CN107661765B - 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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CN107661765B
CN107661765B CN201610603025.XA CN201610603025A CN107661765B CN 107661765 B CN107661765 B CN 107661765B CN 201610603025 A CN201610603025 A CN 201610603025A CN 107661765 B CN107661765 B CN 107661765B
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nanocarbon material
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weight
body according
metal compound
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CN107661765A (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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a nano carbon material forming body, a preparation method and application thereof, a forming method of a nano carbon material and a hydrocarbon dehydrogenation reaction method. 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 an aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material containing an O element and at least one metal element selected from a transition metal element, a group IA metal element and a group IIA metal element, and a heat-resistant inorganic oxide for binding 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 solution in which a raw material nanocarbon material is dispersed in a closed container, wherein at least one peroxide and at least one metal compound are dispersed in the aqueous dispersion solution, the metal compound is selected from a basic metal compound and a transition metal compound, a metal element in the basic metal compound is selected from a group IA metal element and a group IIA metal element, and the temperature of the aqueous dispersion solution is in the range of 80-300 ℃ during the reaction.
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material molded body, the method 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 nanocarbon material which has been surface-treated, the surface-treated nanocarbon material containing an O element and at least one metal element selected from a transition metal element, a group IA metal element and a group IIA metal element, as determined by X-ray photoelectron spectroscopy.
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, 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, drying and optionally calcining the formed product, the aqueous dispersion containing a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nanocarbon material being an unpretreated nanocarbon material and/or a treated nanocarbon material, the treated nanocarbon material containing an O element and at least one metal element selected from a transition metal element, a group IA metal element and a group IIA metal element as determined by X-ray photoelectron spectroscopy.
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 present invention, "in the range of x to x" includes two boundary values when a numerical range is expressed. 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.
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 contains an O element and at least one metal element (hereinafter, sometimes also referred to as a nanocarbon material containing a metal atom).
The contents of the O element and the metal element in the nano carbon material can be selected according to the source of the nano carbon material and can also be selected according to the specific application occasion of the nano carbon material forming body. Generally, the content of the O element may be 1 to 15 wt%, preferably 2 to 12 wt%, more preferably 5 to 10 wt% in terms of the element, based on the total amount of the nanocarbon material; the content of the metal element may be 0.2 to 20% by weight, preferably 0.5 to 18% by weight, more preferably 1 to 9% by weight. Wherein, the content of each element is measured by adopting an X-ray photoelectron spectroscopy. The samples were dried at a temperature of 150 ℃ for 3 hours in a helium atmosphere before testing.
In the present invention, the X-ray photoelectron spectroscopy was carried out on an ESCALab250 type X-ray photoelectron spectrometer equipped with ThermoAvantage V5.926 software, manufactured by Thermo Scientific, with the excitation source being monochromatized AlK α X-ray, the energy being 1486.6eV, the power being 150W, the transmission energy for narrow scan being 30eV, the base vacuum at the time of analytical test being 6.5X 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.
According to the molded body of the first aspect of the present invention, the metal element is selected from the group consisting of transition metal elements, group IA metal elements and group IIA metal elements.
Specific examples of the group IA metal element and the group IIA metal element may include, but are not limited to, one or two or more of lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium. Preferably, the group IA metal element and the group IIA metal element are one or more of sodium, potassium, magnesium, calcium, and barium, so that when the nanocarbon material molded body is used as a catalyst for a dehydrogenation reaction of hydrocarbons, better catalytic performance can be obtained.
The transition metal element may be selected from the group consisting of a group IIIB metal element, a group IVB metal element, a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IB metal element, and a group IIB metal element in the periodic table of elements. Specific examples of the transition metal element may include, but are not limited to, scandium, yttrium, rare earth metal elements (e.g., lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc. Preferably, the transition metal element is selected from group VIII metal elements, in which case higher catalytic activity can be obtained when the nanocarbon material molded body is used as a catalyst for dehydrogenation reaction of hydrocarbon. The transition metal element is more preferably selected from group VIII metal elements, and further preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
According to the molded body of the first aspect of the present invention, the nanocarbon material may contain only a transition metal element, may contain only a group IA metal element and/or a group IIA metal element, and may contain both a transition metal element and a metal element selected from group IA and group IIA. In one embodiment, the metal element is a group IA metal element and/or a group IIA metal element (hereinafter, the nanocarbon material according to this embodiment is referred to as a basic metal element-containing nanocarbon material). In another embodiment, the metal element is a transition metal element (hereinafter, the nanocarbon material according to this embodiment is referred to as a transition metal element-containing nanocarbon material). Although the nanocarbon material according to the present invention may contain the metal element, it is preferable to optimize the content and the existence form of each element in the nanocarbon material according to the kind of the metal element contained in the nanocarbon material, from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body as a catalyst for dehydrogenation reaction of hydrocarbons, and the nanocarbon material according to the above two embodiments will be described in detail below.
According to the alkali metal element-containing nanocarbon material of the present invention, the content of the O element may be 2 to 12% by weight, preferably 2.5 to 10% by weight, and more preferably 5 to 8% by weight, the content of the C element may be 78 to 97.5% by weight, preferably 85 to 96.5% by weight, and more preferably 88 to 94% by weight, and the total amount of the metal element may be 0.5 to 10% by weight, preferably 1 to 5% by weight, and more preferably 1 to 4% by weight, based on the total amount of the nanocarbon material and calculated as an element.
According to the nanocarbon material containing an alkali metal element of the present invention, the total content of oxygen element determined by X-ray photoelectron spectroscopy is IO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tMay be in the range of 0.02 to 0.3, preferably in the range of 0.05 to 0.25, more preferably in the range of 0.08 to 0.2. The content of O element determined by the peak in the range of 531.0-533.5eV in the X-ray photoelectron spectrum is IO nm，IO nm/IO tMay be in the range of 0.7 to 0.98, preferably in the range of 0.75 to 0.95, more preferably in the range of 0.8 to 0.92.
In the present invention, the area of the peak of O1s in the X-ray photoelectron spectrum is represented as AO 1The peaks in the O1s spectrum were divided into two groups, and the area of the peak (corresponding to the oxygen species bound to the metal atom) in the range of 529.5-530.8eV was designated AO 2The area of the peak in the range of 531.0 to 533.5eV (corresponding to the oxygen species not bonded to the metal atom) is denoted as AO 3Wherein, IO m/IO t＝AO 2/AO 1，IO nm/IO t＝AO 3/AO 1。
Containing an alkali metal element according to the present inventionNanocarbon material having an amount of 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, i.e., 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 0.3 to 1.5, preferably in the range of 0.3 to 1.2, more preferably in the range of 0.5 to 1, and further preferably in the range of 0.6 to 0.9.
In the present invention, the peaks in the X-ray photoelectron spectrum in the range of 531.0 to 533.5eV (corresponding to oxygen species not bonded to the metal atom) are further divided into two groups of peaks, i.e., a peak in the range of 531.0 to 532.5eV (corresponding to C ═ O species) and a peak in the range of 532.6 to 533.5eV (corresponding to C-O species), and the area of the peak in the range of 531.0 to 532.5eV is designated as AO 4The area of the peak in the range of 532.6 to 533.5eV is designated as AO 5，IO c/IO e＝AO 4/AO 5。
According to the alkali metal element-containing nanocarbon material of the invention, the content of the C element determined from a peak in the range of 284.7 to 284.9eV in an X-ray photoelectron spectrum may be 65 to 95% by weight, preferably 75 to 85% by weight, based on the total amount of the C element determined from the X-ray photoelectron spectrum in the nanocarbon material; the total content of the C element determined from a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum may be 5-35% by weight, preferably 15-25% 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 3C-member determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrumContent of element is AC 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。
An alkali metal element-containing nanocarbon material according to the present invention, in which 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 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 eMay be in the range of 0.4 to 2, preferably in the range of 0.45 to 1.5, more preferably in the range of 0.8 to 1.3, and further preferably in the range of 0.9 to 1.2.
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。
According to the transition metal element-containing nanocarbon material of the present invention, the content of the O element may be 1 to 15% by weight, preferably 3 to 13% by weight, more preferably 5 to 10% by weight, based on the total amount of the nanocarbon material and calculated as an element; the total amount of metal elements may be 0.4 to 20 wt%, preferably 2 to 18 wt%, more preferably 4 to 9 wt%; the content of the element C may be 65 to 98.6% by weight, preferably 69 to 95% by weight, more preferably 81 to 91% by weight.
According to the transition metal element-containing nanocarbon material of the present invention, the total content of oxygen element in the nanocarbon material as determined by X-ray photoelectron spectroscopy is IO tDetermined from the peak in the range of 529.5-530.8eV in the X-ray photoelectron spectrumHas the content of O element of IO m，IO m/IO tMay be in the range of 0.01 to 0.6, preferably in the range of 0.02 to 0.5, more preferably in the range of 0.03 to 0.4, and further preferably in the range of 0.09 to 0.18. The content of O element determined by the peak in the range of 531.0-533.5eV in the X-ray photoelectron spectrum is IO nm，IO nm/IO tMay be in the range of 0.4 to 0.99, preferably in the range of 0.5 to 0.98, more preferably in the range of 0.6 to 0.97, and further preferably in the range of 0.82 to 0.91.
According to the transition metal element-containing nanocarbon material of the invention, the amount of the O element (i.e., C ═ O) determined from the peak in the range of 531.0 to 532.5eV in the 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 eIn the range of 0.2 to 1, preferably in the range of 0.25 to 0.9, more preferably in the range of 0.4 to 0.75.
According to the transition metal element-containing nanocarbon material of the present invention, the content of the C element determined from a peak in the range of 284.7 to 284.9eV in an X-ray photoelectron spectrum may be 60 to 95% by weight, preferably 60 to 80% by weight, based on the total amount of the C element determined from the X-ray photoelectron spectrum in the nanocarbon material; the total content of the C element determined from a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum may be 5-40% by weight, preferably 20-40% by weight.
According to the transition metal element-containing nanocarbon material of the present invention, 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 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 eMay be in the range of 0.3 to 2, preferably in the range of 0.4 to 1.6, more preferably in the range of 0.8 to 1.4.
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 288.6-288.8eV means all peaks having a binding energy in the range of 288.6-288.8eV corresponding to the peak top.
According to the nanocarbon material molded body of the present invention, the nanocarbon material may exist in various forms, and specifically, 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 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. According to the nanocarbon material molded body, the nanocarbon material is preferably a multiwalled carbon nanotube.
According to the nanocarbon material molded body of the present invention, the specific surface area of the multi-walled carbon nanotube is preferably 50 to 500m2In this way, the catalytic properties of the shaped bodies, in particular as catalysts for the dehydrogenation of hydrocarbon materials, can be further improved. The specific surface area of the multi-walled carbon nanotube is more preferably 90-300m2(ii)/g, more preferably 120-2(ii) in terms of/g. In the present invention, the specific surface area is measured by a nitrogen adsorption BET method.
According to the nano carbon material forming body, the weight loss rate of the multi-wall carbon nano tube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01 to 0.5, which enables better catalytic performance, particularly when used as a catalyst for dehydrogenation of hydrocarbons. w is a500/w800More preferably in the range of 0.02 to 0.4, still more preferably in the range of 0.05 to 0.15. In the present invention, w800＝W800－W400，w500＝W500－W400，W400The mass loss rate, W, measured at a temperature of 400 deg.C800Is at 800 deg.CMass loss rate, W, measured at temperature500Is 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 non-metallic hetero atoms other than oxygen atoms and nitrogen atoms, such as sulfur atoms and phosphorus atoms, in the nanocarbon material may be a conventional content. Generally, according to the nanocarbon material molded body of the present invention, the total amount of non-metallic hetero atoms (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, more preferably 0.1% by weight or less, and further preferably 0.05% by weight or less. According to the nanocarbon material molded body of the present invention, the nanocarbon material may contain other metal atoms in addition to the metal elements selected from the group consisting of the metal elements, and the other metal atoms may be derived from a catalyst used in the production of the nanocarbon material, for example. The content of the other metal atom is generally 2.5% by weight or less, preferably 2% by weight or less, more preferably 1% by weight or less, still more preferably 0.5% by weight or less, and particularly 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 ℃ under an oxygen or oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃).
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 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. 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 nanocarbon material is dispersed, in which at least one peroxide and at least one metal compound are dispersed, in a closed vessel, wherein the temperature of the aqueous dispersion is in the range of 80 to 300 ℃ during the reaction.
The peroxide refers to a compound containing an-O-O-bond in the molecular structure. In particular, the peroxide may be selected from hydrogen peroxide and organic peroxides of formula I,
Figure BDA0001061381070000051
in the formula I, R1And R2Each is selected from H, C4-C12Alkyl of (C)6-C12Aryl of (C)7-C12Aralkyl and
Figure BDA0001061381070000052
and R is1And R2Not simultaneously being H or R3Is C4-C12Straight or branched alkyl or C6-C12Aryl group of (1).
In the present invention, C4-C12Specific examples of alkyl groups of (a) include, but are not limited to, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, hexyl (including various isomers of hexyl), cyclohexyl, octyl (including various isomers of octyl), nonyl (including various isomers of nonyl), decyl (including various isomers of decyl), undecyl (including various isomers of undecyl), and dodecyl (including various isomers of dodecyl).
In the present invention, C6-C12Specific examples of aryl groups of (a) include, but are not limited to, phenyl, naphthyl, methylphenyl, and ethylphenyl. In the present invention, C7-C12Specific examples of the aralkyl group of (a) include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl and phenyl-n-butyl.
Specific examples of the peroxide may include, but are not limited to: hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, dicumyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide and lauroyl peroxide.
The metal compound is selected from the group consisting of a basic metal compound and a transition metal compound.
The metal element in the basic metal compound is selected from group IA metal elements and group IIA metal elements, and specific examples thereof may include, but are not limited to, lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium. Preferably, the metal element is selected from sodium, potassium, magnesium, calcium and barium, so that better catalytic performance can be obtained when the nanocarbon material formed body is used as a catalyst for a dehydrogenation reaction of hydrocarbon. The basic metal compound is preferably selected from the group consisting of hydroxides and basic salts. More preferably, the basic metal compound is selected from the group consisting of a hydroxide containing a metal element, a carbonate containing the metal element, and a bicarbonate containing the metal element. Specific examples of the basic metal compound may include, but are not limited to: one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, and barium bicarbonate. The basic metal compound is preferably one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, and barium bicarbonate, from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body in the hydrocarbon dehydrogenation reaction.
The metal element in the transition metal compound is selected from transition metal elements (i.e., the metal compound is preferably selected from transition metal-containing compounds). The metal element in the transition metal compound may be specifically selected from, but not limited to, a group IIIB metal element, a group IVB metal element, a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IB metal element, and a group IIB metal element in the periodic table of elements. Specific examples of the metal element in the transition metal compound may include, but are not limited to, scandium, yttrium, rare earth metal elements (e.g., lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc. Preferably, the metal element in the transition metal compound is selected from group VIII metal elements, and in this case, the nanocarbon material molded body can obtain higher catalytic activity when used as a catalyst for a hydrocarbon dehydrogenation reaction. More preferably, the metal element in the transition metal compound is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The transition metal compound may be selected from transition metal nitrates, transition metal acetates, transition metal carbonates, transition metal sulfates, transition metal hydroxycarbonates, transition metal gluconates, transition metal hydroxides, transition metal chlorides, and transition metal complexes, and more preferably from transition metal acetates, transition metal gluconates, transition metal carbonates, transition metal hydroxycarbonates, transition metal hydroxides, and transition metal complexes (e.g., palladium ammine nitrate and palladium acetylacetonate).
The transition metal compound may be specifically selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobalt sulfate, basic cobalt carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, ferrous acetate, ferrous gluconate, ferric sulfate, basic iron carbonate, ferric chloride, ferric hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, zinc hydroxide, copper nitrate, copper acetate, copper sulfate, copper hydroxycarbonate, copper chloride, copper hydroxide, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, cerium nitrate, cerium carbonate, cerium chloride, cerium hydroxide, ruthenium nitrate, ruthenium chloride, ruthenium hydroxide, palladium nitrate, palladium chloride, palladium hydroxide, platinum nitrate, platinum chloride, rhodium nitrate, palladium ammine nitrate (e.g., palladium tetraammine nitrate), rhodium chloride, and palladium acetylacetonate.
According to the molded article of the second aspect of the present invention, the metal compound may be a basic metal compound, a transition metal compound, or a combination of a basic metal compound and a transition metal compound. In one embodiment, the metal compound is a basic metal compound. In another embodiment, the metal compound is a transition metal compound. Although the catalytic activity of the nanocarbon material molded body as a catalyst for dehydrogenation reaction of hydrocarbons can be improved by subjecting the raw nanocarbon material and the metal compound to hydrothermal treatment in the presence of a peroxide, it is preferable to optimize the reaction conditions depending on the kind of the metal compound from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body.
When the metal compound is a basic metal compound, the raw material nanocarbon material: peroxide: the weight ratio of the basic metal compound is preferably in the range of 1: 0.02-20: in the range of 0.01 to 10, the nanocarbon material containing a metal atom thus prepared can obtain a further improved catalytic effect when used as a catalyst for a dehydrogenation reaction of hydrocarbons. Raw material nano carbon material: peroxide: the weight ratio of the basic metal compound is more preferably in the range of 1: 0.2-16: in the range of 0.02 to 5, more preferably in the range of 1: 0.5-5: in the range of 0.05 to 1, more preferably in the range of 1: 1-2: 0.1-0.2.
When the metal compound is a basic metal compound, the raw material nanocarbon material: h2The weight ratio of O is preferably in the range of 1: 2-500, the structural morphology of the nanocarbon material during processing is better retained when the amount of water is within this range, for example: 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 in the range of 1: 10 to 400, more preferably in the range of 1: in the range of 50-200.
In a preferred embodiment, the peroxide is hydrogen peroxide when the metal compound is a basic metal compound, and the metal element in the basic metal compound is selected from the group consisting of magnesium, calcium and barium. In another preferred embodiment, the peroxide is an organic peroxide represented by formula I, and the metal element of the basic metal compound is selected from sodium and potassium. The nanocarbon material molded bodies according to the above two preferred examples can obtain higher catalytic activity when used as a catalyst for dehydrogenation reaction of hydrocarbons.
When the metal compound is a transition metal compound, the raw material nanocarbon material: peroxide: the weight ratio of the metal compounds is preferably in the range of 1: 0.01-20: 0.01 to 10, the nanocarbon material containing a metal atom thus prepared can obtain a further improved catalytic reaction effect when used as a catalyst for a dehydrogenation reaction of hydrocarbons. Raw material nano carbon material: peroxide: the weight ratio of the metal compounds is more preferably in the range of 1: 0.1-18: in the range of 0.02 to 5, more preferably in the range of 1: 0.2-15: in the range of 0.05 to 4, more preferably in the range of 1: 0.5-2: in the range of 0.1 to 1.
When the metal compound is a transition metal compound, the raw material nanocarbon material: h2The weight ratio of O is preferably in the range of 1: 2-500, the structural morphology of the nanocarbon material during processing is better retained when the amount of water is within this range, for example: for carbon nanotubes, they are not substantially cut during processing. Raw material nano carbon material: h2The weight ratio of O is more preferably in the range of 1: in the range of 5 to 400, further preferably in the range of 1: 10-350, more preferably in the range of 1: in the range of 25-100.
In the case where the metal compound is a transition metal compound, in a preferred example, the peroxide is hydrogen peroxide, and the metal element in the metal compound is selected from the group consisting of iron, cobalt and nickel. In another preferred embodiment, the peroxide is an organic peroxide of formula I, and the metal element in the metal compound is selected from the group consisting of ruthenium, rhodium, palladium, and platinum.
According to the shaped article of the second aspect of the present invention, the temperature of the aqueous dispersion during the reaction is preferably in the range of 90 to 240 ℃. When the temperature of the aqueous dispersion is within the above range, the structural morphology of the raw nanocarbon material is not significantly affected. The temperature of the aqueous dispersion during the reaction is more preferably in the range of 120-220 ℃.
The duration of the reaction can be selected according to the temperature of the reaction. In general, the duration of the reaction may be in the range of 0.5 to 144 hours, preferably in the range of 0.5 to 96 hours, more preferably in the range of 2 to 72 hours, further preferably in the range of 10 to 60 hours, and still further preferably in the range of 12 to 36 hours.
According to the molded article of the second aspect of the present invention, the aqueous dispersion can be formed by various methods which are conventionally used, and for example, the raw nanocarbon material can be dispersed in water (preferably deionized water) and then the peroxide and the metal compound can be added 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 200kHz, preferably 14 to 140 kHz; the duration of the ultrasonic oscillation may be 0.1 to 6 hours, preferably 0.5 to 4 hours. The peroxide and the metal compound may be each provided in the form of a solution (preferably an aqueous solution) depending on the kind thereof, or may be each 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 300m2(ii)/g, more preferably 100-260m2(ii)/g, more preferably 120-190m2/g。
When the raw material nano carbon material is the multi-walled carbon nanotube, the weight loss rate of the multi-walled carbon nanotube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range 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, in which case the drying can be carried out at a temperature of 120-400 ℃, preferably at a temperature of 150-350 ℃, more preferably at a temperature of 180-300 ℃, and the duration of the drying can be selected according to 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 II:
Figure BDA0001061381070000091
in the formula II, R4、R5、R6And R7Each 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 alkali can be one or more than two of hydrazine, urea, amine, alcohol amine and quaternary ammonium alkali.
The quaternary ammonium base can be various organic quaternary ammonium bases, and the amine can be various NH3In which at least one hydrogen is replaced by a hydrocarbyl group, preferably an alkyl group, the alcohol amine may be any of a variety of NH3Wherein at least one hydrogen is substituted with a hydroxyl-containing hydrocarbon group (preferably an alkyl group). Specifically, the quaternary ammonium base can be a quaternary ammonium base shown in a formula III,
Figure BDA0001061381070000101
in the formula III, R8、R9、R10And R11Are the same or different and are each C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r8、R9、R10And R11Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
The amine may be an aliphatic amine of formula IV and of formula R15(NH2)2One or more of the substances shown,
Figure BDA0001061381070000102
in the formula IV, R12、R13And R14Are each H, C1-C6Alkyl or C6-C12And R is an aryl group of12、R13And R14Not 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 present invention, C6-C12Specific examples of aryl groups of (a) include, but are not limited to, phenyl, naphthyl, methylphenyl, and ethylphenyl.
General formula R15(NH2)2In, R15Can be C1-C6Alkylene or C6-C12An arylene 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. In the present invention, C6-C12Specific examples of the arylene group of (a) include, but are not limited to, phenylene and naphthylene.
The alcohol amine may be an aliphatic alcohol amine represented by formula V,
Figure BDA0001061381070000103
in the formula V, R16、R17And R18Each is-R16OH or hydrogen, and R16、R17And R18At least one of which is-R19OH，R19Is C1-C4An alkylene group of (a). In the present invention, C1-C4Alkylene of (A) includes C1-C4Linear alkylene of (A) and (C)3-C4Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, and tert-butylene.
Specific examples of the base may include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, urea, hydrazine, 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, diisobutylamine, triisobutylamine, tert-butylamine, n-pentylamine, di-n-pentylamine, tri-n-pentylamine, neopentylamine, isopentylamine, diisopentylamine, triisopentylamine, tert-pentylamine, n-hexylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecyldimethylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, triethanolamine, triisopropanolamine, diethanolamine, di-n-propanolamine, di-n-butylamine, di-butyla, Tri-n-propanolamine, di-n-butanolamine, tri-n-butanolamine, 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 various isomers thereof, such as tetra-N-propylammonium hydroxide and tetra-i-propylammonium hydroxide), tetrabutylammonium hydroxide (including various isomers thereof, such as tetra-N-butylammonium hydroxide, tetra-sec-butylammonium hydroxide, tetra-i-butylammonium hydroxide and tetra-tert-butylammonium hydroxide), and tetrapentylammonium hydroxide (including various isomers thereof).
In a preferred embodiment, the base is an organic base, which further improves the catalytic activity of the finally prepared nanocarbon material shaped body as a catalyst for a dehydrogenation reaction of hydrocarbons. In the preferred embodiment, the base is a template agent for synthesizing the titanium silicalite molecular sieve, such as a quaternary ammonium base shown in formula III, so that the prepared nano carbon material formed body has higher crushing strength and shows further improved catalytic activity when used as a catalyst for hydrocarbon dehydrogenation reaction.
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 0.1 to 10: 1, preferably 0.2 to 5: 1, more preferably 0.3 to 2: 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 silicon molecular sieve containing heteroatom (such as 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 heavy liquid discharge 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, that is, a liquid mixture remaining after the molecular sieve is separated from the mixture obtained by hydrothermal modification rearrangement, and is also referred to as a rearranged mother liquor, a modified mother liquor, a rearranged filtered waste liquor, a modified filtered raw liquor or a rearranged filtered 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, titanium siliconIn the heavy liquid discharge of the molecular sieve, 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% by weight, more preferably 1 to 4% by weight; 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-. 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 from 50 to 200 deg.C, preferably at a temperature of from 80 to 180 deg.C, more preferably at a temperature of from 120 to 180 deg.C. 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 300-800 deg.C, preferably no higher than 650 deg.C. 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 300-500 deg.C, more preferably at a temperature of not higher than 450 deg.C. When the calcination is carried out in an oxygen-free atmosphere, the calcination is preferably carried out at a temperature of 400-800 deg.C, more preferably at a temperature of not higher than 750 deg.C. 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 origins can be treated. 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, before the mixture is formed, it is preferable to subject the mixture to hydrothermal treatment in a closed vessel, which not only significantly improves the strength of the finally produced formed body, but also significantly improves the final strength of the finally produced formed bodyCatalytic properties of the shaped bodies prepared. 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 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. The specific surface area of the multi-walled carbon nanotube can be 50-500m2A/g, preferably from 80 to 300m2A/g, more preferably 90 to 250m2(ii) in terms of/g. The weight loss rate of the multi-walled carbon nano-tube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800Preferably in the range of 0.01-0.5. 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, which contains an O element and at least one metal element selected from the group consisting of transition metal elements, group IA metal elements and group IIA metal elements, as determined by X-ray photoelectron spectroscopy. The transition metal element, the group IA metal element and the group IIA metal element are the same as those described in the first aspect of the present invention, and are not described in detail here. The content of the metal element may be selected according to the specific application of the finally prepared nanocarbon material molding. When the finally prepared nanocarbon material molded body is used as a catalyst for dehydrogenation reaction of hydrocarbon, the content of the O element may be 1 to 15% by weight, preferably 2 to 12% by weight, more preferably 5 to 10% by weight, based on the total amount of the nanocarbon material and calculated as element; the content of the metal element may be 0.2 to 20% by weight, preferably 0.5 to 18% by weight, more preferably 1 to 9% 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, forming the 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 process of the fifth aspect of the invention, the aqueous dispersion preferably further contains at least one treating agent selected from the group consisting of a base, a peroxide and a metal compound, the base being different from the metal 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 base is the same as the base used in the process of the third aspect of the invention and in the same amount, and will not be described in detail here. The peroxide may be a peroxide as mentioned in the molded article according to the second aspect of the present invention and will not be described herein.
The metal compound may be a basic metal compound and/or a transition metal compound.
The metal element in the basic metal compound is selected from group IA metal elements and group IIA metal elements, and specific examples thereof may include, but are not limited to, lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium. Preferably, the metal element is selected from sodium, potassium, magnesium, calcium and barium, so that better catalytic performance can be obtained when the nanocarbon material formed body is used as a catalyst for a dehydrogenation reaction of hydrocarbon. The basic metal compound is preferably selected from the group consisting of hydroxides and basic salts. More preferably, the basic metal compound is selected from the group consisting of a hydroxide containing a metal element, a carbonate containing the metal element, and a bicarbonate containing the metal element. Specific examples of the basic metal compound may include, but are not limited to: one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, and barium bicarbonate. The basic metal compound is preferably one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, and barium bicarbonate, from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body in the hydrocarbon dehydrogenation reaction.
The metal element in the transition metal compound is selected from transition metal elements (i.e., the metal compound is preferably selected from transition metal-containing compounds). The metal element in the transition metal compound may be specifically selected from, but not limited to, a group IIIB metal element, a group IVB metal element, a group VB metal element, a group VIB metal element, a group VIIB metal element, a group VIII metal element, a group IB metal element, and a group IIB metal element in the periodic table of elements. Specific examples of the metal element in the transition metal compound may include, but are not limited to, scandium, yttrium, rare earth metal elements (e.g., lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc. Preferably, the metal element in the transition metal compound is selected from group VIII metal elements, and in this case, the nanocarbon material molded body can obtain higher catalytic activity when used as a catalyst for a hydrocarbon dehydrogenation reaction. More preferably, the metal element in the transition metal compound is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The transition metal compound may be selected from transition metal nitrates, transition metal acetates, transition metal carbonates, transition metal sulfates, transition metal hydroxycarbonates, transition metal gluconates, transition metal hydroxides, transition metal chlorides, and transition metal complexes, and more preferably from transition metal acetates, transition metal gluconates, transition metal carbonates, transition metal hydroxycarbonates, transition metal hydroxides, and transition metal complexes (e.g., palladium ammine nitrate and palladium acetylacetonate).
The transition metal compound may be specifically selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobalt sulfate, basic cobalt carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, ferrous acetate, ferrous gluconate, ferric sulfate, basic iron carbonate, ferric chloride, ferric hydroxide, zinc nitrate, zinc acetate, zinc sulfate, basic zinc carbonate, zinc chloride, zinc hydroxide, copper nitrate, copper acetate, copper sulfate, copper hydroxycarbonate, copper chloride, copper hydroxide, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, cerium nitrate, cerium carbonate, cerium chloride, cerium hydroxide, ruthenium nitrate, ruthenium chloride, ruthenium hydroxide, palladium nitrate, palladium chloride, palladium hydroxide, platinum nitrate, platinum chloride, rhodium nitrate, palladium ammine nitrate (e.g., palladium tetraammine nitrate), rhodium chloride, and palladium acetylacetonate.
The treating agent is preferably an alkali and at least one selected from peroxides and metal compounds, from the viewpoint of further improving the strength of the finally produced nanocarbon material shaped body and the catalytic performance in the hydrocarbon dehydrogenation reaction.
In one embodiment, the treating agent is a base, preferably an organic base. From the viewpoint of further improving the strength of the produced molded article and the catalytic effect in the dehydrogenation reaction of hydrocarbons, the base is more preferably a quaternary ammonium base, and is further preferably a template for synthesizing a titanium silicalite, such as a quaternary ammonium base represented by formula III.
In a more preferred embodiment, the treating agents are bases, peroxides, and metal compounds. In the preferred embodiment, the base is preferably an organic base, more preferably a quaternary ammonium base, and even more preferably a templating agent for synthesizing a titanium silicalite, such as the quaternary ammonium base shown in formula III. By introducing quaternary ammonium base during hydrothermal treatment, the strength and catalytic performance of the molded body can be effectively improved. In this preferred embodiment, it is particularly preferred that at least a portion of the base and at least a portion of the binder source are derived from a molecular sieve preparation liquor.
In this more preferred embodiment, the metal compound may be a basic metal compound and/or a transition metal compound. When the metal compound is a basic metal compound, in a preferred example, the peroxide is hydrogen peroxide, and the metal element in the basic metal compound is selected from magnesium, calcium, and barium; in another preferred embodiment, the peroxide is an organic peroxide represented by formula I, and the metal element of the basic metal compound is selected from sodium and potassium. When the metal compound is a transition metal compound, in a preferred example, the peroxide is hydrogen peroxide, and the metal element in the metal compound is selected from iron, cobalt and nickel; in another preferred embodiment, the peroxide is an organic peroxide of formula I, and the metal element in the metal compound is selected from the group consisting of ruthenium, rhodium, palladium, and platinum.
In comparison with the nanocarbon material according to the second aspect of the present invention (i.e., the raw nanocarbon material is first hydrothermally treated together with a peroxide and a metal compound and then shaped in the presence of a base), this preferred embodiment not only uses a lower amount of the metal compound, but also produces a shaped body that exhibits strength and catalytic performance comparable to or even higher than those produced by shaping after the hydrothermal treatment. In this more preferred embodiment, the molar ratio of the base, the peroxide and the metal compound may be 1: 0.1-10: 0.02 to 1.5, preferably 1: 0.4-7: 0.07-0.8.
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 0.1 to 10: 1, preferably 0.1 to 8: 1, more preferably 0.3 to 4: 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. 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 (e.g., 94 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-. 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. Method according to the inventionIt is particularly suitable for dehydrogenating alkanes to give alkenes. 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, 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, or a combination of two or more thereof.
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 content of the carrier gas may be 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 200-650 ℃, preferably at a temperature of 300-600 ℃, more preferably at a temperature of 350-550 ℃, even more preferably at a temperature of 400-450 ℃ 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 process for dehydrogenation of hydrocarbons of the present invention,the duration of the contacting may be selected based on the temperature of the contacting, and may be expressed in terms of the weight hourly space velocity of the feed as the contacting is carried out 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--1E.g. 2000--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 during analytical testing-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 BDA0001061381070000161
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 3300 DV 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 34 were used to prepare nanocarbon materials containing metal atoms.
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 140kHz and the time was 1 hour. Then, hydrogen peroxide as a peroxide and barium hydroxide as a basic metal compound were added and mixed uniformly to obtain an aqueous dispersion, wherein the hydrogen peroxide and the basic metal compound were each provided in the form of a 25 wt% aqueous solution in terms of the raw material nanocarbon material: peroxide: basic metal compound: h2The weight ratio of O is 1: 1: 0.1: 100 parts by weight.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at a temperature of 120 ℃ 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. Drying the collected solid substance at normal pressure (1 atm, the same applies below) and 120 deg.C for 12 hr to obtain the metal atom-containing nano carbon material with its 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, and the three-necked flask was placed in an oil bath at a temperature of 120 ℃ and reacted under reflux at normal pressure for 24 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 12 hours to obtain the metal atom-containing nano carbon material.
Preparation example 3
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 1, except that, in step (1), the nanocarbon material was multi-walled carbon nanotubes B (available from Shandong Dazhan nanomaterial Co., Ltd.).
Preparation example 4
A nanocarbon material containing metal atoms was produced in the same manner as in production 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 24 hours.
Preparation example 5
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 4 hours. Then, hydrogen peroxide as a peroxide and calcium hydroxide as an alkali metal compound were added and mixed uniformly to obtain an aqueous dispersion, wherein the hydrogen peroxide was supplied as a 30 wt% aqueous solution, and the calcium hydroxide was supplied as a 30 wt% aqueous dispersion, as raw materials of the nanocarbon material: peroxide: basic metal compound: h2The weight ratio of O is 1: 2: 0.1: feeding at the ratio of 200.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 180 ℃ under autogenous pressure for 12 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. Will receiveDrying the collected solid substance at 150 deg.C under normal pressure for 6 hr to obtain the nano carbon material containing metal atoms, its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 6
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 5, except that, in step (1), the nanocarbon material used as a raw material was a multi-walled carbon nanotube D (available from Shandong Dazhang nanomaterial Co., Ltd.).
Preparation example 7
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 5, 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 240 ℃ under autogenous pressure for 12 hours.
Preparation example 8
A nanocarbon material containing a metal atom was produced in the same manner as in production example 5, except that in step (1), calcium hydroxide was replaced with an equimolar amount of potassium hydroxide.
Preparation example 9
A nanocarbon material containing a metal atom was produced in the same manner as in production example 5, except that in step (1), hydrogen peroxide was replaced with an equimolar amount of t-butyl hydroperoxide.
Preparation example 10
A nanocarbon material containing a metal atom was produced in the same manner as in production example 5, except that, in step (1), hydrogen peroxide was replaced with an equimolar amount of dicumyl peroxide.
Preparation example 11
The same method as in preparation example 1 was used to prepare a nanocarbon material containing metal atoms, except that:
in the step (1), after dispersing the raw material nanocarbon material in deionized water, adding and uniformly mixing tert-butyl hydroperoxide as peroxide and potassium hydroxide as an alkali metal compound to obtain an aqueous dispersion, wherein the tert-butyl hydroperoxide is provided in the form of a 10 wt% aqueous solution, and the potassium hydroxide is 20 wt%Providing in the form of an aqueous solution, the carbon nano-material: peroxide: basic metal compound: h2The weight ratio of O is 1: 2: 0.2: feeding at a ratio of 120;
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 160 ℃ under autogenous pressure.
Preparation example 12
The same aqueous dispersion as in production example 11 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 160 ℃ to conduct a 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 12 hours to obtain the metal atom-containing nano carbon material.
Preparation example 13
A nanocarbon material containing metal atoms was produced in the same manner as in production example 11, except that in step (2), the resulting aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 220 ℃ under autogenous pressure for 36 hours.
Preparation example 14
A nanocarbon material containing metal atoms was produced in the same manner as in production example 11, except that the nanocarbon material was a multiwall carbon nanotube B.
Preparation example 15
The same method as in preparation example 5 was used to prepare a nanocarbon material containing metal atoms, except that: in the step (1), the aqueous solution for preparing the aqueous dispersion contains t-butyl hydroperoxide as a peroxide and potassium hydroxide as a basic metal compound, wherein the carbon nanomaterial: peroxide: basic metal compound: h2The weight ratio of O is 1: 1: 0.1: feeding at a ratio of 50; 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 120 ℃ under the autogenous pressure.
Preparation example 16
A nanocarbon material containing metal atoms was produced in the same manner as in production example 15, except that in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner and reacted at a temperature of 90 ℃ under autogenous pressure for 24 hours.
Preparation example 17
A nanocarbon material containing a metal atom was produced in the same manner as in production example 15, except that t-butyl hydroperoxide was replaced with hydrogen peroxide in an equimolar amount.
Preparation example 18
(1) Dispersing 20g of multi-walled carbon nanotubes A serving as a raw material nanocarbon material in deionized water, wherein the dispersion is performed under ultrasonic oscillation conditions which include: frequency of 14kHz for 0.5 hour, then hydrogen peroxide and cobalt acetate as a metal compound were added and mixed uniformly to obtain an aqueous dispersion, wherein the hydrogen peroxide was supplied in the form of a 30 wt% aqueous solution as a raw material nanocarbon material: hydrogen peroxide: metal compound (b): h2The weight ratio of O is 1: 1: 0.5: 100 parts by weight.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at a temperature of 110 ℃ 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 120 deg.C under normal pressure for 12 hr to obtain nano carbon material containing metal atoms, and its composition, specific surface area and w500/w800Listed in table 3.
Preparation example 19
The same aqueous dispersion as in preparation example 18 was placed in a three-necked flask equipped with a condenser, and the three-necked flask was placed in an oil bath at 110 ℃ and reacted under reflux at 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 12 hours to obtain the metal atom-containing nano carbon material.
Preparation example 20
A nanocarbon material containing metal atoms was produced in the same manner as in production example 18, except that in step (1), the nanocarbon material was a multiwall carbon nanotube B.
Preparation example 21
A nanocarbon material containing metal atoms was produced in the same manner as in production example 18, except that in the step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner and reacted at a temperature of 90 ℃ under autogenous pressure for 36 hours.
Preparation example 22
Dispersing 20g of multiwall carbon nanotube C as a raw material nanocarbon material in deionized water, wherein the dispersion is carried out under ultrasonic oscillation conditions, and the ultrasonic oscillation conditions comprise: frequency of 90kHz for 2 hours, then hydrogen peroxide and nickel acetate as a metal compound were added and mixed uniformly to obtain an aqueous dispersion, wherein the hydrogen peroxide and the metal compound were provided in the form of 30 wt% aqueous solutions, respectively, based on the raw material nanocarbon material: hydrogen peroxide: metal compound (b): h2The weight ratio of O is 1: 2: 1: 50 parts of the raw materials.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at 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. Drying the collected solid substance at 160 deg.C under normal pressure for 10 hr to obtain nanometer carbon material containing metal atoms, and its composition, specific surface area and w500/w800Listed in table 3.
Preparation example 23
A nanocarbon material containing metal atoms was produced in the same manner as in production example 22, except that, in step (1), the nanocarbon material was a multiwall carbon nanotube D.
Preparation example 24
A nanocarbon material containing metal atoms was produced in the same manner as in production example 22, except that in the step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 220 ℃ under autogenous pressure for 24 hours.
Preparation example 25
A nanocarbon material containing a metal atom was produced in the same manner as in preparation example 22, except that in step (1), hydrogen peroxide was replaced with an equimolar amount of t-butyl hydroperoxide.
Preparation example 26
A nanocarbon material containing a metal atom was prepared in the same manner as in preparation example 22, except that hydrogen peroxide was replaced with an equimolar amount of dibenzoyl peroxide.
Preparation example 27
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 18, except that: in the step (1), tert-butyl hydroperoxide as a peroxide and palladium acetylacetonate as a metal compound are added to deionized water in which a raw material nanocarbon material is dispersed, and uniformly mixed to obtain an aqueous dispersion, wherein the palladium acetylacetonate is supplied in the form of a 30 wt% aqueous solution, and the tert-butyl hydroperoxide is supplied in the form of a 30 wt% aqueous dispersion, in terms of the raw material nanocarbon material: peroxide: metal compound (b): h2The weight ratio of O is 1: 0.5: 0.1: 25 in proportion; in the step (2), the obtained aqueous dispersion is placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 48 hours at the temperature of 120 ℃ under autogenous pressure.
Preparation example 28
The same aqueous dispersion as in preparation example 27 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 normal pressure and 120 ℃ for 12 hours to obtain the metal atom-containing nano carbon material.
Preparation example 29
A nanocarbon material containing metal atoms was produced in the same manner as in production example 27, except that in step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner and reacted at a temperature of 80 ℃ under autogenous pressure for 48 hours.
Preparation example 30
A nanocarbon material containing metal atoms was produced in the same manner as in production example 27, except that the nanocarbon material was a multiwall carbon nanotube B.
Preparation example 31
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 22, except that: in the step (1), cumene hydroperoxide as a peroxide and palladium acetate as a metal compound are added to deionized water in which a raw nanocarbon material is dispersed, to obtain an aqueous dispersion, wherein the palladium acetate is provided in the form of a 20 wt% aqueous solution, and the cumene hydroperoxide is provided in the form of a 30 wt% aqueous dispersion, based on the raw nanocarbon material: peroxide: metal compound (b): h2The weight ratio of O is 1: 1: 0.2: feeding at a ratio of 50; 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 32
A nanocarbon material containing metal atoms was produced in the same manner as in production example 31, except that in step (1), the nanocarbon material was a multiwall carbon nanotube D.
Preparation example 33
A nanocarbon material containing metal atoms was produced in the same manner as in production example 31, 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 210 ℃ under autogenous pressure for 24 hours.
Preparation example 34
A nanocarbon material containing a metal atom was produced in the same manner as in production example 31, except that cumene hydroperoxide was replaced with an equimolar amount of hydrogen peroxide in step (1).
Figure BDA0001061381070000211
Figure BDA0001061381070000221
Examples 1 to 80 are for illustrating the nanocarbon material molded body according to the present invention and the method for preparing the same.
Examples 1-80 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. Then, the reaction solution was transferred to a high-pressure reactor equipped with a stirrer, and subjected to hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, and the resulting reaction mixture was mixedFiltering the product, collecting crystallized 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 30% by mass aqueous hydrogen peroxide which had been cooled to 5 ℃ in advance was added 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 wt%, and the content of tetrapropylammonium hydroxide wasIt 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 Ti-Beta molecular sieve 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. After cooling, the solid-liquid mixture obtained was centrifuged to obtain a solid and a crystallization mother liquor (numbered 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.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The 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, transferring the obtained mixture into a high-pressure reaction kettle equipped with a stirring device, carrying out hydrothermal crystallization for 10 days at 175 ℃ under autogenous pressure, filtering the obtained reaction mixture, and collecting 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 0.504 wt% and the content of tetrapropylammonium hydroxide was 45 wt%.
Examples 1 to 44
The nanocarbon materials were molded by the following methods, respectively, under the conditions given in table 4.
The nanocarbon material is uniformly mixed with a binder source and an optional treating agent at ambient temperature (25 ℃), the obtained mixture is sent into a strip-shaped mold to be dried and optionally roasted to obtain a nanocarbon material forming body (a part of the forming body is randomly selected and ground to obtain a sample strip with the length of 3-5mm for measuring the crushing resistance and the porosity, the results are listed in table 4), the rest forming body is crushed and sieved to obtain a granular forming body, and the average particle size (particle size for short) of the granular forming body is listed in table 4.
TABLE 4
Figure BDA0001061381070000241
Figure BDA0001061381070000251
1: the amount of the nanocarbon material is 10g2: tetrapropylammonium hydroxide3: tetraethyl ammonium hydroxide4: the amount is calculated by oxide
5: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Examples 45 to 76
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 77
The difference from example 45 is that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then directly molded without hydrothermal treatment.
Example 78
The difference from example 45 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 hydrothermal treatment temperature as in example 45 for the same time period as in example 45, and the mixture obtained by the reflux reaction was fed into a mold.
Example 79
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 80
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.
TABLE 5
Figure BDA0001061381070000261
Figure BDA0001061381070000271
1: the amount of the nanocarbon material is 10g2: tetrapropylammonium hydroxide3: tetramethyl ammonium hydroxide4: the amount is calculated by oxide
5: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Test examples 1 to 80
The catalysts prepared in examples 1-80 were tested for catalytic performance in the following order.
0.5g of each of the granular molded bodies prepared in examples 1 to 80 was packed as a catalyst in a general-purpose fixed bed micro quartz tube reactor each having quartz sand sealed at both ends, and a gas containing n-butane and oxygen (n-butane concentration of 2.18 vol%, n-butane/oxygen molar ratio of 0.5: 1, and the balance nitrogen as a carrier gas) was charged at 0MPa (gauge pressure) and 410 ℃ for 3800h-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 the multi-walled carbon nanotubes A, B, C and D were tested in turn using the same method as in test examples 1-80. The results of the experiment are listed in table 6.
TABLE 6
Figure BDA0001061381070000272
Figure BDA0001061381070000281
Figure BDA0001061381070000291
Figure BDA0001061381070000301
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 (134)

1. A nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material, the nanocarbon material containing an O element and at least one metal element selected from the group consisting of transition metal elements, group IA metal elements and group IIA metal elements, the content of the O element being 1 to 15% by weight and the content of the metal element being 0.2 to 20% by weight, based on the total amount of the nanocarbon material and calculated as the elements;
when the metal element is selected from transition metal elements, the total content of oxygen elements in the nano carbon material determined by X-ray photoelectron spectroscopy is IO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.01 to 0.6, the amount of O element 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 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 0.25-0.75;
when the metal elements are selected from the group IA metal elements and the group IIA metal elements, the total content of oxygen elements in the nano carbon material determined by X-ray photoelectron spectroscopy is IO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.02 to 0.3, the amount of O element determined by a peak in the range of 531.0 to 532.5eV in an X-ray photoelectron spectrum is IO cFrom X-ray photoelectron spectroscopyThe amount of O element determined by the peak in the range of 532.6-533.5eV is IO e，IO c/IO eIn the range of 0.6-1.5;
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 is dispersed in a closed container, wherein at least one peroxide and at least one metal compound are dispersed in the aqueous dispersion, the metal compound is selected from a basic metal compound and a transition metal compound, a metal element in the basic metal compound is selected from a group IA metal element and a group IIA metal element, the temperature of the aqueous dispersion is in the range of 80-300 ℃ during the reaction, and the duration of the reaction is in the range of 0.5-96 hours;
in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the raw material nanocarbon material: peroxide: the weight ratio of the alkali metal compound is 1: 0.02-20: in the range of 0.01 to 10;
in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the nanocarbon material: peroxide: the weight ratio of the metal compound is 1: 0.01-20: in the range of 0.01 to 10;
in the method for preparing the nano-carbon material, the peroxide is selected from hydrogen peroxide and organic peroxide shown in a formula I,
Figure FDA0002448514360000011
in the formula I, R1And R2Each is selected from H, C4-C12Alkyl of (C)6-C12Aryl of (C)7-C12Aralkyl and
Figure FDA0002448514360000012
and R is1And R2Not simultaneously being H or R3Is C4-C12Straight or branched alkyl or C6-C12Aryl group of (1).
2. The molded body according to claim 1, wherein the content of the O element is 2 to 12% by weight and the content of the metal element is 0.5 to 18% by weight, in terms of element, based on the total amount of the nanocarbon material.
3. The molded body according to claim 2, wherein the content of the O element is 5 to 10% by weight and the content of the metal element is 1 to 9% by weight, in terms of element, based on the total amount of the nanocarbon material.
4. Shaped body according to any one of claims 1 to 3, wherein the metal element is selected from group VIII metal elements, group IA metal elements and group IIA metal elements.
5. The molded body according to claim 4, wherein the metal element is one or more of iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, sodium, potassium, magnesium, barium, and calcium.
6. Shaped body according to claim 1, wherein the metallic element is selected from the group VIII metallic elements and the nanocarbon material has a total oxygen content I determined by X-ray photoelectron spectroscopyO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.09-0.18;
in the nanocarbon material, 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 0.4-0.75.
7. The molded body according to claim 6, wherein the metal element is one or two or more of iron, ruthenium, cobalt, rhodium, nickel, palladium, and platinum.
8. Shaped body according to claim 6 or 7, wherein the amount of C element in the nanocarbon material, determined by a peak in the range 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 0.3-2.
9. Shaped body according to claim 8, wherein IC c/IC eIn the range of 0.4-1.6.
10. Shaped body according to claim 9, wherein IC c/IC eIn the range of 0.8-1.4.
11. The molded body according to claim 6 or 7, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum is 60-95% by weight and the total content of C element determined from a peak in the range of 286.0-288.8eV in X-ray photoelectron spectrum is 5-40% by weight, based on the total amount of C element in the nanocarbon material determined by X-ray photoelectron spectrum.
12. The molded body according to claim 11, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum is 60-80% by weight and the total content of C element determined from a peak in the range of 286.0-288.8eV in X-ray photoelectron spectrum is 20-40% by weight, based on the total amount of C element determined from X-ray photoelectron spectrum in the nanocarbon material.
13. The molded body according to claim 6 or 7, wherein the content of the O element is 1 to 15% by weight, the total amount of the metal element is 0.4 to 20% by weight, and the content of the C element is 65 to 98.6% by weight, in terms of element, based on the total amount of the nanocarbon material.
14. The molded body according to claim 13, wherein the content of the O element is 3 to 13% by weight, the total amount of the metal element is 2 to 18% by weight, and the content of the C element is 69 to 95% by weight, in terms of the element, based on the total amount of the nanocarbon material.
15. The molded body according to claim 14, wherein the content of the O element is 5 to 10% by weight, the total amount of the metal element is 4 to 9% by weight, and the content of the C element is 81 to 91% by weight, in terms of the element, based on the total amount of the nanocarbon material.
16. Shaped body according to claim 1, wherein the metal element is selected from group IA and group IIA metal elements, and the nanocarbon material has a total content of oxygen elements I, determined by X-ray photoelectron spectroscopyO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.05-0.25;
in the nanocarbon material, 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 0.6-1.2.
17. The molded body according to claim 16, wherein the metal element is one or two or more of sodium, potassium, magnesium, barium and calcium, and the nanocarbon material has a total content of oxygen element I determined by X-ray photoelectron spectroscopyO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.08-0.2;
in the nanocarbon material, 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 0.6-1.
18. The shaped body of claim 17, wherein IO c/IO eIn the range of 0.6-0.9.
19. The shaped body according to any one of claims 16 to 18, wherein the amount of C element in the nanocarbon material, as determined by a peak in the range of 288.6-288.8eV in X-ray photoelectron spectroscopy, 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 0.4-2.
20. The shaped body of claim 19, wherein IC c/IC eIn the range of 0.45-1.5.
21. The shaped body of claim 20, wherein IC c/IC eIn the range of 0.8-1.3.
22. The shaped body of claim 21, wherein IC c/IC eIn the range of 0.9-1.2.
23. The shaped body according to any one of claims 16 to 18, wherein the content of C element determined from a peak in the range of 284.7 to 284.9eV in X-ray photoelectron spectroscopy is 65 to 95% by weight and the total content of C element determined from a peak in the range of 286.0 to 288.8eV in X-ray photoelectron spectroscopy is 5 to 35% by weight, based on the total amount of C element in the nanocarbon material determined by X-ray photoelectron spectroscopy.
24. The molded body according to claim 23, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum is 75-85% by weight and the total content of C element determined from a peak in the range of 286.0-288.8eV in X-ray photoelectron spectrum is 15-25% by weight, based on the total amount of C element determined from X-ray photoelectron spectrum in the nanocarbon material.
25. The shaped body according to any one of claims 16 to 18, wherein the content of the element O is 2 to 12 wt%, the content of the element C is 78 to 97.5 wt%, and the total amount of the metal elements is 0.5 to 10 wt%, based on the total amount of the nanocarbon material and calculated as elements.
26. The molded body according to claim 25, wherein the content of the O element is 2.5 to 10% by weight, the content of the C element is 85 to 96.5% by weight, and the total amount of the metal elements is 1 to 5% by weight, based on the total amount of the nanocarbon material and calculated as elements.
27. The molded body according to claim 26, wherein the content of the O element is 5 to 8 wt%, the content of the C element is 88 to 94 wt%, and the total amount of the metal elements is 1 to 4 wt%, based on the total amount of the nanocarbon material and calculated as elements.
28. Shaped body according to any one of claims 1-3, 6, 7 and 16-18, wherein the nanocarbon material is carbon nanotubes.
29. The shaped body according to claim 28, wherein the nanocarbon material is a multiwall carbon nanotube.
30. The shaped body according to claim 29, wherein the multi-walled carbon nanotubes have a specific surface area of 50-500m2In the range of/g.
31. The shaped body according to claim 30, wherein the multi-walled carbon nanotubes have a specific surface area of 90-300m2In the range of/g.
32. The shaped body as claimed in claim 31, wherein the specific surface area of the multi-walled carbon nanotubes is 120-180m2In the range of/g.
33. The shaped body as claimed in claim 29, wherein the weight loss of the multiwalled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The weight loss rate in the temperature range 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.
34. The shaped body of claim 33, wherein w is500/w800In the range of 0.02-0.4.
35. The shaped body of claim 34, wherein w is500/w800In the range of 0.05-0.15.
36. The molded body according to claim 1, wherein in the method for producing a nanocarbon material, the metal element in the transition metal compound is selected from group VIII metal elements;
the basic metal compound is selected from the group consisting of hydroxides and basic salts.
37. The molded body according to claim 36, wherein in the method for producing a nanocarbon, the metal element in the transition metal compound is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium, and platinum;
the basic metal compound is selected from the group consisting of hydroxides, carbonates and bicarbonates.
38. The molded body according to claim 37, wherein in the method for producing a nanocarbon material, the transition metal compound is selected from the group consisting of metal acetates, metal gluconates, metal carbonates, metal hydroxycarbonates, metal hydroxides, and metal complexes;
the alkaline metal compound is one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium hydroxide, barium carbonate, calcium bicarbonate, barium hydroxide and magnesium hydroxide.
39. The shaped body according to any one of claims 1 and 36 to 38, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the metal compound is 0.1-18: 0.02-5.
40. The molded body according to claim 39, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the metal compound is 1: 0.2-15: 0.05-4.
41. The molded body according to claim 40, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the metal compound is 1: 0.5-2: in the range of 0.1 to 1.
42. The shaped body according to any one of claims 1 and 36 to 38, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: 2-500.
43. The molded body according to claim 42, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: 5-400.
44. The molded body according to claim 43, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: 10-350.
45. The molded body according to claim 44, wherein in the method for producing a nanocarbon material, the metal compound is a transition metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: in the range of 25-100.
46. The shaped body according to any one of claims 1 and 36 to 38, wherein in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the alkali metal compound is 1: 0.2-16: 0.02-5.
47. The molded body according to claim 46, wherein in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the alkali metal compound is 1: 0.5-5: 0.05-1.
48. The molded body according to claim 47, wherein in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the ratio of the raw nanocarbon material: peroxide: the weight ratio of the alkali metal compound is 1: 1-2: 0.1-0.2.
49. According to claims 1 and 36 to 38The molded body according to any one of the above processes, wherein the metal compound is a basic metal compound, and the ratio of the raw material nanocarbon material: h2The weight ratio of O is 1: 2-500.
50. The molded body according to claim 49, wherein in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: 10-400.
51. The molded body according to claim 50, wherein in the method for producing a nanocarbon material, the metal compound is a basic metal compound, and the ratio of the raw nanocarbon material: h2The weight ratio of O is 1: in the range of 50-200.
52. Shaped body according to any one of claims 1 and 36 to 38, wherein in the method for the production of nanocarbon materials the temperature of the aqueous dispersion is kept in the range of 90 to 240 ℃ during the reaction.
53. The shaped body as claimed in claim 52, wherein in the process for preparing the nanocarbon material, the temperature of the aqueous dispersion is maintained in the range of 120-220 ℃.
54. Shaped body according to any one of claims 1 and 36 to 38, wherein in the method for the production of nanocarbon material the duration of the reaction is in the range of 2 to 72 hours.
55. The shaped body according to claim 54, wherein in the method of producing the nanocarbon material the duration of the reaction is in the range of 12-36 hours.
56. The molded body according to any one of claims 1 and 36 to 38, wherein in the method for producing a nanocarbon material, a content of an N element is not more than 0.2 wt%, a content of an O element is not more than 1.5 wt%, and a total amount of metal elements is 2.5 wt% or less in the raw nanocarbon material.
57. The molded body according to claim 56, wherein in the method for producing a nanocarbon material, a content of an N element in the raw nanocarbon material is not more than 0.02% by weight, a content of an O element is not more than 0.3% by weight, and a total amount of metal elements is 0.5% by weight or less.
58. The shaped body according to any one of claims 1 and 36 to 38, wherein in the method for producing a nanocarbon material, the raw nanocarbon material is carbon nanotubes.
59. The shaped body according to claim 58, wherein in the method for producing a nanocarbon material, the starting nanocarbon material is multi-walled carbon nanotubes.
60. The shaped body according to claim 59, wherein, in the method for producing a nanocarbon material, the multi-walled carbon nanotubes have a specific surface area of 50 to 500m2/g。
61. The molded body as claimed in claim 60, wherein, in the preparation method of the nano-carbon material, the specific surface area of the multi-walled carbon nanotube is 120-190m2/g。
62. The shaped body as claimed in claim 59, wherein, in the process for preparing the nanocarbon material, the total weight loss ratio of the multi-walled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The total weight loss rate in the temperature range 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.
63. The shaped body according to claim 62, wherein in the process for the preparation of the nanocarbon material, w500/w800In the range of 0.02-0.4.
64. The shaped body according to any one of claims 1 and 36 to 38, wherein the method for preparing the nanocarbon material further comprises separating solid matter from the mixture obtained by the reaction, and drying the separated solid matter.
65. The shaped body according to claim 64, wherein in the method for producing a nanocarbon material, the drying is carried out at a temperature of 50-400 ℃ and the duration of the drying is not more than 48 hours.
66. The shaped body according to claim 65, wherein in the method for producing the nanocarbon material, the drying is carried out at a temperature of 80-180 ℃ and the duration of the drying is 4-24 hours.
67. The shaped body according to claim 66, wherein in the method of producing the nanocarbon material, the duration of the drying is 6 to 12 hours.
68. The shaped body according to any one of claims 1 to 3,6, 7, 16 to 18 and 36 to 38, wherein the nanocarbon material is present in an amount of 6 to 94% by weight and the heat-resistant inorganic oxide is present in an amount of 6 to 94% by weight, based on the total amount of the shaped body.
69. The shaped body according to claim 68, 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.
70. The shaped body according to claim 69, wherein the nanocarbon material is present in an amount of 40-90 wt.% and the heat-resistant inorganic oxide is present in an amount of 10-60 wt.%, based on the total amount of the shaped body.
71. The shaped body according to claim 70, wherein the nanocarbon material is present in an amount of 70 to 90 wt% and the heat-resistant inorganic oxide is present in an amount of 10 to 30 wt%, based on the total amount of the shaped body.
72. The molded body according to any one of claims 1 to 3,6, 7, 16 to 18 and 36 to 38, wherein the heat-resistant inorganic oxide is one or two or more of alumina, silica and titania.
73. The shaped body according to claim 72, wherein the heat-resistant inorganic oxide comprises silicon oxide.
74. The shaped body according to claim 73, 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.
75. The shaped body according to claim 74, wherein the silicon oxide is present in an amount of 20 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
76. The shaped body according to claim 75, wherein the silicon oxide is present in an amount of 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
77. A process for the preparation of a nanocarbon material shaped body, which process comprises mixing a nanocarbon material with a binder source, shaping the resulting mixture to give a shaped body, drying and optionally firing the shaped body, the binder source is selected from a refractory inorganic oxide and/or a precursor of a refractory inorganic oxide, the nano carbon material is a nano carbon material without surface treatment and a nano carbon material with surface treatment, or the nano carbon material is a nano carbon material with surface treatment, and the nano carbon material with the surface treatment contains O element and at least one metal element determined by X-ray photoelectron spectroscopy, the metal element is selected from transition metal elements, group IA metal elements and group IIA metal elements, the surface-treated nanocarbon material is a nanocarbon material described in any one of claims 1 to 67.
78. The method of claim 77, wherein said mixture further comprises at least one base.
79. A process as claimed in claim 78, wherein the base is selected from organic bases.
80. The method of claim 79, wherein the organic base is selected from the group consisting of quaternary ammonium bases, aliphatic amines, and aliphatic alcohol 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 as in claim 81, wherein the organic base is selected from quaternary ammonium bases represented by formula III,
Figure FDA0002448514360000091
in the formula III, R8、R9、R10And R11Are the same or different and are each C1-C4Alkyl group of (1).
83. The method of any of claims 78-82, wherein the molar ratio of the base to the binder source is from 0.1 to 10: 1, the binder source is calculated by oxide.
84. The method of claim 83, wherein the molar ratio of the base to the binder source is from 0.2-5: 1, the binder source is calculated by oxide.
85. The method of claim 84, wherein the molar ratio of the base to the binder source is 0.3-2: 1, the binder source is calculated by oxide.
86. The method of any one of claims 77-82, wherein prior to shaping the mixture, the method further comprises subjecting the mixture to a hydrothermal treatment.
87. The method as claimed in claim 86, 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.
88. The method as claimed in claim 87, wherein the hydrothermal treatment is carried out at a temperature of 120-180 ℃ and the duration of the hydrothermal treatment is 6-12 hours.
89. The method of any of claims 77-82, 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 liquid that is a mixture of one or more of a crystallization mother liquor of the silicon-containing molecular sieve and a heavy liquid of the silicon-containing molecular sieve.
90. The method of claim 89, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a heavy liquid discharge of an all-silicon molecular sieve, a crystallization mother liquid and/or a heavy liquid discharge of a titanium-silicon molecular sieve, and a crystallization mother liquid and/or a heavy liquid discharge of a silicon-aluminum molecular sieve.
91. A process 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 article, drying and optionally calcining the formed article, the aqueous dispersion containing a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nano carbon material is a nano carbon material without surface treatment and a nano carbon material with surface treatment, or the nano carbon material is a nano carbon material with surface treatment, and the nano carbon material with the surface treatment contains O element and at least one metal element determined by X-ray photoelectron spectroscopy, the metal element is selected from transition metal elements, group IA metal elements and group IIA metal elements, the surface-treated nanocarbon material is a nanocarbon material described in any one of claims 1 to 67.
92. The molding method of claim 91, wherein the aqueous dispersion further comprises at least one treatment agent, the treatment agent being one or a combination of two or more selected from the group consisting of a base, a peroxide, and a metal compound, the base being different from the metal compound.
93. The molding method of claim 92, wherein the base is an organic base.
94. The molding process of claim 93, wherein the base is selected from the group consisting of quaternary ammonium bases, aliphatic amines, and aliphatic alcohol amines.
95. The molding process of claim 94, wherein the base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
96. The molding method of claim 95, wherein the base is selected from quaternary ammonium bases represented by formula III,
Figure FDA0002448514360000101
in the formula III, R8、R9、R10And R11Are the same or different and are each C1-C4Alkyl group of (1).
97. The method of claim 92, wherein the peroxide is selected from the group consisting of hydrogen peroxide and organic peroxides of formula I,
Figure FDA0002448514360000111
in the formula I, R1And R2Each is selected from H, C4-C12Alkyl of (C)6-C12Aryl of (C)7-C12Aralkyl and
Figure FDA0002448514360000112
and R is1And R2Not simultaneously being H or R3Is C4-C12Straight or branched alkyl or C6-C12Aryl group of (1).
98. The method of claim 97, wherein the peroxide is selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, and dicumyl peroxide.
99. The method of claim 92, wherein the treatment agent is a base and at least one selected from a peroxide and a metal compound.
100. The method of claim 99, wherein the treatment agents are bases, peroxides, and metal compounds.
101. The process of claim 100, wherein the molar ratio of base, peroxide, and metal compound is 1: 0.1-10: 0.02-1.5.
102. The method of claim 101, wherein the molar ratio of base, peroxide, and metal compound is 1: 0.4-7: 0.07-0.8.
103. The method of claim 92, wherein the metal compound is selected from the group consisting of transition metal salts, basic metal compounds and transition metal complexes, and the metal element in the basic metal compound is selected from the group consisting of group IA metal elements and group IIA metal elements.
104. The method of claim 103, wherein said basic metal compound is selected from the group consisting of a hydroxide comprising said metallic element and a basic salt comprising said metallic element.
105. The method of claim 104, wherein said basic metal compound is selected from the group consisting of a hydroxide comprising said metallic element, a carbonate comprising said metallic element, and a bicarbonate comprising said metallic element.
106. The method of claim 105, wherein the basic metal compound is one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, calcium bicarbonate, potassium bicarbonate, and barium bicarbonate.
107. A process as set forth in claim 103 wherein said transition metal salt is selected from the group of transition metal acetates, transition metal oxalates, and transition metal hydroxycarbonates.
108. The method of claim 103 or 107, wherein the transition metal element is selected from group VIII metal elements.
109. The method of claim 108, wherein the transition metal element is selected from the group consisting of iron, ruthenium, cobalt, rhodium, nickel, palladium, and platinum.
110. A method as claimed in any of claims 92 to 107 wherein the molar ratio of treating agent to binder source is in the range 0.1 to 10: 1, the binder source is calculated by oxide.
111. The method of claim 110 wherein the molar ratio of treating agent to binder source is from 0.1 to 8: 1, the binder source is calculated by oxide.
112. The method of claim 111 wherein the molar ratio of treating agent to binder source is 0.3-4: 1, the binder source is calculated by oxide.
113. The method of any of claims 91-107, 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 liquid that is a mixture of one or more of a crystallization mother liquor of a silicalite and a heavy reject of a silicalite.
114. The method of claim 113, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a heavy liquid discharge of an all-silica molecular sieve, a crystallization mother liquid and/or a heavy liquid discharge of a titanium-silica molecular sieve, and a crystallization mother liquid and/or a heavy liquid discharge of a silico-alumina molecular sieve.
115. The method of any of claims 77-82 and 91-107, wherein the refractory inorganic oxide is one or more of alumina, silica and titania.
116. The method of claim 115, wherein the refractory inorganic oxide comprises silicon oxide.
117. The method of claim 116, wherein the silica is present in an amount of 10-100 wt.% based on the total amount of refractory inorganic oxide.
118. The method as claimed in claim 117, wherein the silicon oxide is present in an amount of 20-99 wt% based on the total amount of the refractory inorganic oxide.
119. The refractory inorganic oxide as recited in claim 118, wherein the silica is present in an amount of from 50 to 99% by weight, based on the total weight of the refractory inorganic oxide.
120. The method of any of claims 77-82 and 91-107, 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%.
121. The method as claimed in claim 120, 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.
122. The method as recited in claim 121, wherein the binder source is used in an amount such that the nanocarbon material is contained in an amount of 85-95 wt% and the refractory inorganic oxide is contained in an amount of 5-15 wt% in the finally prepared molded body.
123. The method of any one of claims 77-82 and 91-107, wherein the drying is performed at a temperature of 50-200 ℃, the duration of the drying being no more than 48 hours;
the calcination is carried out at a temperature of 300-800 ℃ and the duration of the calcination is 1-12 hours.
124. The method as recited in claim 123, wherein the drying is carried out at a temperature of 120-180 ℃, the duration of the drying being 3-24 hours;
the calcination is carried out at a temperature of 300-650 ℃ and the duration of the calcination is 2-4 hours.
125. The method of claim 124, wherein the duration of drying is 5-15 hours.
126. A nanocarbon material shaped body prepared by the method of any one of claims 77-125.
127. Use of a nanocarbon material shaped body according to any one of claims 1 to 76 and 126 as a catalyst for dehydrogenation reactions of hydrocarbons.
128. The use of claim 127, wherein the hydrocarbon is an alkane.
129. The use of claim 128, wherein the hydrocarbon is C2-C12Of (a) an alkane.
130. The use of claim 129, wherein the hydrocarbon is n-butane.
131. A hydrocarbon dehydrogenation reaction process comprising contacting a hydrocarbon with the nanocarbon material shaped body of any one of claims 1-76 and 126 under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
132. The method of claim 131, wherein the hydrocarbon is an alkane.
133. The method of claim 132, wherein the hydrocarbon is C2-C12Of (a) an alkane.
134. The method of claim 133, wherein the hydrocarbon is n-butane.
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