CN107661767B

CN107661767B - Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method

Info

Publication number: CN107661767B
Application number: CN201610603207.7A
Authority: CN
Inventors: 史春风; 荣峻峰; 于鹏
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-07-27
Filing date: 2016-07-27
Publication date: 2020-07-28
Anticipated expiration: 2036-07-27
Also published as: CN107661767A

Abstract

A nano carbon material forming body, a preparation method and application thereof, a forming method of the nano carbon material and a hydrocarbon dehydrogenation reaction method. The invention discloses a nano carbon material forming body, which contains a nano carbon material and a heat-resistant inorganic oxide for bonding and forming the nano carbon material, wherein the content of the nano carbon material is 6-94 wt%, the content of a bonding agent is 6-94 wt%, and the nano carbon material contains at least one metal element selected from transition metal elements, IA group metal elements and IIA group metal elements. The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.

Description

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

Technical Field

The invention relates to the technical field of nano carbon material forming, in particular to a nano carbon material forming body and a preparation method thereof, and also relates to application of the nano carbon material forming body as a catalyst for hydrocarbon dehydrogenation reaction.

Background

Dehydrogenation of hydrocarbons is an important type of reaction, for example, most lower alkenes are obtained by dehydrogenation of lower alkanes. Dehydrogenation reactions can be classified into two types, direct dehydrogenation reactions (i.e., oxygen does not participate) and oxidative dehydrogenation reactions (i.e., oxygen does participate), depending on whether oxygen participates.

Various types of nanocarbon materials have been demonstrated to have catalytic effects on both direct dehydrogenation reactions and oxidative dehydrogenation reactions of hydrocarbon materials.

In the hydrocarbon oxidative dehydrogenation process using the nano-carbon material as the catalyst, for example, a fixed bed reaction process is adopted, the nano-carbon material needs to be molded, and the molded body needs to meet the following two requirements: (1) the catalyst has certain strength to avoid the molded body from being crushed in the reaction process, and on one hand, the pressure drop of a catalyst bed layer is increased due to fine particles or powder formed by crushing, so that the production and operation cost is increased, and the production danger is increased; on the other hand, the fine particles or powder formed by crushing can cause catalyst loss and product separation complication if the fine particles or powder is carried out by reaction products; (2) the nano carbon material has certain porosity to improve the specific surface area of the formed body, so that the nano carbon material in the formed body can be more fully contacted with reaction materials.

As an example of shaping nanocarbon materials, researchers have attempted to load Carbon Nanotubes (CNTs) on the surface of SiC foams to form CNT/SiC foams. Although CNTs anchor well to the surface of the SiC foam, the loading of CNTs is low, typically reaching only 0.5-4 wt%.

Therefore, how to form the nanocarbon material into a formed body with high strength in a wide nanocarbon material content range still remains a technical problem to be solved urgently.

Disclosure of Invention

The invention aims to provide a nano carbon material forming body and a preparation method thereof, wherein the nano carbon material forming body not only has higher strength, but also can adjust the content of a nano carbon material in a wider range.

According to one aspect of the present invention, there is provided a nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the binder is contained in an amount of 6 to 94% by weight, based on the total amount of the molded body, and the nanocarbon material contains at least one metal element selected from the group consisting of a transition metal element, a group IA metal element and a group IIA metal element.

According to a second aspect of the present invention, there is provided a nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the binder is contained in an amount of 6 to 94% by weight, based on the total amount of the molded body;

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 nitrogen-containing compound and at least one metal compound are dissolved in the aqueous dispersion, and the nitrogen-containing compound is selected from NH₃Hydrazine and urea, wherein the metal compound is selected from alkali metal compounds and transition metal compounds, the metal element in the alkali metal compounds is selected from IA group metal elements and IIA group metal elements, and the temperature of the aqueous dispersion is in the range of 80-300 ℃ in the reaction process.

According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material molded body, which comprises mixing a nanocarbon material with a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, molding the obtained mixture to obtain a molded body, drying and optionally firing the molded body, and determining from X-ray photoelectron spectroscopy that the nanocarbon material contains at least one metal element selected from a transition metal element, a group IA metal element and a group IIA metal element.

According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.

According to a fifth aspect of the present invention, there is provided a method for forming a nanocarbon material, comprising subjecting a nanocarbon material to a 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 a nanocarbon material which has not been subjected to a surface treatment and/or a nanocarbon material which has been subjected to a surface treatment, the nanocarbon material which has been subjected to a surface treatment containing 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 are to be understood to encompass values close to those ranges or values, for a range of values, between the endpoints of each range, and individual values, and between individual values, may be combined with each other to provide one or more new ranges of values, which ranges of values are to be considered specifically disclosed herein.

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 at least one metal element (hereinafter, sometimes also referred to as a nanocarbon material containing a metal atom).

The nanocarbon material generally contains an O element and an N element. The contents of the O element, the N 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. In general, the content of the N element may be 0.2 to 10% by weight, preferably 0.5 to 6% by weight, more preferably 1 to 4% by weight, in terms of element, based on the total amount of the nanocarbon material; the content of the element O may be 1 to 15% by weight, preferably 1.2 to 9% by weight, more preferably 2 to 8% by weight; the content of the metal element may be 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 4% by weight.

In the invention, 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. Wherein X-ray photoelectron spectroscopy is performed by Thermo Scientific equipped with a TherThe test is carried out on an ESCA L ab250 type X-ray photoelectron spectrometer of mo Avantage V5.926 software, an excitation source is monochromatic Al K α X-ray, the energy is 1486.6eV, the power is 150W, the transmission energy used by narrow scanning is 30eV, and the basic vacuum during the analysis test is 6.5 × 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 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.

The content of the element O in the nanocarbon material containing an alkali metal element according to the present invention may be 1 to 10% by weight, preferably 1.2 to 8% by weight, more preferably 1.3 to 7.5% by weight, and still more preferably 2 to 6% by weight, in terms of the element, based on the total amount of the nanocarbon material; the content of the N element may be 0.2 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 0.8 to 4% by weight, and further preferably 1 to 3.5% by weight; the total amount of the metal elements may be 0.1 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight, and further preferably 2.5 to 4% by weight; the content of the element C may be 75 to 98.7% by weight, preferably 79.5 to 97.8% by weight, more preferably 83.5 to 96.9% by weight, and further preferably 86.5 to 94.5% by weight.

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 I_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^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 0.06 to 0.2, and further preferably in the range of 0.09 to 0.18. Determined from the peak in the range of 531.0-533.5eV in the X-ray photoelectron spectrumHas the content of O element of I_O ^nm，I_O ^nm/I_O ^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 0.94, and further preferably in the range of 0.82 to 0.91.

In the present invention, the area of the peak of O1s in the X-ray photoelectron spectrum is represented as A_O 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 A_O 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 A_O ³Wherein, I_O ^m/I_O ^t＝A_O ²/A_O ¹，I_O ^nm/I_O ^t＝A_O ³/A_O ¹。

According to the nanocarbon material containing an alkali metal element of the present 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 I_O ^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 I_O ^e，I_O ^c/I_O ^eMay be in the range of 0.1 to 3, preferably in the range of 0.8 to 2.5, preferably in the range of 1 to 2, more preferably in the range of 1.2 to 1.6.

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 A_O ⁴The area of the peak in the range of 532.6 to 533.5eV is designated as A_O ⁵，I_O ^c/I_O ^e＝A_O ⁴/A_O 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 the X-ray photoelectron spectrum may be 60 to 98% by weight, preferably 65 to 95% by weight, more preferably 70 to 92% by weight, still more preferably 80 to 92% by weight, based on the total amount of the C element in the nanocarbon material determined by the X-ray photoelectron spectrum; the total content of the C element determined from a peak in the range of 286.0 to 288.8eV in the X-ray photoelectron spectrum may be 2 to 40% by weight, preferably 5 to 35% by weight, more preferably 8 to 30% by weight, still more preferably 8 to 20% by weight.

In the present invention, the area A of the peak of C1s spectrum in the X-ray photoelectron spectrum_C 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 A_C ²The area of a peak in the range of 286.0-288.8eV is designated as A_C ³The content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum (A)_C ²/A_C ¹Total content of C element determined from peak in range of 286.0-288.8eV in X-ray photoelectron spectrum_C ³/A_C 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 I_C ^cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is I_C ^e，I_C ^c/I_C ^eMay be in the range of 0.3 to 2, preferably in the range of 0.5 to 1.5, more preferably in the range of 0.7 to 1.

In the present invention, the 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 286.0-286.2eV288.6-288.8eV (corresponding to carboxyl, anhydride, and ester-type carbon species), and the area of the peak in the range of 286.0-286.2eV is designated as A_C ⁴The area of a peak in the range of 288.6-288.8eV is designated as A_C ⁵，I_C ^c/I_C ^e＝A_C ⁵/A_C ⁴。

According to the nano carbon material containing the alkali metal element, the total amount of N element in the nano carbon material is determined as I by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tMay be in the range of 0.5 to 1, preferably in the range of 0.7 to 1, preferably in the range of 0.8 to 1, more preferably in the range of 0.9 to 0.96.

According to the nano carbon material containing the alkali metal element, the content of N element determined by a peak in a range of 400.6-401.5eV in an X-ray photoelectron spectrum is low or even no. Generally, the amount of N element determined by a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is I_N ^g，I_N ^g/I_N ^tIs not higher than 0.3, and is generally in the range of 0 to 0.2, preferably in the range of 0.04 to 0.1.

In the present invention, the total amount A of N element is determined from the area of the peak of N1s in the X-ray photoelectron spectrum_N ¹The peaks of N1s in the X-ray photoelectron spectrum were divided into two groups, i.e., a peak in the range of 400.6 to 401.5eV (corresponding to a graphite-type nitrogen species) and a peak in the range of 398.5 to 400.1eV (a nitrogen species other than graphite-type nitrogen), and the area of the peak in the range of 400.6 to 401.5eV was designated as A_N ²The area of the peak in the range of 398.5-400.1eV is designated as A_N ³，I_N ^c/I_N ^t＝A_N ³/A_N ¹，I_N ^g/I_N ^t＝A_N ²/A_N ¹When the obtained ratio is less than 0.01, the plant is considered to be free of such speciesAnd the content of the species is recorded as 0.

The transition metal element-containing nanocarbon material according to the present invention may contain an O element in an amount of 0.2 to 15 wt%, preferably 2 to 12 wt%, more preferably 3 to 9 wt%, and further preferably 4 to 8 wt%, based on the total amount of the nanocarbon material and calculated as an element; the content of the N element may be 0.3 to 10% by weight, preferably 1 to 6% by weight, more preferably 1.1 to 5% by weight, and further preferably 2 to 4% by weight; the total amount of the metal elements may be 0.5 to 10% by weight, preferably 1.2 to 6% by weight, more preferably 1.5 to 5.5% by weight, and still more preferably 2 to 3.5% by weight; the content of the element C may be 65 to 99% by weight, preferably 76 to 95.8% by weight, more preferably 80.5 to 94.4% by weight, and still more preferably 84.5 to 92% 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 I_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^tMay be in the range of 0.02 to 0.2, preferably in the range of 0.05 to 0.18, more preferably in the range of 0.08 to 0.15. According to the nanocarbon material containing a metal atom of the present invention, the content of O element determined by a peak in the range of 531.0 to 533.5eV in an X-ray photoelectron spectrum is I_O ^nm，I_O ^nm/I_O ^tMay be in the range of 0.8 to 0.98, preferably in the range of 0.82 to 0.95, more preferably in the range of 0.85 to 0.92.

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 I_O ^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 I_O ^e，I_O ^c/I_O ^eMay be in the range of 0.2 to 1, preferably in the range of 0.5 to 0.99.

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 70 to 92% 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 to 288.8eV in the X-ray photoelectron spectrum may be 5 to 40% by weight, preferably 8 to 30% 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 I_C ^cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is I_C ^e，I_C ^c/I_C ^eMay be in the range of 0.2 to 2, preferably in the range of 0.4 to 1.5, more preferably in the range of 0.6 to 1.2.

According to the transition metal element-containing nanocarbon material of the invention, the total amount of N elements in the nanocarbon material is I determined by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tMay be in the range of 0.5 to 1, preferably in the range of 0.7 to 1, more preferably in the range of 0.85 to 0.95.

According to the transition metal element-containing nanocarbon material of the present invention, the content of N element determined by a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is low or even no. Generally, the amount of N element determined by a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is I_N ^g，I_N ^g/I_N ^tIs not higher than 0.35, and is generally in the range of 0.05 to 0.25, preferably in the range of 0.05 to 0.12.

In the present invention, the position of each peak is determined by the binding energy corresponding to the peak top of the peak, and the peak determined by the above-mentioned range refers to a peak having the binding energy corresponding to the peak top within the range, and may include one peak or two or more peaks within the range. For example: the peak in the range of 398.5-400.1eV means all peaks having a binding energy in the range of 398.5-400.1eV corresponding to the peak top.

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.C₈₀₀The mass loss rate, W, measured at a temperature of 800 deg.C₅₀₀Is the mass loss rate determined at a temperature of 500 ℃; the weight loss rate is measured in an air atmosphere by adopting a thermogravimetric analyzer, the test initial temperature is 25 ℃, and the temperature is increasedThe temperature 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 material nanocarbon material is dispersed in a closed container, wherein at least one nitrogen-containing compound and at least one metal compound are dispersed in the aqueous dispersion, and the temperature of the aqueous dispersion is in the range of 70-300 ℃ during the reaction.

The nitrogen-containing compound is selected from NH₃Hydrazine and urea.

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 the group consisting of metal nitrates, metal acetates, metal carbonates, metal sulfates, metal hydroxycarbonates, metal hydroxides, metal chlorides, metal oxalates, and metal complexes, and more preferably from the group consisting of metal acetates, metal oxalates, metal hydroxycarbonates, and metal complexes (e.g., palladium ammine nitrate, ruthenium acetylacetonate, and rhodium acetylacetonate).

The transition metal compound may be specifically selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, nickel hydroxycarbonate, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt hydroxycarbonate, cobalt chloride, cobalt hydroxide, iron nitrate, ferrous acetate, ferric sulfate, ferric hydroxycarbonate, ferric chloride, ferric hydroxide, zinc nitrate, zinc acetate, zinc sulfate, zinc hydroxycarbonate, 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 nitrate (e.g., tetraamminepalladium nitrate), rhodium chloride, palladium acetylacetonate, iron oxalate, nickel (ll) nitrate, cobalt (ll) acetate, cobalt (ll) sulfate, cobalt hydroxide, cobalt (ll) chloride, cobalt (ll) hydroxide, iron, Palladium acetate, ruthenium acetate, rhodium acetate, ruthenium acetylacetonate and rhodium 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 the nitrogen-containing compound, 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: nitrogen-containing compounds: the weight ratio of the basic metal compound is preferably in the range of 1: 0.01-20: in the range of 0.01 to 20, the nanocarbon material molded body can obtain further improved catalytic reaction effect when used as a catalyst for dehydrogenation reaction of hydrocarbon. Raw material nano carbon material: nitrogen-containing compounds: the weight ratio of the basic metal compound is more preferably in the range of 1: 0.02-10: in the range of 0.02 to 15, further preferably in the range of 1: 0.05-5: in the range of 0.05 to 12, more preferably in the range of 1: 0.05-2.5: in the range of 0.1 to 10, particularly preferably in the range of 1: 0.05-1: in the range of 0.5-5.

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: 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 250, further preferably in the range of 1: in the range of 20 to 200, more preferably in the range of 1: in the range of 50-160.

When the metal compound is a basic metal compound, in a preferred embodiment, the nitrogen-containing compound is ammonia, the metal element in the metal compound is selected from group IIA metal elements, more preferably from magnesium, calcium, and barium, and the metal compound is preferably a carbonate and/or a bicarbonate. In another preferred embodiment, the nitrogen-containing compound is hydrazine, the metal element in the metal compound is selected from group IIA metal elements, preferably from magnesium, calcium and barium, and the metal compound is preferably a hydroxide. In yet another preferred example, the nitrogen-containing compound is urea, the metal element in the metal compound is selected from group IA metal elements, preferably from lithium, sodium and potassium, and the metal compound is preferably a bicarbonate. The nanocarbon material molded bodies according to the above three 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: nitrogen-containing compounds: the weight ratio of the transition metal compound is preferably in the range of 1: 0.01-10: in the range of 0.01 to 10, the catalytic effect of the nanocarbon material molded body as a catalyst for dehydrogenation reaction of hydrocarbon can be further improved. Raw material nano carbon material: nitrogen-containing compounds: the weight ratio of the transition metal compound is more preferably in the range of 1: 0.02-5: in the range of 0.05 to 8, further preferably in the range of 1: 0.02-2: in the range of 0.06 to 6, more preferably in the range of 1: 0.02-1: in the range of 0.08 to 5, particularly preferably in the range of 1: 0.02-0.5: in the range of 0.5-5.

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 250, further preferably in the range of 1: in the range of 10 to 200, more preferably in the range of 1: in the range of 20 to 200, particularly preferably in the range of 1: 40-200.

When the metal compound is a transition metal compound, in a preferred example, the nitrogen-containing compound is NH₃The metal element in the metal compound is selected from iron, cobalt and nickel, and the metal compound is preferably selected from one or more of metal acetate and metal oxalate. In another preferred embodiment, the nitrogen-containing compound is hydrazine, the metal element in the metal compound is selected from palladium and platinum, and the metal compound is preferably a metal acetate and a metal complex (e.g., ethylene glycol)Palladium acetylacetonate and tetraamminepalladium nitrate). In still another preferred example, the nitrogen-containing compound is urea, the metal element in the metal compound is selected from ruthenium and rhodium, and the metal compound is preferably a metal complex (e.g., ruthenium acetylacetonate and rhodium acetylacetonate).

According to the shaped body of the second aspect of the present invention, the temperature of the aqueous dispersion during the reaction is preferably in the range of 120-240 ℃.

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 10 to 72 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 aqueous dispersion can be obtained by dispersing a raw material nanocarbon material in water (preferably deionized water) and then adding the nitrogen-containing compound and the metal compound. 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 200 kHz; the duration of the ultrasonic oscillation may be 0.1 to 6 hours, preferably 1 to 4 hours. The nitrogen-containing compound 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。

The nano carbon material is multi-wall carbonWhen the nano-tube is used, 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/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-C₁₀Of (2) aOne or more of aluminum salts (such as aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate).

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 I:

in the formula I, R₁、R₂、R₃And R₄Each 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 urea, hydrazine, 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 II,

in the formula II, R₅、R₆、R₇And R₈Are 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: r₅、R₆、R₇And R₈Each of which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl orA tertiary butyl group.

The amine may be an aliphatic amine of formula III and of formula R₁₂(NH₂)₂One or more of the substances shown,

in the formula III, R₉、R₁₀And R₁₁Are each H, C₁-C₆Alkyl or C₆-C₁₂And R is an aryl group of₉、R₁₀And R₁₁Not 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 R₁₂(NH₂)₂In, R₁₂Can 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 IV,

in the formula IV, R₁₃、R₁₄And R₁₅Each is-R₁₆OH or hydrogen, and R₁₃、R₁₄And R₁₅At least one of which is-R₁₆OH，R₁₆Is 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 II, 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 0.15 to 8: 1, more preferably 0.4 to 7: 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, in heavy liquid discharge of titanium silicalite, SiO is used₂The content of elemental silicon is generally 0.01 to 10% by weight, preferably 0.02 to 5% by weight, more preferably 0.5 to 2% by weight; with TiO₂The content of titanium element is generally 0.0001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, more preferably 0.01 to 0.08% by weight; the content of the base is generally 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 1 to 4% by weight. As an example, in the crystallization mother liquor of the silicon-aluminum molecular sieve, SiO is used₂The content of elemental silicon is generally 0.05 to 10% by weight, preferably 0.1 to 8% 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 unmodified nanocarbon materials and modified nanocarbon materials. In the invention, the surface of the nano carbon material is detected by adopting an X-ray photoelectron spectroscopy method, if the total content of elements except C element in the detected nano carbon material surface elements is below 2 weight percent, the nano carbon material is regarded as the nano carbon material without modification treatment, otherwise, the nano carbon material is regarded as the nano carbon 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, the mixture is preferably subjected to hydrothermal treatment in a closed container, so that not only the strength of the finally prepared formed body can be remarkably improved, but also the catalytic performance of the finally prepared formed body can be remarkably improved. 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 300m²(ii)/g, more preferably 100-250m²(ii)/g, more preferably 120-²(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 to 0.5, more preferably in the range of 0.02 to 0.3, and further preferably in the range of 0.05 to 0.15. As an example, the nanocarbon material without surface treatment may be a raw nanocarbon material in the molded body according to the second aspect of the invention.

In another embodiment, the nanocarbon material is a modified nanocarbon material, and the surface-treated nanocarbon material contains 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 hydrocarbons, the content of the metal element may be 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 4% by weight, based on the total amount of the modified nanocarbon material. The modified nanocarbon material generally further contains an element N and an element O, and the content of the element N may be 0.2 to 10% by weight, preferably 0.5 to 6% by weight, and more preferably 1 to 4% by weight, based on the total amount of the modified nanocarbon material; the content of the element O may be 1 to 15% by weight, preferably 1.2 to 9% by weight, more preferably 2 to 8% by weight.

Specifically, the modified 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.

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 unmodified nanocarbon materials or modified 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 comprises at least one treating agent which is at least one base and/or at least one metal compound, the base being selected from ammonia and organic bases, the organic bases preferably being selected from hydrazine, urea, amines, alcohol amines and quaternary ammonium bases. 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 metal compound is preferably a transition metal compound and/or a basic metal compound. In one embodiment, the metal compound is a transition metal compound. In another embodiment, the metal compound is a basic metal compound.

The organic base may be the organic base described in the process of the third aspect of the invention and will not be described in detail here.

In a preferred embodiment, the treating agent is a base and a metal compound, and the base is NH₃One or more than two of hydrazine and urea, wherein the metal compound is a basic metal compound. 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 the base and the basic metal compound and then molded), the preferred embodiment not only reduces the amount of the basic metal compound used, but also produces a molded article showing thatCompared with the formed body prepared by forming after hydrothermal treatment, the strength and the catalytic performance are equivalent to or even higher than those of the formed body. In a preferred embodiment, the base is ammonia, the metal element of the metal compound is selected from group IIA metal elements, more preferably from magnesium, calcium and barium, and the metal compound is preferably a carbonate and/or bicarbonate. In another preferred embodiment, the base is hydrazine, the metal element of the metal compound is selected from group IIA metal elements, preferably from magnesium, calcium and barium, and the metal compound is preferably a hydroxide. In yet another preferred example, the nitrogen-containing compound is urea, the metal element in the metal compound is selected from group IA metal elements, preferably from lithium, sodium and potassium, and the metal compound is preferably a bicarbonate.

In this preferred embodiment, the molar ratio of metal compound to base may be from 0.01 to 0.5: 1, preferably 0.05 to 0.3: 1.

in another preferred embodiment, the base is a quaternary ammonium base, preferably a template agent for synthesizing a titanium silicalite molecular sieve, such as the quaternary ammonium base shown in formula II. 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.

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 0.2 to 8: 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 be applied to various typesThe hydrocarbons are dehydrogenated to yield unsaturated hydrocarbons, such as olefins. The process according to the invention is particularly suitable for dehydrogenating alkanes, thereby obtaining 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, 6-trimethylheptane, 2,3, 3-trimethylheptane, 2,4, 4-trimethylheptane, 2-methyl-3-ethylheptane, 2-methyl-4-ethylheptaneAnd one or a combination of two or more of the group-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.

The hydrocarbon is more preferably one or two or more of propane, n-butane, isobutane and phenylethane, and further preferably n-butane.

According to the hydrocarbon dehydrogenation reaction method of the present invention, the reaction may be carried out in the presence or absence of oxygen. Preferably in the presence of oxygen. When carried out in the presence of oxygen, the amount of oxygen may be conventionally selected. Generally, the molar ratio of hydrocarbon to oxygen may be from 0.01 to 100: 1, preferably 0.1 to 10: 1, more preferably 0.2 to 5: 1, most preferably 0.5-2: 1.

according to the hydrocarbon dehydrogenation reaction method, the hydrocarbon and optional oxygen can be fed into the reactor by the carrier gas to contact and react with the heteroatom-containing nano carbon material. The carrier gas may be a commonly used gas that does not chemically interact with the reactants and the reaction product under the reaction conditions and does not undergo decomposition, such as one or a combination of two or more of nitrogen, carbon dioxide, a noble gas, and water vapor. The amount of carrier gas may be conventionally selected. Generally, the carrier gas may be present in an amount of 30 to 99.5% by volume, preferably 50 to 99% by volume, more preferably 70 to 98% by volume.

In the process for the dehydrogenation of hydrocarbons according to the present invention, the temperature of the contacting may be conventionally selected to be sufficient for the dehydrogenation of hydrocarbons to take place. Generally, the contacting may be carried out at a temperature of 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 hydrocarbon dehydrogenation process of the present invention, the duration of the contacting can be selected according to the contacting temperature, such as the duration of the contacting can be expressed in terms of the weight hourly space velocity of the feed when 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. 3000-^-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 X-ray photoelectron spectrometer model ESCA L ab250 equipped with ThermoAvantage V5.926 software, from Thermo Scientific, with an excitation source of monochromated AlK α X rays, an energy of 1486.6eV, a power of 150W, a transmission energy of 30eV for narrow scans, and a base vacuum of 6.5 × 10 for analytical tests^-10mbar, electron binding energy was corrected for the C1s peak (284.0eV) of elemental carbon, data processed on Thermo Avantage software, and quantified in the analytical module using the sensitivity factor method. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.

In the following preparation examples, thermogravimetric analysis was carried out on a TA5000 thermal analyzer under air atmosphere at a temperature rise rate of 10 ℃/min and at a temperature range of room temperature (25 ℃) to 1000 ℃. The samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing. The method adopts ASAP2000 type N of Micromertrics corporation in America₂The physical adsorption apparatus measures the specific surface area.

The properties of the multi-walled carbon nanotubes as the raw nanocarbon material in the following preparation examples are listed in table 1 below.

TABLE 1

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 40 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 14kHz and the time was 0.5 hour. Then, NH is added₃And barium bicarbonate to obtain an aqueous dispersion, wherein the carbon nanomaterial: NH (NH)₃: barium bicarbonate: h₂The weight ratio of O is 1: 0.05: 4.25: 100 parts by weight.

(2) The resulting aqueous dispersion was reacted in a high-pressure autoclave with a polytetrafluoroethylene liner at a temperature of 120 ℃ under autogenous pressure for 36 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid substance at normal pressure (1 atm, the same 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 subjected to reflux reaction under normal pressure for 36 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 6 hours to obtain the 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 the step (2), the obtained aqueous dispersion was reacted in an autoclave equipped with a polytetrafluoroethylene inner liner under autogenous pressure at a temperature of 90 ℃ for 36 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 2 hours. Then, NH is added₃And calcium bicarbonate to obtain an aqueous dispersion, wherein the carbon nanomaterial: NH (NH)₃: calcium bicarbonate: h₂The weight ratio of O is 1: 0.2: 5: 120, is charged.

(2) The resulting aqueous dispersion was reacted in a high-pressure autoclave with a polytetrafluoroethylene liner at a temperature of 170 ℃ 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 6 hr to obtain nanometer carbon material containing metal atoms, and its composition, specific surface area and w₅₀₀/w₈₀Listed in table 2.

Preparation example 6

A nanocarbon material containing a metal atom was prepared in the same manner as in preparation example 5, except that, in step (1), calcium hydrogencarbonate was replaced with an equimolar amount of sodium hydrogencarbonate.

Preparation example 7

The same method as in preparation example 1 was used to prepare a nanocarbon material containing metal atoms, except that: in the step (1), dispersing a raw material nano carbon material in deionized water, and then adding hydrazine and magnesium hydroxide to obtain an aqueous dispersion, wherein the weight ratio of the raw material nano carbon material: hydrazine: magnesium hydroxide: h₂The weight ratio of O is 1: 1: 4: feeding at a ratio of 150; in the step (2), the obtained aqueous dispersion is reacted for 36 hours in a high-pressure reaction kettle with a polytetrafluoroethylene lining at the temperature of 160 ℃ under autogenous pressure.

Preparation example 8

The same aqueous dispersion as in preparation example 7 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 ℃ and subjected to reflux reaction under normal pressure for 36 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 12 hours to obtain the metal atom-containing nano carbon material.

Preparation example 9

The same method as in preparation example 5 was used to prepare a nanocarbon material containing metal atoms, except that: in the step (1), dispersing a raw material nano carbon material in deionized water, and then adding hydrazine and barium hydroxide to obtain an aqueous dispersion, wherein the weight ratio of the raw material nano carbon material: hydrazine: barium hydroxide: h₂The weight ratio of O is 1: 0.1: 0.5: 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 48 hours at the temperature of 140 ℃ under autogenous pressure.

Preparation example 10

A nanocarbon material containing metal atoms was produced in the same manner as in production example 9, except that, in step (1), the nanocarbon material was a multiwall carbon nanotube D.

Preparation example 11

A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 9, except that barium hydroxide was replaced with an equimolar amount of sodium hydroxide.

Preparation example 12

The same method as in preparation example 1 was used to prepare a nanocarbon material containing metal atoms, except that: in the step (1), dispersing a raw material nano carbon material in deionized water, and then adding urea and sodium bicarbonate to obtain an aqueous dispersion, wherein the raw material nano carbon material comprises the following components in percentage by weight: urea: sodium bicarbonate: h₂The weight ratio of O is 1: 1: 1: 160, feeding in proportion; in the step (2), the obtained aqueous dispersion is reacted for 12 hours in a high-pressure reaction kettle with a polytetrafluoroethylene lining at the temperature of 150 ℃ under the autogenous pressure.

Preparation example 13

The same aqueous dispersion as in preparation example 12 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 150 ℃ and subjected to a reflux reaction under normal pressure for 12 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 14

A nanocarbon material containing metal atoms was produced in the same manner as in production example 12, 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), dispersing the raw material nano carbon material in deionized water, and then adding urea and potassium bicarbonate to uniformly disperse to obtain a water dispersion, wherein the weight ratio of the raw material nano carbon material: urea: the weight ratio of the potassium bicarbonate to the water is 1: 0.2: 2: feeding at a ratio of 100; in the step (2), the obtained aqueous dispersion is reacted for 24 hours at 180 ℃ under autogenous pressure in a high-pressure reaction kettle with a polytetrafluoroethylene lining.

Preparation example 16

A nanocarbon material containing a metal atom was produced in the same manner as in production example 15, except that potassium hydrogencarbonate was replaced with calcium hydrogencarbonate in an equimolar amount.

Preparation example 17

(1) Dispersing 20g of multi-walled carbon nanotubes A serving as a raw material nanocarbon material in deionized water under ultrasonic oscillation conditions, wherein the ultrasonic oscillation conditions comprise: the frequency was 140kHz and the time was 0.5 hour. Then, NH is added₃(provided in the form of a 36 wt% aqueous solution) and nickel acetate as a metal compound, thereby obtaining an aqueous dispersion, wherein, as the raw material nanocarbon material: NH (NH)₃: metal compound (b): h₂The weight ratio of O is 1: 0.2: 5: 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 140 ℃ 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 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 18

The same aqueous dispersion as in preparation example 17 was placed in a three-necked flask equipped with a condenser, and the three-necked flask was placed in an oil bath at a temperature of 140 ℃ 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 nano carbon material containing the metal atoms.

Preparation example 19

A nanocarbon material containing metal atoms was produced in the same manner as in production example 17, except that in step (1), the nanocarbon material was a multiwall carbon nanotube B.

Preparation example 20

A nanocarbon material containing metal atoms was produced in the same manner as in production example 17, 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 70 ℃ under autogenous pressure for 24 hours.

Preparation example 21

Dispersing 20g of multi-walled carbon nanotubes C serving as a raw material nanocarbon material in deionized water under ultrasonic oscillation conditions, wherein the ultrasonic oscillation conditions comprise: the frequency was 90kHz and the time was 4 hours. Then, NH is added₃(provided in the form of a 36 wt% aqueous solution) and iron oxalate as a metal compound, thereby obtaining an aqueous dispersion, wherein, as the raw material nanocarbon material: NH (NH)₃: metal compound (b): h₂The weight ratio of O is 1: 0.02: 2.5: 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 240 ℃ 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. After drying the collected solid matter at 160 ℃ for 8 hours under normal pressure, a nanocarbon material containing metal atoms was obtained, the property parameters of which are listed in table 3.

Preparation example 22

A nanocarbon material containing metal atoms was produced in the same manner as in production example 21, 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 280 ℃ under autogenous pressure for 12 hours.

Preparation example 23

A nanocarbon material containing a metal atom was produced in the same manner as in production example 21, except that in step (1), iron oxalate was replaced with an equimolar amount of palladium acetate.

Preparation example 24

A nanocarbon material containing a metal atom was produced in the same manner as in production example 21, except that in step (1), iron oxalate was replaced with an equimolar amount of ruthenium acetate.

Preparation example 25

A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 17, except that: in the step (1), a raw material nanocarbon material is dispersed in deionized water, and then hydrazine (provided in the form of a50 wt% aqueous solution) and palladium acetate as a metal compound are added to obtain an aqueous dispersion, wherein, in terms of the raw material nanocarbon material: hydrazine: metal compound (b): h₂The weight ratio of O is 1: 0.2: 4.5: feeding at a ratio of 100; 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 180 ℃ under the autogenous pressure.

Preparation example 26

The same aqueous dispersion as in preparation example 25 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 180 ℃ 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 27

A nanocarbon material containing metal atoms was produced in the same manner as in production example 25, 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 260 ℃ under autogenous pressure for 24 hours.

Preparation example 28

A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 21, except that: in the step (1), a raw material nanocarbon material is dispersed in deionized water, and then hydrazine and palladium acetylacetonate as a metal compound are added to obtain an aqueous dispersion, wherein the weight ratio of the raw material nanocarbon material: hydrazine: metal compound (b): h₂The weight ratio of O is 1: 0.5: 4.5: feeding at a ratio of 50; step (2)) The aqueous dispersion obtained was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at a temperature of 120 ℃ under autogenous pressure for 72 hours.

Preparation example 29

A nanocarbon material containing metal atoms was produced in the same manner as in production example 28, except that in step (1), the nanocarbon material was a multiwall carbon nanotube D.

Preparation example 30

A nanocarbon material containing metal atoms was produced in the same manner as in production example 28, 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 60 ℃ under autogenous pressure for 72 hours.

Preparation example 31

A nanocarbon material containing a metal atom was produced in the same manner as in production example 28, except that palladium acetylacetonate was replaced with an equimolar amount of nickel oxalate.

Preparation example 32

A nanocarbon material containing a metal atom was produced in the same manner as in production example 28, except that palladium acetylacetonate was replaced with an equimolar amount of rhodium acetate.

Preparation example 33

A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 17, except that: in the step (1), a raw material nanocarbon material is dispersed in deionized water, and then urea and ruthenium acetylacetonate, which is a metal compound, are added to obtain an aqueous dispersion, wherein the weight ratio of the raw material nanocarbon material: urea: metal compound (b): h₂The weight ratio of O is 1: 0.5: 0.1: feeding at a ratio of 80; 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 180 ℃ under autogenous pressure.

Preparation example 34

The same aqueous dispersion as in preparation example 33 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 180 ℃ and subjected to reflux reaction under normal pressure for 36 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at normal pressure and 120 ℃ for 12 hours to obtain the metal atom-containing nano carbon material.

Preparation example 35

A nanocarbon material containing metal atoms was produced in the same manner as in production example 33, 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 80 ℃ under autogenous pressure for 36 hours.

Preparation example 36

A nanocarbon material containing metal atoms was produced in the same manner as in production example 33, except that the nanocarbon material was a multiwall carbon nanotube B.

Preparation example 37

A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 21, except that: in the step (1), a raw material nanocarbon material is dispersed in deionized water, and then urea and rhodium acetylacetonate as a metal compound are added to obtain an aqueous dispersion, wherein the weight ratio of the raw material nanocarbon material: urea: metal compound (b): h₂The weight ratio of O is 1: 0.4: 1: feeding at a ratio of 40; in the step (2), the obtained aqueous dispersion is placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 12 hours at the temperature of 150 ℃ under the autogenous pressure.

Preparation example 38

A nanocarbon material containing metal atoms was produced in the same manner as in production example 37, 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 70 ℃ under autogenous pressure for 12 hours.

Preparation example 39

A nanocarbon material containing a metal atom was produced in the same manner as in production example 37, except that rhodium acetylacetonate was replaced with an equimolar amount of ferrous acetate.

Preparation example 40

A nanocarbon material containing a metal atom was produced in the same manner as in production example 37, except that rhodium acetylacetonate was replaced with an equimolar amount of palladium acetate.

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 CO₂Adding 15g of tetraethyl titanate and 800g of 25 wt% tetrapropyl ammonium hydroxide aqueous solution into an atmosphere reactor, stirring for 1 hour, raising the temperature to 80-90 ℃, continuing stirring for 5 hours, adding deionized water into the reaction liquid until the total volume of the reaction liquid is 1.5L, transferring the reaction liquid into a high-pressure reaction kettle with a stirring device, and self-generating pressure at 175 DEG CAnd (3) carrying out hydrothermal crystallization under force for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, and roasting the filtered solid in an 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 with stirring to give a white, colloidal suspension, which was then cooled to 5 ℃, then 1.8L% by mass aqueous hydrogen peroxide solution at 30% was added thereto, which had been cooled to 5 ℃ beforehand, and was kept at 5 ℃ for 2 hours with intermittent stirring to give an orange clear solution, then 2.4L% by mass aqueous tetrapropylammonium hydroxide solution at 25% by mass, which had been cooled to 5 ℃ beforehand, was 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 elementThe amount was 0.04 wt% and the content of tetrapropylammonium hydroxide was 1.6 wt%. 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 CO₂455g of tetraethyl silicate is placed in a heat-resistant glass container, 15g of aluminum isopropoxide is added with stirring, 800g of a 25% tetrapropylammonium hydroxide aqueous solution is added, the mixture is mixed for 4 hours, the mixture is heated and stirred at 80-90 ℃ for 5 hours, ethanol is completely expelled, then water is added to 1.5L, the obtained mixture is transferred to a high-pressure reaction kettle with a stirring device, hydrothermal crystallization is carried out at 175 ℃ under autogenous pressure for 10 days, the obtained reaction mixture is filtered, and crystallization mother liquor is collected.

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 38

The nanocarbon materials were molded by the following methods, respectively, under the conditions given in table 4.

The nanocarbon material was mixed with a binder source at ambient temperature (25 ℃) respectively, the resulting mixture was fed into a bar mold and dried and optionally calcined to obtain nanocarbon material moldings (a portion of the moldings was randomly selected and ground to obtain a sample bar of 3-5mm in length for measuring crushing strength and porosity, the results are listed in table 4), and the remaining moldings were crushed and sieved to obtain granular moldings, the average particle size (particle size for short) of which is listed in table 4.

TABLE 4

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 39 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 39 is that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.

Example 78

The difference from example 39 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 39 for the same time as the hydrothermal treatment in example 39, and the mixture obtained by the reflux reaction was fed into a mold.

Example 79

The difference from example 42 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 80

The difference from example 42 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 42 for the same time as the hydrothermal treatment in example 42, and the mixture obtained by the reflux reaction was fed into a mold.

TABLE 5

¹: the amount of the nanocarbon material is 10g²: tetramethyl ammonium hydroxide³: the amount is calculated by oxide

⁴: 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 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 1.98% by volume, n-butane and oxygen molar ratio of 0.5: 1, and the balance nitrogen as a carrier gas) was charged at 0MPa (gauge pressure) and 430 ℃ for 4000 hours^-1The reaction was carried out while feeding the weight hourly space velocity of (a) into the reactor, the composition of the reaction mixture output from the reactor was continuously monitored, and the n-butane conversion and the total olefin selectivity were calculated, and the results of the reaction for 3 hours and 24 hours are shown in Table 6.

Testing of comparative examples 1-4

The catalytic performance of the multi-walled carbon nanotubes A, B, C and D were tested in turn using the same method as in test examples 1-80.

TABLE 6

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

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 being contained in an amount of 6 to 94% by weight and the binder being contained in an amount of 6 to 94% by weight based on the total amount of the molded body, the nanocarbon material containing at least one metal element selected from the group consisting of transition metal elements, group IA metal elements, group IIA metal elements, N elements and O elements, the N element being contained in an amount of 0.2 to 10% by weight, the O element being contained in an amount of 1 to 15% by weight and the metal element being contained in an amount of 0.1 to 10% by weight based on the total amount of the nanocarbon material and calculated as elements;

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 I_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^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 I_O ^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 I_O ^e，I_O ^c/I_O ^eIn the range of 1-2, the total amount of N element in the nano carbon material is I determined by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tIn the range of 0.7 to 1, the amount of C element determined by a peak in the range of 288.6 to 288.8eV in an X-ray photoelectron spectrum is I_C ^cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is I_C ^e，I_C ^c/I_C ^eIn the range of 0.7 to 1;

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 I_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^tIn the range of 0.02 to 0.3, the amount of O element in the nanocarbon material, which is determined by a peak in the range of 531.0 to 532.5eV in an X-ray photoelectron spectrum, is I_O ^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 I_O ^e，I_O ^c/I_O ^eIn the range of 0.5-0.99, the total amount of N element in the nano carbon material is I determined by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tIn the range of 0.5 to 1, the amount of C element determined by a peak in the range of 288.6 to 288.8eV in an X-ray photoelectron spectrum is I_C ^cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is I_C ^e，I_C ^c/I_C ^eIn the range of 0.4-1.5;

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 the aqueous dispersion solution contains at least one nitrogen-containing compound and at least one metal compound, and the nitrogen-containing compound is selected from NH₃Hydrazine and urea, wherein the metal compound is selected from alkali metal compounds and transition metal compounds, the metal element in the alkali metal compounds is selected from IA group metal elements and IIA group metal elements, and the temperature of the aqueous dispersion is 80-300 ℃ in the reaction processIn the range of DEG C;

the preparation method of the nano carbon material forming body comprises the steps of mixing a nano carbon material with a binder source, forming the obtained mixture to obtain a forming body, drying and optionally roasting the forming body, wherein the binder source is selected from a heat-resistant inorganic oxide and/or a precursor of the heat-resistant inorganic oxide, at least part of the binder source is from a molecular sieve preparation liquid, and the molecular sieve preparation liquid is a mixed liquid of one or more than two of a crystallization mother liquid and/or a re-drainage liquid of a titanium-silicon molecular sieve and a crystallization mother liquid and/or a re-drainage liquid of a silicon-aluminum molecular sieve;

wherein before the mixture is formed, the method further comprises the step of carrying out hydrothermal treatment on the mixture, wherein the hydrothermal treatment is carried out at the temperature of 100-200 ℃, and the duration of the hydrothermal treatment is 0.5-24 hours.

2. The molded body according to claim 1, wherein the content of N element is 0.5 to 6% by weight, the content of O element is 1.2 to 9% by weight, and the content of the metal element is 1 to 8% by weight, based on the total amount of the nanocarbon material and calculated as elements.

3. The molded body according to claim 2, wherein the content of N element is 1 to 4% by weight, the content of O element is 2 to 8% by weight, and the content of metal element is 2 to 4% by weight, based on the total amount of the nanocarbon material and calculated as element.

4. 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 spectroscopy_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^tIn the range of 0.05-0.25;

in the nano carbon material, the energy spectrum of X-ray photoelectron is 531.0-532.5eVThe amount of the peak-determined O element is I_O ^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 I_O ^e，I_O ^c/I_O ^eIn the range of 1.2-1.6;

in the nano carbon material, the total amount of N elements in the nano carbon material is determined as I by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tIn the range of 0.8-1.

5. Shaped body according to claim 4, wherein I_O ^m/I_O ^tIn the range of 0.06-0.2, I_N ^c/I_N ^tIn the range of 0.9-0.96.

6. Shaped body according to claim 5, wherein I_O ^m/I_O ^tIn the range of 0.09-0.18.

7. The molded body according to any one of claims 1 and 4 to 6, wherein the metal element is one or two or more selected from sodium, potassium, magnesium, calcium and barium.

8. The shaped body according to any one of claims 4 to 6, wherein the content of O element is 1 to 10% by weight, the content of N element is 0.2 to 5% by weight, the content of metal element is 0.1 to 10% by weight, and the content of C element is 75 to 98.7% by weight, based on the total amount of the nanocarbon material and calculated as elements.

9. The molded body according to claim 8, wherein the content of O element is 1.2 to 8% by weight, the content of N element is 0.5 to 4.5% by weight, the content of metal element is 0.5 to 8% by weight, and the content of C element is 79.5 to 97.8% by weight, based on the total amount of the nanocarbon material and calculated as elements.

10. The molded body according to claim 9, wherein the content of the element O is 1.3 to 7.5% by weight, the content of the element N is 0.8 to 4% by weight, the content of the element metal is 1 to 5% by weight, and the content of the element C is 83.5 to 96.9% by weight, based on the total amount of the nanocarbon material and calculated as elements.

11. The molded body according to claim 10, wherein the content of the O element is 2 to 6% by weight, the content of the N element is 1 to 3.5% by weight, the total amount of the metal elements is 2.5 to 4% by weight, and the content of the C element is 86.5 to 94.5% by weight, based on the total amount of the nanocarbon material and calculated as elements.

12. Shaped body according to claim 1, wherein the metallic element is selected from transition metallic elements and the nanocarbon material has a total content of oxygen, determined by X-ray photoelectron spectroscopy, of I_O ^tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is I_O ^m，I_O ^m/I_O ^tIn the range of 0.05-0.25;

determining the total amount of N element in the nano carbon material as I by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 398.5-400.1eV in the X-ray photoelectron spectrum is I_N ^c，I_N ^c/I_N ^tIn the range of 0.7-1.

13. The shaped body according to claim 12, wherein I_O ^m/I_O ^tIn the range of 0.06-0.2, I_N ^c/I_N ^tIn the range of 0.85-0.95.

14. Shaped body according to any one of claims 1 and 12 to 13, wherein the metallic element is selected from group VIII metals.

15. Shaped body according to claim 14, wherein the metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.

16. Shaped body according to any one of claims 12 to 13, wherein the nanocarbon material has an amount of C element I, determined by a peak in the range 288.6-288.8eV in the X-ray photoelectron spectrum_C ^cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is I_C ^e，I_C ^c/I_C ^eIn the range of 0.6-1.2.

17. The shaped body according to any one of claims 12 to 13, wherein the content of the element O is 1 to 10 wt%, the content of the element N is 0.2 to 5 wt%, the content of the element metal is 0.1 to 10 wt%, and the content of the element C is 75 to 98.7 wt%, based on the total amount of the nanocarbon material and calculated as elements.

18. The molded body according to claim 17, wherein the content of the O element is 1.2 to 8% by weight, the content of the N element is 0.5 to 4.5% by weight, the content of the metal element is 0.5 to 8% by weight, and the content of the C element is 79.5 to 97.8% by weight, based on the total amount of the nanocarbon material and calculated as elements.

19. The molded body according to claim 18, wherein the content of the element O is 1.3 to 7.5% by weight, the content of the element N is 0.8 to 4% by weight, the content of the element metal is 1 to 5% by weight, and the content of the element C is 83.5 to 96.9% by weight, based on the total amount of the nanocarbon material and calculated as elements.

20. The molded body according to claim 19, wherein the content of the element O is 2 to 6% by weight, the content of the element N is 1 to 3.5% by weight, the total amount of the metal elements is 2.5 to 4% by weight, and the content of the element C is 86.5 to 94.5% by weight, based on the total amount of the nanocarbon material and calculated as elements.

21. The shaped body according to any one of claims 1 to 6 and 12 to 13, wherein the total amount of N elements in the nanocarbon material is I as determined by X-ray photoelectron spectroscopy_N ^tThe amount of N element determined from a peak in the range of 400.6 to 401.5eV in the X-ray photoelectron spectrum is I_N ^g，I_N ^g/I_N ^tIs not higher than 0.35.

22. The shaped body of claim 21, wherein I_N ^g/I_N ^tIn the range of 0.05-0.25.

23. The shaped body of claim 22, wherein I_N ^g/I_N ^tIn the range of 0.05-0.12.

24. The molded body according to claim 1, wherein when the metal element is selected from the group consisting of group IA metal elements and group IIA metal elements, the content of C element determined by a peak in the range of 284.7-284.9eV in X-ray photoelectron spectroscopy is 60-98% by weight, and the total content of C element determined by a peak in the range of 286.0-288.8eV in X-ray photoelectron spectroscopy is 2-40% by weight, based on the total amount of C element determined by X-ray photoelectron spectroscopy in the nanocarbon material;

when the metal element is selected from transition metal elements, the content of the C element determined by a peak in the range of 284.7-284.9eV in the X-ray photoelectron spectrum is 60-95 wt%, and the total content of the C element determined by a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum is 5-40 wt%, based on the total amount of the C element determined by the X-ray photoelectron spectrum in the nanocarbon material.

25. The shaped body according to claim 24, wherein when the metal element is selected from the group consisting of group IA metal elements and group IIA metal elements, the content of C element determined by a peak in the range of 284.7-284.9eV in X-ray photoelectron spectroscopy is 80-92% by weight, and the total content of C element determined by a peak in the range of 286.0-288.8eV in X-ray photoelectron spectroscopy is 8-20% by weight, based on the total amount of C element determined by X-ray photoelectron spectroscopy in the nanocarbon material;

when the metal element is selected from transition metal elements, the content of the C element determined by a peak in the range of 284.7-284.9eV in the X-ray photoelectron spectrum is 70-92% by weight, and the total content of the C element determined by a peak in the range of 286.0-288.8eV in the X-ray photoelectron spectrum is 8-30% by weight, based on the total amount of the C element determined by the X-ray photoelectron spectrum in the nanocarbon material.

26. Shaped body according to any one of claims 1-6 and 12-13, wherein the nanocarbon material is carbon nanotubes.

27. The shaped body according to claim 26, wherein the nanocarbon material is a multiwall carbon nanotube.

28. The shaped body according to claim 27, wherein the multi-walled carbon nanotubes have a specific surface area of 50 to 500m²/g。

29. The shaped body according to claim 28, wherein the multi-walled carbon nanotubes have a specific surface area of 90-300m²/g。

30. The shaped body as claimed in claim 29, wherein the multi-walled carbon nanotubes have a specific surface area of 120-180m²/g。

31. The shaped body as claimed in claim 27, wherein the total weight loss of the multiwalled 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.

32. The shaped body of claim 31, wherein w is₅₀₀/w₈₀₀In the range of 0.02-0.4.

33. The shaped body of claim 32, wherein w is₅₀₀/w₈₀₀In the range of 0.05-0.15.

34. The molded body according to claim 1, 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: nitrogen-containing compounds: the weight ratio of the metal compound is 1: 0.01-20: 0.01-20.

35. The molded body according to claim 34, wherein in the method for producing a nanocarbon material, the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the metal compound is 1: 0.05-1: in the range of 0.5-5.

36. The shaped body according to claim 34 or 35, wherein in the method for producing a nanocarbon material, the raw nanocarbon material: h₂The weight ratio of O is 1: 2-500.

37. The molded body according to claim 36, wherein in the method for producing a nanocarbon material, the raw nanocarbon material: h₂The weight ratio of O is 1: 50-160.

38. The molded body according to claim 1, wherein in the method for producing a nanocarbon material, the metal compound is selected from the group consisting of a transition metal compound, a raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the metal compound is 1: 0.01-10: in the range of 0.01-10.

39. The molded body according to claim 38, wherein in the method for producing a nanocarbon material, the raw nanocarbon material: nitrogen-containing compounds: the weight ratio of the metal compound is 1: 0.02-0.5: in the range of 0.5-5.

40. The molded body according to claim 38 or 39, wherein in the method for producing a nanocarbon material, the ratio of the raw nanocarbon material: h₂The weight ratio of O is 1: 2-500.

41. The molded body according to claim 40, wherein in the method for producing a nanocarbon material, the ratio of the raw nanocarbon material: h₂The weight ratio of O is 1: 40-200.

42. The shaped body according to any one of claims 1, 34 and 35, wherein in the method for producing a nanocarbon material, the basic metal compound is selected from a hydroxide containing the metal element and a basic salt containing the metal element.

43. The molded body according to claim 42, wherein in the method for producing a nanocarbon material, the basic metal compound is selected from the group consisting of a hydroxide containing the metal element, a carbonate containing the metal element, and a bicarbonate containing the metal element.

44. The molded body according to claim 43, wherein in the method for producing a nanocarbon material, 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.

45. Shaped body according to any one of claims 1, 38 and 39, wherein in the method for the production of a nanocarbon material the transition metal compound is selected from the group consisting of transition metal acetates, transition metal oxalates, transition metal hydroxycarbonates, and transition metal complexes.

46. The shaped body according to claim 45, wherein in the process for producing the nanocarbon material, the transition metal element is selected from group VIII metal elements.

47. The shaped body according to claim 46, wherein in the method for producing a nanocarbon material, the transition metal element is selected from the group consisting of iron, ruthenium, cobalt, rhodium, nickel, palladium, and platinum.

48. The molded body as claimed in claim 1, wherein in the method for preparing the nanocarbon, the temperature of the aqueous dispersion is maintained within the range of 120-240 ℃ during the reaction.

49. Shaped body according to claim 1 or 48, wherein in the method for the production of nanocarbon materials the duration of the reaction is in the range of 0.5-144 hours.

50. The shaped body according to claim 49, wherein in the method for producing a nanocarbon material, the duration of the reaction is in the range of 10-72 hours.

51. The shaped body according to any one of claims 1, 34 to 35, 38, 39 and 48, wherein in the method for producing a nanocarbon material, the content of N element is not more than 0.2 wt%, the content of O element is not more than 1.5 wt%, and the total amount of metal elements is 2.5 wt% or less in the raw nanocarbon material.

52. The molded body according to claim 51, wherein in the method for producing a nanocarbon material, the raw nanocarbon material contains N in an amount of not more than 0.02 wt%, O in an amount of not more than 0.3 wt%, and the total amount of metal elements is not more than 0.5 wt%.

53. The shaped body according to any one of claims 1, 34 to 35, 38, 39 and 48, wherein in the method for producing a nanocarbon material, the raw nanocarbon material is carbon nanotubes.

54. The shaped body according to claim 53, wherein in the method for producing a nanocarbon material, the starting nanocarbon material is a multiwall carbon nanotube.

55. The molded body according to claim 54, wherein in the method for producing a nanocarbon material, the multi-walled carbon nanotubes have a specific surface area of 50 to 500m²/g。

56. The molded body as claimed in claim 55, wherein in the preparation method of the nano-carbon material, the specific surface area of the multi-walled carbon nanotube is 120-190m²/g。

57. The molded body as claimed in claim 54, wherein in the preparation method of the nano-carbon material, the total weight loss rate of the multi-walled carbon nanotube 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.

58. The shaped body according to claim 57, wherein in the process for the preparation of the nanocarbon material, w₅₀₀/w₈₀₀In the range of 0.02-0.4.

59. The shaped body according to any one of claims 1, 34 to 35, 38, 39 and 48, wherein the method for producing a nanocarbon material further comprises separating solid matter from the mixture obtained by the reaction, and drying the separated solid matter.

60. The shaped body according to claim 59, wherein in the process for the preparation of the 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.

61. The shaped body according to claim 60, wherein in the method for producing a nanocarbon material, the drying is carried out at a temperature of 80-180 ℃ and the duration of the drying is 4-24 hours.

62. The shaped body according to claim 61, wherein in the method for producing a nanocarbon material, the duration of drying is 6 to 12 hours.

63. The shaped body according to any one of claims 1 to 6, 12 to 13, 34 to 35, 38, 39 and 48, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the heat-resistant inorganic oxide is contained in an amount of 6 to 94% by weight, based on the total amount of the shaped body.

64. The shaped body according to claim 63, 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.

65. The shaped body according to claim 64, wherein the nanocarbon material is present in an amount of 40 to 90 wt% and the heat-resistant inorganic oxide is present in an amount of 10 to 60 wt%, based on the total amount of the shaped body.

66. The shaped body according to claim 65, 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.

67. The molded body according to any one of claims 1 to 6, 12 to 13, 34 to 35, 38, 39 and 48, wherein the heat-resistant inorganic oxide is one or two or more of alumina, silica and titania.

68. The shaped body according to claim 67, wherein the heat-resistant inorganic oxide comprises silicon oxide.

69. The shaped body according to claim 68, 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.

70. The shaped body according to claim 69, 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.

71. The shaped body according to claim 70, 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.

72. A method for producing a nanocarbon material molded body, which comprises mixing a nanocarbon material with a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, molding the obtained mixture to obtain a molded body, drying and optionally firing the molded body, the nanocarbon material being a nanocarbon material which has not been surface-treated and a nanocarbon material which has been surface-treated, or the nanocarbon material being a nanocarbon material which has been surface-treated, the nanocarbon material having been surface-treated containing 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, the nanocarbon material being the nanocarbon material according to any one of claims 1 to 62, at least part of the binder source is from a molecular sieve preparation liquid, and the molecular sieve preparation liquid is a mixed liquid of one or more than two of a crystallization mother liquid and/or a heavy discharge liquid of a titanium-silicon molecular sieve and a crystallization mother liquid and/or a heavy discharge liquid of a silicon-aluminum molecular sieve;

wherein before the mixture is formed, the method further comprises the step of carrying out hydrothermal treatment on the mixture, wherein the hydrothermal treatment is carried out at the temperature of 100-180 ℃, and the duration of the hydrothermal treatment is 0.5-24 hours.

73. The method of claim 72, wherein the mixture further comprises at least one base.

74. A process according to claim 73, wherein the base is selected from organic bases.

75. The method of claim 74, wherein said organic base is selected from the group consisting of quaternary ammonium bases, aliphatic amines, and aliphatic alcohol amines.

76. The method of claim 75, wherein the organic base is selected from templating agents for synthesizing titanium silicalite molecular sieves.

77. The method of claim 76, wherein the quaternary ammonium hydroxide is of formula II,

in the formula II, R₅、R₆、R₇And R₈Are the same or different and are each C₁-C₄Alkyl group of (1).

78. The method of any of claims 73-77, wherein the molar ratio of the base to the binder source is 0.1-10: 1, the binder source is calculated by oxide.

79. The method of claim 78, wherein the molar ratio of the base to the binder source is from 0.15-8: 1, the binder source is calculated by oxide.

80. The method of claim 79, wherein the molar ratio of the base to the binder source is from 0.4-7: 1, the binder source is calculated by oxide.

81. The method as claimed in claim 72, wherein the hydrothermal treatment is carried out at a temperature of 120-180 ℃ and the duration of the hydrothermal treatment is 6-12 hours.

82. The method of any of claims 72-77, wherein at least a portion of the optional organic base and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor and/or a re-drainage of a titanium silicalite molecular sieve and a crystallization mother liquor and/or a re-drainage of a silicoaluminophosphate molecular sieve.

83. 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 article, and 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 nanocarbon material being a nanocarbon material which has not been surface-treated and a nanocarbon material which has been surface-treated, or the nanocarbon material being a nanocarbon material which has been surface-treated and contains 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, the surface-treated nanocarbon material being the nanocarbon material according to any one of claims 1 to 62, at least part of the binder source is from a molecular sieve preparation liquid, and the molecular sieve preparation liquid is a mixed liquid of one or more than two of a crystallization mother liquid and/or a heavy discharge liquid of a titanium-silicon molecular sieve and a crystallization mother liquid and/or a heavy discharge liquid of a silicon-aluminum molecular sieve;

wherein the hydrothermal treatment is carried out at a temperature of 100-200 ℃, and the duration of the hydrothermal treatment is 6-24 hours.

84. The method of claim 83, wherein the aqueous dispersion further comprises at least one treating agent, the treating agent being at least one base and/or at least one metal compound, the base being selected from ammonia and organic bases.

85. The method of claim 84, wherein said organic base is selected from the group consisting of hydrazine, urea, amines, alcohol amines, and quaternary ammonium bases.

86. The method of claim 84, wherein said metal compound is a transition metal salt and/or a basic metal compound, wherein the metal element in said basic metal compound is selected from the group consisting of group IA metal elements and group IIA metal elements.

87. The method of claim 84, wherein the treatment agent is a quaternary ammonium base.

88. The method of claim 87, wherein the treatment agent is selected from templating agents for synthesizing titanium silicalite molecular sieves.

89. The method of claim 88, wherein the treating agent is selected from a quaternary ammonium base represented by formula II,

90. The method of claim 84, wherein the treatment agent is a base and a metal compound, the base being NH₃One or more of hydrazine and urea, and the molar ratio of the metal compound to the base is 0.01 to 0.5: 1.

91. the process of claim 90, wherein the molar ratio of the metal compound to the base is from 0.05-0.3: 1.

92. the method of claim 84, wherein the treating agent is a base and a basic metal compound, the base being NH₃One or more of hydrazine and urea.

93. A process as set forth in claim 92 wherein said base is ammonia and the metal element in said metal compound is selected from the group consisting of group IIA metal elements.

94. The method of claim 93, wherein the metal element in the metal compound is selected from the group consisting of magnesium, calcium, and barium.

95. A process as set forth in claim 92 wherein said base is hydrazine and the metal element of said metal compound is selected from group IIA metal elements.

96. The method of claim 95, wherein the metallic element in the metal compound is selected from the group consisting of magnesium, calcium, and barium.

97. The method of claim 86, 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.

98. The method of claim 97, 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.

99. The method of claim 98, 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.

100. The method of claim 86, wherein the transition metal salt is selected from the group consisting of a transition metal acetate, a transition metal oxalate, a transition metal hydroxycarbonate, and a transition metal complex.

101. The method of claim 100, wherein the transition metal element is selected from group VIII metal elements.

102. The method of claim 100, wherein the transition metal element is selected from the group consisting of iron, ruthenium, cobalt, rhodium, nickel, palladium, and platinum.

103. The method of any of claims 83-102, wherein the molar ratio of the treating agent to the binder source is 0.1-10: 1, the binder source is calculated by oxide.

104. The method of claim 103, wherein the molar ratio of the treating agent to the binder source is from 0.2 to 8: 1, the binder source is calculated by oxide.

105. The method of any of claims 83-102, wherein at least a portion of the optional organic base and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor and/or a re-drainage of a titanium silicalite molecular sieve and a crystallization mother liquor and/or a re-drainage of a silicoaluminophosphate molecular sieve.

106. The method of any of claims 72-77 and 83-102, wherein the refractory inorganic oxide is one or more of alumina, silica, and titania.

107. The method of claim 106, wherein the refractory inorganic oxide comprises silicon oxide.

108. The method as claimed in claim 107, wherein the silicon oxide is present in an amount of 10-100% by weight, based on the total amount of the refractory inorganic oxide.

109. The method as claimed in claim 108, wherein the silica is present in an amount of 20-99 wt% based on the total amount of the refractory inorganic oxide.

110. The method as claimed in claim 109, wherein the silica is present in an amount of 50-99 wt.% based on the total amount of the refractory inorganic oxide.

111. The method of any of claims 84-102, 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%.

112. The method as recited in claim 111, wherein the binder source is used in an amount such that the nanocarbon material is contained in an amount of 75-95 wt% and the refractory inorganic oxide is contained in an amount of 5-25 wt% in the finally prepared molded body.

113. The method as claimed in claim 112, 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.

114. The method of any of claims 72-77 and 83-102, 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.

115. The method as recited in claim 114, wherein the drying is performed 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.

116. The method of claim 115, wherein the drying is for a duration of 5-15 hours.

117. A nanocarbon material shaped body prepared by the method of any one of claims 72-116.

118. Use of a nanocarbon material shaped body as claimed in any one of claims 1 to 71 and 117 as a catalyst for dehydrogenation reactions of hydrocarbons.

119. The use of claim 118, wherein the hydrocarbon is an alkane.

120. The use of claim 119, wherein the hydrocarbon is C₂-C₁₂Of (a) an alkane.

121. The use of claim 120, wherein the hydrocarbon is n-butane.

122. A hydrocarbon dehydrogenation reaction process comprising contacting a hydrocarbon with the nanocarbon material shaped body of any one of claims 1-71 and 117 under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.

123. The method of claim 122, wherein the hydrocarbon is an alkane.

124. The method of claim 123, wherein the hydrocarbon is C₂-C₁₂Of (a) an alkane.

125. The method of claim 124, wherein the hydrocarbon is n-butane.