except that:
in the step (1), dispersing the raw material nano carbon material in deionized water, and then adding urea and n-butylamine to be uniformly mixed, thereby obtaining an aqueous dispersion, wherein the weight ratio of the raw material nano carbon material: urea: n-butylamine: h2The weight ratio of O is 1: 4: 8: feeding at a ratio of 150; in the step (2), the obtained aqueous dispersion is placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 24 hours at the temperature of 160 ℃ under the autogenous pressure.
Preparation example 35
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 34, except that in step (1), the nanocarbon material used was a multiwall carbon nanotube D preparation example.
Preparation example 36
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 34, except that, in step (1), urea: the molar ratio of n-butylamine is 1: 2.5.
preparation example 37
A nanocarbon material containing hetero atoms was produced in the same manner as in production example 34, except that in the step (2), the obtained aqueous dispersion was reacted in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner at a temperature of 190 ℃ under autogenous pressure for 24 hours.
Preparation example 38
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 34, except that n-butylamine was replaced with an equimolar amount of diethanolamine.
Preparation example 39
A heteroatom-containing nanocarbon material was prepared in the same manner as in preparation example 34, except that n-butylamine was replaced with an equimolar amount of tetramethylammonium hydroxide.
Preparation example 40
A heteroatom-containing nanocarbon material was produced in the same manner as in production example 34, except that n-butylamine was replaced with ethylenediamine in an amount of 0.5 times the molar amount of n-butylamine in production example 34.
Figure BDA0001061592100000191
Figure BDA0001061592100000201
Examples 1 to 95 are for explaining nanocarbon material molded bodies according to the present invention and a method for preparing the same.
Examples 1-95 refer to the following binder sources.
Silica sol: purchased from Zhejiang Yuda chemical Co., Ltd, and the content of silica was 25% by weight
Tetraethyl orthosilicate: from Zhang Jiagang Xinya chemical Co Ltd (TES number)
Aluminum sol: purchased from Shandong Chilida chemical Co., Ltd., and having an alumina content of 12% by weight
Aluminum isopropoxide: purchased from Beijing Germany island gold technologies Co Ltd (number IPOA)
Titanium oxide: purchased from Shandong Zhengyuan nanometer materials engineering Co., Ltd, and has a particle diameter of 5-10nm
Tetraethyl titanate: from Jinyu chemical Limited liability company (TET)
(1) Crystallization mother liquor of titanium silicon molecular sieve
Titanium silicalite TS-1 was prepared according to the method of US4410501, example 1, and the crystallization mother liquor was collected. The specific operation process is as follows:
455g of tetraethylorthosilicate were placed in a reactor equipped with a stirring device and free of CO2In the reactor under the atmosphere, 15g of tetraethyl titanate and 800g of 25% strength by weight aqueous tetrapropylammonium hydroxide solution were then added. After stirring for 1 hour, raising the temperature to 80-90 ℃, and continuing stirring for 5 hours. Deionized water was then added to the reaction solution until the total volume of the reaction solution was 1.5L. And then, transferring the reaction liquid into a high-pressure reaction kettle with a stirring device, carrying out hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, and roasting the filtered solid in air atmosphere at 550 ℃ for 6 hours to obtain the titanium silicalite TS-1.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 1.2% by weight in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 3.1% by weight. Concentrating the crystallization mother liquor (concentrated solution number TS-A) to SiO based on the total amount of the concentrated solution2The content of silicon element was 3.6% by weight in terms of TiO2The content of titanium element was 0.12% by weight, and the content of tetrapropylammonium hydroxide was 9.3% by weight.
(2) Crystallization mother liquor of titanium silicon molecular sieve
The titanium silicalite TS-1 was prepared according to the method of US4410501, example 2, and the crystallization mother liquor was collected. The specific operation process is as follows:
150g tetraethyl titanate was slowly added dropwise to 2.5L distilled water and hydrolyzed under stirring to give a white colloidal suspension which was then cooled to 5 ℃; then 1.8L of a 30% aqueous solution of hydrogen peroxide having been cooled to 5 ℃ in advanceAdded thereto and kept at 5 ℃ for 2 hours with intermittent stirring to give an orange clear solution; then 2.4L of 25% strength by mass aqueous tetrapropylammonium hydroxide solution which had previously been cooled to 5 ℃ were added to the orange clear solution, and after 1 hour 500g of SiO were added2Carefully mixing silica sol with the content of 40%, and standing the obtained mixture at normal temperature overnight; finally, the mixture is heated and stirred for 6 hours at 70-80 ℃. And transferring the obtained mixture into a high-pressure reaction kettle with a stirring device, carrying out hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, roasting the filtered solid phase for 6 hours in an air atmosphere at 550 ℃, and obtaining the titanium silicalite TS-1 through X-ray diffraction analysis.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 2.8 wt.% in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 1.6% by weight. Concentrating the crystallized mother liquor (concentrated solution number TS-B) to SiO based on the total amount of the concentrated solution2The content of silicon element is 7 wt% in terms of TiO2The content of titanium element was 0.1% by weight, and the content of tetrapropylammonium hydroxide was 4% by weight.
(3) Crystallization mother liquor of titanium silicon molecular sieve
The titanium silicalite Ti-Beta was prepared as described in J.chem.Soc.chem.Commun, 1992, 589-590 and the crystallization mother liquor was collected during the solid-liquid separation. The preparation process comprises the following steps:
tetraethyl titanate and amorphous silica gel Aerosil 200 were added to an aqueous tetraethylammonium hydroxide (TEAOH) solution with stirring at room temperature, followed by the addition of a suitable amount of aluminum nitrate, the molar composition of the gel formed being A12O3：TiO2：SiO2：H2O: TEAOH ═ 1: 12: 388: 6000: 108, transferring the formed glue solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining for dynamic crystallization, wherein the crystallization temperature is 130 ℃, the stirring speed is 60rpm, and the crystallization time is 3 d. Cooling, centrifuging the solid-liquid mixture to obtain solid and crystallized mother liquorNumber TS-C). And washing the separated solid with water until the pH value is about 9, drying at 80 ℃ for 5h, and roasting at 580 ℃ in an air atmosphere for 5h to obtain the titanium silicalite Ti-Beta.
The detection shows that the total amount of the crystallization mother liquor (with the number of TS-C) is taken as the reference, and SiO is taken as the reference2The content of silicon element was 3.4 wt% in terms of TiO2The content of titanium element was 0.3% by weight, and the content of tetraethylammonium hydroxide was 13.1% by weight.
(4) Rearrangement liquid of titanium-silicon molecular sieve
The method of embodiment 9 of the chinese application 99126289.1 is used to obtain the heavy liquid discharge of the titanium silicalite molecular sieve, and the specific preparation process is as follows:
according to TS-1 molecular sieve (g): tetraethylammonium hydroxide (mol): water (mole) ═ 100: 0.25: 60, placing the mixture into a stainless steel sealed reaction kettle, and placing the mixture for 3 days at a constant temperature of 175 ℃ and an autogenous pressure. Cooling, releasing pressure, and filtering to obtain filtrate, i.e. the heavy discharge liquid of the titanium-silicon molecular sieve.
Through detection, the total amount of the heavy discharge liquid is taken as a reference, and SiO is taken2The content of silicon element was 1.1% by weight in terms of TiO2The content of titanium element was 0.02% by weight, and the content of tetrapropylammonium hydroxide was 3.6% by weight. Concentrating the rearranged solution (the concentrated solution is numbered TS-D) to SiO based on the total amount of the rearranged solution2The content of elemental silicon was 4.4% by weight in terms of TiO2The content of titanium element was 0.08% by weight, and the content of tetrapropylammonium hydroxide was 14.4% by weight.
(5) Crystallization mother liquor of silicon-aluminum molecular sieve
Referring to US4410501, example 1, a silicon aluminum molecular sieve is prepared using aluminum isopropoxide as an aluminum source instead of tetraethyl titanate as a titanium source, and the crystallization mother liquor is collected. The specific operation process is as follows:
in the absence of CO2In a heat-resistant glass vessel, 455g of tetraethyl silicate was placed in the vessel, 15g of aluminum isopropoxide was added with stirring, 800g of an aqueous 25% tetrapropylammonium hydroxide solution was added, the mixture was mixed for 4 hours, and the mixture was heated at 80 to 90 ℃ and stirred for 5 hours, thereby completely removing ethanol. Then adding water to 1.5L to obtainThe resulting mixture was transferred to a high-pressure reaction vessel equipped with a stirring device, subjected to hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, and the resulting reaction mixture was filtered to collect a crystallization mother liquor.
The detection shows that the total amount of the crystallization mother liquor (the crystallization mother liquor is numbered AS-F) is taken AS the reference, and SiO is taken AS the reference2The content of silicon element calculated as Al was 2.3 wt%2O3The content of aluminum element was 0.14% by weight, and the content of tetrapropylammonium hydroxide was 12.5% by weight. Concentrating the crystallization mother liquor (concentrated solution number is AS-E) to SiO based on the total amount of the concentrated solution2The content of silicon element calculated as Al was 8.28 wt%2O3The content of aluminum element was 0.50 wt%, and the content of tetrapropylammonium hydroxide was 45 wt%.
Examples 1 to 48
The nanocarbon materials were molded by the following methods, respectively, under the conditions given in table 4.
The nanocarbon material was mixed with a binder source at ambient temperature (25 ℃) respectively, the resulting mixture was fed into a bar mold and dried and optionally calcined to obtain nanocarbon material moldings (a portion of the moldings was randomly selected and ground to obtain a sample bar of 3-5mm in length for measuring crushing strength and porosity, the results are listed in table 4), and the remaining moldings were crushed and sieved to obtain granular moldings, the average particle size (particle size for short) of which is listed in table 4.
TABLE 4
Figure BDA0001061592100000221
Figure BDA0001061592100000231
1: the amount of the nanocarbon material is 10g2: tetrapropylammonium hydroxide3: tetraethyl ammonium hydroxide4: the amount is calculated by oxide5: where an additional treatment agent is added in addition to the treatment agent contained in the binder sourceThe type and amount of the physical agent
Examples 49 to 91
The following methods were used to shape the nanocarbon materials according to the conditions given in table 5, respectively:
mixing the nano carbon material with a binder source and an optional treating agent respectively, then placing the obtained mixture into a sealed high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment under autogenous pressure. After the temperature in the high-pressure reaction kettle is reduced to the ambient temperature, the reaction kettle is opened, the obtained slurry is sent into a strip-shaped mold to be dried and optionally roasted to obtain a nano-carbon material forming body (a part of the forming body is randomly selected to be ground to obtain a sample strip with the length of 3-5mm for measuring the crushing resistance strength and the porosity, the result is listed in table 5), the rest forming body is crushed and then screened to obtain a granular forming body, and the average particle size of the granular forming body is listed in table 5.
Example 92
The difference from example 49 is that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.
Example 93
The difference from example 49 is that a mixture of a nanocarbon material and a binder source was placed in a three-necked flask, a reflux reaction was carried out at the same temperature as the hydrothermal treatment temperature in example 49 for the same time as the hydrothermal treatment in example 49, and the mixture obtained by the reflux reaction was charged into a mold.
Example 94
The difference from example 54 is that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.
Example 95
The difference from example 54 is that a mixture of a nanocarbon material and a binder source was placed in a three-necked flask, a reflux reaction was carried out at the same temperature as the hydrothermal treatment temperature in example 54 for the same time as the hydrothermal treatment in example 54, and the mixture obtained by the reflux reaction was fed into a mold.
TABLE 5
Figure BDA0001061592100000241
Figure BDA0001061592100000251
1: the amount of the nanocarbon material is 10g2: tetrapropylammonium hydroxide3: tetraethyl ammonium hydroxide4: the amount is calculated by oxide5: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Test examples 1 to 95
The catalysts prepared in examples 1-95 were tested for catalytic performance in the following order.
0.25g of each of the granular molded bodies prepared in examples 1 to 95 was packed as a catalyst in a general fixed bed microtube reactor each having quartz sand sealed at both ends, and a gas containing n-butane and oxygen (n-butane concentration of 2.08 vol%, n-butane/oxygen molar ratio of 0.5: 1, and the balance nitrogen as a carrier gas) was fed at 0MPa (gauge pressure) and 425 ℃ for 2000 hours-1The reaction was carried out while feeding the weight hourly space velocity of (a) into the reactor, the composition of the reaction mixture output from the reactor was continuously monitored, and the n-butane conversion and the total olefin selectivity were calculated, and the results of the reaction for 3 hours and 24 hours are shown in Table 6.
Testing of comparative examples 1-4
The catalytic performance of multi-walled carbon nanotubes A, B, C and D were tested in turn using the same method as in test examples 1-95.
TABLE 6
Figure BDA0001061592100000252
Figure BDA0001061592100000261
Figure BDA0001061592100000271
Figure BDA0001061592100000281
Figure BDA0001061592100000291
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (117)

1. A nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material, wherein the nanocarbon material contains an O element and an N element, and the content of the O element is 4.5 to 7% by weight, the content of the N element is 3.5 to 4.5% by weight, and the content of the C element is 88.5 to 92% by weight, based on the total amount of the nanocarbon material and calculated as the elements;
the amount of O element determined by a peak in the range of 531.0-532.5eV in an X-ray photoelectron spectrum is IO cThe amount of O element determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eIn the range of 1.4-2The inside of the enclosure;
in the nano carbon material, the total amount of N elements in the nano carbon material containing the heteroatom is determined to be I by X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is IN c，IN c/IN tIn the range of 0.7 to 1;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material, at least one nitrogen-containing compound selected from NH and at least one organic base are dispersed in a closed vessel3Hydrazine and urea, the organic base being selected from amines and quaternary ammonium bases, the temperature of the aqueous dispersion being maintained in the range of 80-250 ℃ during the reaction, the duration of the reaction being in the range of 0.5-96 hours, the starting nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.01-20: 0.01-20, raw material nano carbon material: h2The weight ratio of O is 1: 2-1000, wherein in the raw material nano carbon material, the content of N element is not higher than 0.2 weight percent, the content of O element is not higher than 1.5 weight percent, the total amount of metal elements is less than 2.5 weight percent, and the organic base is a compound shown in a formula I, a compound shown in a formula II, a compound shown in a formula III and a general formula R12(NH2)2One or more of the substances represented by R12Is C1-C6The alkylene group of (a) is,
Figure FDA0002373827740000011
in the formula I, R1、R2、R3And R4Each is C1-C20Alkyl or C6-C12Aryl of (a);
Figure FDA0002373827740000012
in the formula II, R5、R6And R7Each is H or C1-C6And R is alkyl of5、R6And R7Not H at the same time;
Figure FDA0002373827740000013
in the formula III, R8、R9And R10Each is-R11OH, hydrogen or C1-C6And R is alkyl of8、R9And R10At least one of which is-R11OH，R11Is C1-C4An alkylene group of (a).
2. The molded body according to claim 1, wherein the total amount of N element in the nanocarbon material containing hetero atoms is I as determined by X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is IN c，IN c/IN tIn the range of 0.75-0.98.
3. Shaped body according to claim 2, wherein IN c/IN tIn the range of 0.8-0.95.
4. Shaped body according to any one of claims 1 to 3, wherein the amount of C element in the nanocarbon material, determined by a peak in the range of 288.6-288.8eV in the X-ray photoelectron spectrum, is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eIn the range of 1.5-4.
5. Shaped body according to claim 4, wherein IC c/IC eIn the range of 1.5-3.5.
6. Shaped body according to claim 5, wherein IC c/IC eIn the range of 1.55-3.
7. The molded body according to any one of claims 1 to 3, wherein the content of C element determined from a peak in the range of 284.7 to 284.9eV in the X-ray photoelectron spectrum is 60 to 98% by weight, and the content of C element determined from a peak in the range of 286.0 to 288.8eV in the X-ray photoelectron spectrum is 2 to 40% by weight, based on the total amount of C element in the nanocarbon material determined by the X-ray photoelectron spectrum.
8. The molded body according to claim 7, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in the X-ray photoelectron spectrum is 65-95% by weight and the content of C element determined from a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum is 5-35% by weight, based on the total amount of C element in the nanocarbon material determined from the X-ray photoelectron spectrum.
9. The molded body according to claim 8, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in the X-ray photoelectron spectrum is 70-90% by weight, and the content of C element determined from a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum is 10-30% by weight, based on the total amount of C element in the nanocarbon material determined from the X-ray photoelectron spectrum.
10. Shaped body according to any one of claims 1 to 3, wherein the total amount of N elements in the nanocarbon material is I as determined by X-ray photoelectron spectroscopyN tThe amount of N element determined from a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is IN g，IN g/IN tIs not higher than 0.3.
11. Shaped body according to claim 10, wherein IN g/IN tIn the range of 0.02-0.25.
12. The shaped body according to claim 11, wherein IN g/IN tIn the range of 0.05-0.2.
13. Shaped body according to any one of claims 1 to 3, wherein the nanocarbon material is carbon nanotubes.
14. The shaped body according to claim 13, wherein the nanocarbon material is a multiwall carbon nanotube.
15. The shaped body according to claim 14, wherein the multi-walled carbon nanotubes have a specific surface area of 50 to 500m2/g。
16. The shaped body according to claim 15, wherein the multi-walled carbon nanotubes have a specific surface area of 80-300m2/g。
17. The shaped body according to claim 16, wherein the multi-walled carbon nanotubes have a specific surface area of 90 to 150m2/g。
18. The shaped body according to claim 17, wherein the multi-walled carbon nanotubes have a specific surface area of 95 to 140m2/g。
19. The shaped body according to claim 14, wherein the multi-walled carbon nanotubes have a total weight loss ratio w in the temperature interval of 400-800 ℃800The total weight loss rate in the temperature interval of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
20. The shaped body of claim 19, wherein w is500/w800In the range of 0.02-0.2.
21. The molded body according to claim 1, wherein the raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-10: 0.02-15.
22. The molded body according to claim 1, wherein the raw material nanocarbon material: h2The weight ratio of O is 1: 5-500.
23. The shaped body according to claim 22, wherein the raw nanocarbon material: h2The weight ratio of O is 1: 10-300.
24. The shaped body according to claim 23, wherein the raw nanocarbon material: h2The weight ratio of O is 1: 20-200.
25. The shaped body according to any one of claims 1 and 21 to 24, wherein the nitrogen-containing compound: the molar ratio of the organic base is 1: 0.05-100.
26. The shaped body of claim 25, wherein the nitrogen-containing compound: the molar ratio of the organic base is 1: 0.1-90.
27. The shaped body of claim 26, wherein the nitrogen-containing compound: the molar ratio of the organic base is 1: 0.4-80.
28. The shaped body according to any one of claims 1 and 21 to 24, wherein the nitrogen-containing compound is ammonia, the organic base is selected from a compound represented by formula III, a raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-10: 0.05 to 8, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.05-5.
29. The shaped body according to claim 28, wherein the organic base is selected from the group consisting of ethanolamine, diethanolamine and triethanolamine.
30. The shaped body according to claim 28, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.03-5: 0.1 to 6, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.1-2.5.
31. The molded body according to claim 30, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.05-2: 0.2 to 5, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.4-0.8.
32. The shaped body according to any one of claims 1 and 21 to 24, wherein the nitrogen-containing compound is hydrazine, the organic base is selected from compounds of formula I, raw nanocarbon materials: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.01-5: 0.02 to 10, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.5-100.
33. The shaped body according to claim 32, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-2.5: 1-9, nitrogen-containing compound: the molar ratio of the organic base is 1: 1-90.
34. The shaped body according to claim 33, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-1.5: 4.5-8, nitrogen-containing compound: the molar ratio of the organic base is 1: 1.1-80.
35. The shaped body according to any one of claims 1 and 21 to 24, wherein the nitrogen-containing compound is urea and the organic base is selected from compounds of formula II and general formula R12(NH2)2The substance represented, raw material nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.02-10: 0.05 to 20, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.1-5.
36. The shaped body according to claim 35, wherein the organic base is selected from ethylenediamine, n-butylamine and hexamethylenediamine.
37. The shaped body according to claim 35, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 0.1-8: 0.5 to 15, nitrogen-containing compound: the molar ratio of the organic base is 1: 0.5-2.
38. The shaped body according to claim 37, wherein the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the organic base is 1: 1-5: 1-10.
39. Shaped body according to any one of claims 1 and 21 to 24, wherein the temperature of the aqueous dispersion is kept in the range of 80 to 250 ℃ during the reaction.
40. Shaped body according to claim 39, wherein the temperature of the aqueous dispersion is maintained in the range of 100 to 180 ℃ during the reaction.
41. The shaped body according to claim 1, wherein the duration of the reaction is in the range of 2 to 72 hours.
42. Shaped body according to claim 41, wherein the duration of the reaction is in the range of 10-40 hours.
43. The molded body according to claim 1, wherein the content of N element in the raw nanocarbon material is not more than 0.02% by weight; the content of the O element is not higher than 0.3 wt%; the total amount of the metal elements is 0.5 wt% or less.
44. The shaped body according to any one of claims 1, 21-24 and 41-43, wherein the raw nanocarbon material is carbon nanotubes.
45. The shaped body according to claim 44, wherein the starting nanocarbon material is multi-walled carbon nanotubes.
46. The shaped body according to claim 45, wherein the multi-walled carbon nanotubes have a specific surface area of 50 to 500m2/g。
47. The shaped body according to claim 46, wherein the multi-walled carbon nanotubes have a specific surface area of 100 to 260m2/g。
48. The shaped body according to claim 47, wherein the multi-walled carbon nanotubes have a specific surface area of 120 to 190m2/g。
49. The shaped body according to claim 45, wherein the multi-walled carbon nanotubes have a total weight loss ratio w in the temperature interval of 400-800 ℃800The total weight loss rate in the temperature interval of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
50. The shaped body of claim 49, wherein w is500/w800In the range of 0.02-0.4.
51. The shaped body according to any one of claims 1, 21 to 24 and 41 to 43, wherein the process further comprises separating solid matter from the mixture obtained from the reaction and drying the separated solid matter.
52. The shaped body according to claim 51, wherein the drying is carried out at a temperature of 50-400 ℃ and the duration of the drying is not more than 48 hours.
53. Shaped body according to claim 52, wherein the drying is carried out at a temperature of 80-180 ℃ and the duration of the drying is 4-24 hours.
54. Shaped body according to claim 53, wherein the duration of drying is from 6 to 12 hours.
55. The shaped body according to any one of claims 1 to 3, 21 to 24 and 41 to 43, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the heat-resistant inorganic oxide is contained in an amount of 6 to 94% by weight, based on the total amount of the shaped body.
56. The shaped body according to claim 55, wherein the nanocarbon material is contained in an amount of 10 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 90% by weight, based on the total amount of the shaped body.
57. The shaped body according to claim 56, wherein the nanocarbon material is contained in an amount of 40 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 60% by weight, based on the total amount of the shaped body.
58. The shaped body according to claim 57, wherein the nanocarbon material is present in an amount of 70-90 wt.% and the heat-resistant inorganic oxide is present in an amount of 10-30 wt.%, based on the total amount of the shaped body.
59. The molded body according to any one of claims 1 to 3, 21 to 24 and 41 to 43, wherein the heat-resistant inorganic oxide is one or two or more of alumina, silica and titania.
60. The shaped body according to claim 59, wherein the heat-resistant inorganic oxide comprises silicon oxide.
61. The shaped body according to claim 60, wherein the silicon oxide is contained in an amount of 10 to 100% by weight, based on the total amount of the heat-resistant inorganic oxide.
62. The shaped body according to claim 61, wherein the silicon oxide is contained in an amount of 20 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
63. The shaped body according to claim 62, wherein the silicon oxide is contained in an amount of 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
64. A method for producing a nanocarbon material molded body, which comprises mixing a nanocarbon material with a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, molding the obtained mixture to obtain a molded body, and drying and optionally firing the molded body, wherein the nanocarbon material is a nanocarbon material which is not surface-treated and a nanocarbon material which is surface-treated, as determined by X-ray photoelectron spectroscopy, and the nanocarbon material which is surface-treated contains an O element and an N element, and the nanocarbon material is the nanocarbon material according to any one of claims 1 to 54.
65. The method of claim 64, wherein the mixture further comprises at least one base.
66. The method of claim 65, wherein the base is one or more of ammonia, a base whose cation is an alkali metal, a base whose cation is an alkaline earth metal, urea, hydrazine, an amine, and a quaternary ammonium base.
67. A process according to claim 66, wherein the base is selected from quaternary ammonium bases.
68. The method of claim 67, wherein the base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
69. A process according to claim 68, wherein the base is selected from compounds of formula I:
Figure FDA0002373827740000071
in the formula I, R1、R2、R3And R4Each is C1-C20Alkyl group of (1).
70. The method of claim 69, wherein, in formula I, R1、R2、R3And R4Each is C1-C6Alkyl group of (1).
71. The method of any of claims 65-70, wherein the molar ratio of the base to the binder source is 0.05-15: 1, the binder source is calculated by oxide.
72. The method of claim 71, wherein the molar ratio of the base to the binder source is from 0.1 to 12: 1, the binder source is calculated by oxide.
73. The method of any of claims 64-70, further comprising subjecting the mixture to a hydrothermal treatment prior to shaping the mixture.
74. The process of claim 73, wherein the hydrothermal treatment is carried out at a temperature of 100-200 ℃ and the duration of the hydrothermal treatment is 0.5-24 hours.
75. The method of claim 74, wherein the hydrothermal treatment is carried out at a temperature of 120-180 ℃ for a duration of 6-12 hours.
76. The method of any of claims 64-70, wherein at least a portion of the binder source, at least a portion of the optional base, and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor of a silicaceous molecular sieve and a rearrangement modification mother liquor of a silicaceous molecular sieve.
77. The method of claim 76, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a rearrangement modification liquid of an all-silicon molecular sieve, a crystallization mother liquid and/or a rearrangement modification liquid of a titanium-silicon molecular sieve, and a crystallization mother liquid and/or a rearrangement modification liquid of a silicon-aluminum molecular sieve.
78. A method for forming a nanocarbon material, which comprises subjecting a nanocarbon material to hydrothermal treatment in an aqueous dispersion, forming a slurry obtained by the hydrothermal treatment to obtain a formed product, and drying and optionally calcining the formed product, wherein the aqueous dispersion contains a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nanocarbon material is a nanocarbon material which is not surface-treated and a surface-treated nanocarbon material, or the nanocarbon material is a surface-treated nanocarbon material which is determined by X-ray photoelectron spectroscopy and contains an O element and an N element, and the surface-treated nanocarbon material is the nanocarbon material according to any one of claims 1 to 54.
79. The method of claim 78, wherein the aqueous dispersion further comprises at least one treating agent, the treating agent being an organic base and/or a nitrogen-containing compound selected from NH3Hydrazine and urea.
80. A process according to claim 79, wherein the organic base is selected from quaternary ammonium bases and amines.
81. The method of claim 80, wherein the organic base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
82. A process according to claim 81, wherein the organic base is selected from compounds of formula I:
Figure FDA0002373827740000081
in the formula I, R1、R2、R3And R4Each is C1-C20Alkyl group of (1).
83. The method of claim 82, wherein, in formula I, R1、R2、R3And R4Each is C1-C6Alkyl group of (1).
84. The method of claim 79, wherein the treating agent is an organic base and/or a nitrogen-containing compound.
85. A process as claimed in claim 84, wherein said organic base is present in an amount of from 20 to 100% by weight, based on the total amount of said treating agent.
86. A process as claimed in claim 85, wherein the organic base is present in an amount of from 35 to 92% by weight, based on the total amount of treatment agent.
87. A process as claimed in claim 79, in which the treating agent is an organic base and/or a nitrogen-containing compound and at least part of the organic base is a quaternary ammonium base.
88. A process as claimed in claim 87, in which the organic base is present in an amount of from 50 to 100% by weight and the quaternary ammonium base is present in an amount of from 40 to 100% by weight, based on the total amount of treatment agent.
89. A process as claimed in claim 88, in which said organic base is present in an amount of from 65 to 92% by weight and said quaternary ammonium hydroxide is present in an amount of from 45 to 92% by weight, based on the total amount of said treating agent.
90. The method of any of claims 79 to 89, wherein the molar ratio of the treating agent to the binder source is from 0.05 to 15: 1, the binder source is calculated by oxide.
91. The method of claim 90, wherein the molar ratio of the treating agent to the binder source is from 0.1 to 12: 1, the binder source is calculated by oxide.
92. The method of claim 91, wherein the molar ratio of the treating agent to the binder source is from 0.5-3.5: 1, the binder source is calculated by oxide.
93. The method of any of claims 78-89, wherein at least a portion of the binder source, at least a portion of the optional organic base, and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor of a silicaceous molecular sieve and a rearrangement-modified mother liquor of a silicaceous molecular sieve.
94. The method of claim 93, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a rearrangement modification liquid of an all-silicon molecular sieve, a crystallization mother liquid and/or a rearrangement modification liquid of a titanium-silicon molecular sieve, and a crystallization mother liquid and/or a rearrangement modification liquid of a silicon-aluminum molecular sieve.
95. The process of any one of claims 78 to 89, wherein the hydrothermal treatment is carried out at a temperature of 100-200 ℃ and the duration of the hydrothermal treatment is 0.5-24 hours.
96. The method of claim 95, wherein the hydrothermal treatment is performed at a temperature of 120-180 ℃ for a duration of 6-12 hours.
97. The method of any of claims 64-70 and 78-89, wherein the refractory inorganic oxide is one or more of alumina, silica and titania.
98. The method of claim 97, wherein the refractory inorganic oxide comprises silicon oxide.
99. The method as claimed in claim 98, wherein the silicon oxide is present in an amount of 10-100 wt% based on the total amount of the refractory inorganic oxide.
100. The method as claimed in claim 99, wherein the silica is present in an amount of 20-99 wt% based on the total amount of the refractory inorganic oxide.
101. The method as claimed in claim 100, wherein the silicon oxide is present in an amount of 50-99 wt% based on the total amount of the refractory inorganic oxide.
102. The method of any of claims 64-70 and 78-89, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 5-95 wt% and the refractory inorganic oxide content is 5-95 wt%.
103. The method of claim 102, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 6-94% by weight and the refractory inorganic oxide content is 6-94% by weight.
104. The method as claimed in claim 103, wherein the binder source is used in an amount such that the nanocarbon material is present in an amount of 75-95 wt% and the refractory inorganic oxide is present in an amount of 5-25 wt% in the finally prepared shaped body.
105. The method of claim 104, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 85-95 wt% and the refractory inorganic oxide content is 5-15 wt%.
106. The method of any one of claims 64-70 and 78-89, wherein the drying is performed at a temperature of 50-200 ℃, the duration of the drying being no more than 48 hours;
the roasting is carried out at a temperature of 300-800 ℃, and the roasting duration is 1-12 hours.
107. The method of claim 106, wherein the drying is performed at a temperature of 120-180 ℃; the duration of the drying is 3-24 hours;
the roasting is carried out at a temperature of 350-650 ℃, and the roasting duration is 2-4 hours.
108. The method of claim 107, wherein the drying is for a duration of 5-15 hours.
109. A nanocarbon material shaped body prepared by the method of any one of claims 64-108.
110. Use of a nanocarbon material shaped body as claimed in any one of claims 1 to 63 and 109 as a catalyst for dehydrogenation reactions of hydrocarbons.
111. The use of claim 110, wherein the hydrocarbon is an alkane.
112. The use of claim 111, wherein the hydrocarbon is C2-C12Of (a) an alkane.
113. The use of claim 112, wherein the hydrocarbon is n-butane.
114. A hydrocarbon dehydrogenation reaction process comprising contacting a hydrocarbon with the nanocarbon material shaped body of any one of claims 1 to 63 and 109 under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
115. The method of claim 114, wherein the hydrocarbon is an alkane.
116. The method of claim 115, wherein the hydrocarbon is C2-C12Of (a) an alkane.
117. The method of claim 116, wherein the hydrocarbon is n-butane.
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