CN107661762B - Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method - Google Patents

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

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CN107661762B
CN107661762B CN201610602560.3A CN201610602560A CN107661762B CN 107661762 B CN107661762 B CN 107661762B CN 201610602560 A CN201610602560 A CN 201610602560A CN 107661762 B CN107661762 B CN 107661762B
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nanocarbon material
weight
shaped body
range
body according
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CN107661762A (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

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

Abstract

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 nano carbon material contains a C element, an O element and at least one metal element, and the metal element is selected from a group IA metal element and a group IIA metal element. The nano carbon material formed body of the invention uses the heat-resistant inorganic oxide as a binder to bond and form the nano carbon material, has high crushing strength and high porosity, and is suitable for being used as a catalyst, in particular a catalyst for dehydrogenation reaction of hydrocarbon.

Description

Nanocarbon material forming body, preparation method and application thereof, forming method of nanocarbon material and hydrocarbon dehydrogenation reaction method
Technical Field
The invention relates to the technical field of nano carbon material forming, in particular to a nano carbon material forming body and a preparation method thereof, and also relates to application of the nano carbon material forming body as a catalyst for hydrocarbon dehydrogenation reaction.
Background
Dehydrogenation of hydrocarbons is an important type of reaction, for example, most lower alkenes are obtained by dehydrogenation of lower alkanes. Dehydrogenation reactions can be classified into two types, direct dehydrogenation reactions (i.e., oxygen does not participate) and oxidative dehydrogenation reactions (i.e., oxygen does participate), depending on whether oxygen participates.
Various types of nanocarbon materials have been demonstrated to have catalytic effects on both direct dehydrogenation reactions and oxidative dehydrogenation reactions of hydrocarbon materials.
In the hydrocarbon oxidative dehydrogenation process using the nano-carbon material as the catalyst, for example, a fixed bed reaction process is adopted, the nano-carbon material needs to be molded, and the molded body needs to meet the following two requirements: (1) the catalyst has certain strength to avoid the molded body from being crushed in the reaction process, and on one hand, the pressure drop of a catalyst bed layer is increased due to fine particles or powder formed by crushing, so that the production and operation cost is increased, and the production danger is increased; on the other hand, the fine particles or powder formed by crushing can cause catalyst loss and product separation complication if the fine particles or powder is carried out by reaction products; (2) the nano carbon material has certain porosity to improve the specific surface area of the formed body, so that the nano carbon material in the formed body can be more fully contacted with reaction materials.
As an example of shaping nanocarbon materials, researchers have attempted to load Carbon Nanotubes (CNTs) on the surface of SiC foams to form CNT/SiC foams. Although CNTs anchor well to the surface of the SiC foam, the loading of CNTs is low, typically reaching only 0.5-4 wt%.
Therefore, how to form the nanocarbon material into a formed body with high strength in a wide nanocarbon material content range still remains a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a nano carbon material forming body and a preparation method thereof, wherein the nano carbon material forming body not only has higher strength, but also can adjust the content of a nano carbon material in a wider range.
According to one aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material containing a C element, an O element, and at least one metal element selected from group IA metal elements and group IIA metal elements, and a heat-resistant inorganic oxide for bonding molding the nanocarbon material.
According to a second aspect of the present invention, there is provided a nanocarbon material molded body containing a nanocarbon material and a heat-resistant inorganic oxide for binding and molding the nanocarbon material;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material and at least one basic metal compound are dispersed in a closed container, wherein a metal element in the basic metal compound is selected from group IA metal elements and group IIA metal elements, and the temperature of the aqueous dispersion is kept within the range of 100-300 ℃ during the reaction.
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material molded body, 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 surface-treated nanocarbon material contains a C element, an O element and at least one metal element selected from 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 an unpretreated nanocarbon material and/or a treated nanocarbon material, the treated nanocarbon material containing a C element, an O element and at least one metal element selected from group IA metal elements and group IIA metal elements, 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 near those ranges or values, and for numerical ranges, between the endpoints of each range and the individual endpoints, and between the individual endpoints, may be combined with each other to provide one or more new numerical ranges, and such numerical ranges 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 a C element, an O element, and at least one metal element (hereinafter, sometimes also referred to as a nanocarbon material containing a metal atom).
According to the molded body of the first aspect of the present invention, in the nanocarbon material, the metal element is selected from group IA metal elements and group IIA metal elements, and specific examples thereof may include, but are not limited to, one or two or more of lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium. Preferably, the metal element is one or more of sodium, potassium, magnesium, calcium and barium, and when the nanocarbon material-containing formed body is used as a catalyst for dehydrogenation reaction of hydrocarbon, better catalytic performance can be obtained. The metal element is more preferably one or two or more selected from magnesium, barium and calcium from the viewpoint of further improving the catalytic performance when the nanocarbon material-containing molded body is used as a catalyst for a hydrocarbon dehydrogenation reaction.
The content of C element, O element and metal element in the nano carbon material can be selected according to the source of the nano carbon material, and can also be selected according to the specific application occasion of the nano carbon material forming body. Generally, the content of the element O may be 1 to 10% by weight, preferably 2 to 8% by weight, more preferably 3 to 7% by weight, and further preferably 5 to 6% by weight, in terms of the element, based on the total amount of the nanocarbon material; the content of the metal element may be 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.5 to 5% by weight, and further preferably 1 to 4% by weight; the content of the element C may be 80 to 98.9% by weight, preferably 84 to 97.8% by weight, more preferably 88 to 96.5% by weight, and still more preferably 90 to 94% 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 the X-ray photoelectron spectroscopy is carried out at Thermo Scientific company equipped with Thermo Avantage V5.926The test is carried out on an ESCA L ab250 type X-ray photoelectron spectrometer of 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 analysis and 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 nanocarbon material has a total content of oxygen element I as determined by X-ray photoelectron spectroscopyO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tGenerally, it is in the range of 0.01 to 0.3, preferably 0.02 to 0.25, more preferably 0.05 to 0.23, and still more preferably 0.09 to 0.18. According to the molded article of the present invention, the nanocarbon material has an O element content I determined by a peak in an X-ray photoelectron spectrum in a range of 531.0 to 533.5eVO nm，IO nm/IO tGenerally, it is in the range of 0.7 to 0.99, preferably in the range of 0.75 to 0.98, more preferably in the range of 0.77 to 0.95, and still more 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 AO 1The peaks in the O1s spectrum were divided into two groups, and the area of the peak (corresponding to the oxygen species bound to the metal atom) in the range of 529.5-530.8eV was designated AO 2The area of the peak in the range of 531.0 to 533.5eV (corresponding to the oxygen species not bonded to the metal atom) is denoted as AO 3Wherein, IO m/IO t＝AO 2/AO 1，IO nm/IO t＝AO 3/AO 1。
According to the molded article of the first aspect of the present invention, the nanocarbon material is one obtained from 531.0 to 53 in X-ray photoelectron spectrumThe amount of O element (i.e., C ═ O) determined by the peak in the 2.5eV range is IO cThe amount of O element (i.e., C-O) determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eGenerally, it is in the range of 0.1 to 3, preferably 1 to 3, more preferably 1.2 to 2.5, still more preferably 1.4 to 2, and still more preferably 1.5 to 1.8.
In the present invention, the peaks in the X-ray photoelectron spectrum in the range of 531.0 to 533.5eV (corresponding to oxygen species not bonded to the metal atom) are further divided into two groups of peaks, i.e., a peak in the range of 531.0 to 532.5eV (corresponding to C ═ O species) and a peak in the range of 532.6 to 533.5eV (corresponding to C-O species), and the area of the peak in the range of 531.0 to 532.5eV is designated as AO 4The area of the peak in the range of 532.6 to 533.5eV is designated as AO 5，IO c/IO e＝AO 4/AO 5。
The molded body according to the first aspect of the present invention may have a content of C element determined from a peak in the range of 284.7-284.9eV in an X-ray photoelectron spectrum of 60-98 wt%, preferably 65-90 wt%, more preferably 75-85 wt%, based on the total amount of C element 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 2 to 40% by weight, preferably 10 to 35% by weight, more preferably 15 to 25% by weight.
In the present invention, the area A of the peak of C1s spectrum in the X-ray photoelectron spectrumC 1Determining the total amount of C element, dividing the peak of C1s in X-ray photoelectron spectrum into two groups, i.e. peak in 284.7-284.9eV (corresponding to graphite type carbon species) and peak in 286.0-288.8eV (corresponding to non-graphite type carbon species), and recording the area of peak in 284.7-284.9eV as AC 2The area of a peak in the range of 286.0-288.8eV is designated as AC 3Content of C element determined from peak in range of 284.7-284.9eV in X-ray photoelectron spectrum＝AC 2/AC 1Total content of C element determined from peak in range of 286.0-288.8eV in X-ray photoelectron spectrumC 3/AC 1。
According to the molded body of the first aspect of the present invention, in the nanocarbon material, the amount of C element determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eGenerally, it is in the range of 0.4 to 2.5, preferably in the range of 1 to 2.5, more preferably in the range of 1.2 to 2.2, still more preferably in the range of 1.5 to 2, and still more preferably in the range of 1.8 to 2.
In the present invention, peaks in the X-ray photoelectron spectrum in the range of 286.0-288.8eV (corresponding to non-graphitic carbon species) are further divided into two groups of peaks, i.e., peaks in the range of 286.0-286.2eV (corresponding to hydroxyl and ether-type carbon species) and peaks in the range of 288.6-288.8eV (corresponding to carboxyl, anhydride and ester-type carbon species), and the area of the peaks in the range of 286.0-286.2eV is designated as AC 4The area of a peak in the range of 288.6-288.8eV is designated as AC 5，IC c/IC e＝AC 5/AC 4。
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 286.0-288.8eV means all peaks having a binding energy in the range of 286.0-288.8eV corresponding to the peak top.
According to the molded body of the first aspect 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 shaped body of the first aspect of the present invention, the specific surface area of the multi-walled carbon nanotubes 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 increased further. The specific surface area of the multi-wall carbon nano-tube is more preferably 80-300m2(ii)/g, more preferably 100-2(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 molded body of the first aspect of the invention, the weight loss rate of the multi-walled carbon nanotube in the temperature interval 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 starting temperature is 25 ℃, and the heating rate is 10 ℃/min; the samples were dried at a temperature of 150 ℃ and 1 atm under a helium atmosphere for 3 hours before testing.
According to the molded body of the first aspect of the present invention, the content of the 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. In general, the total amount of non-metallic hetero atoms (such as sulfur atom and phosphorus atom) other than oxygen atom and nitrogen atom 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. The nanocarbon material may contain other metal atoms in addition to the metal elements selected from the group consisting of the above 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. The composition of the shaped bodies can be determined by X-ray fluorescence spectroscopy. In the examples disclosed in the present invention, the composition of the molded article calculated from the charged amount was substantially the same as the composition of the molded article measured by X-ray fluorescence spectrometry with an error of 1% or less.
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: an aqueous dispersion in which a raw material nanocarbon material and at least one basic metal compound are dispersed is reacted in a closed vessel.
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 dehydrogenation reaction of hydrocarbon. The metal element is more preferably selected from magnesium, barium and calcium from the viewpoint of further improving the catalytic performance of the produced nanocarbon material formed body as a catalyst for hydrocarbon dehydrogenation reaction.
The basic metal compound is preferably selected from the group consisting of a hydroxide containing the metal element and a basic salt containing the metal element. The basic metal compound is more preferably 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. 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 two or more of calcium hydroxide, barium carbonate, calcium hydrogen carbonate, barium hydroxide, and magnesium hydroxide, and more preferably one or two or more of calcium hydroxide, magnesium hydroxide, and barium hydroxide, from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body in the hydrocarbon dehydrogenation reaction.
The solid content of the aqueous dispersion is based on the fact that the raw material nano carbon material can be uniformly dispersed. Preferably, the raw material nanocarbon material: the weight ratio of the alkali metal compound is 1: 0.01-5. Raw material nano carbon material: the weight ratio of the basic metal compound is more preferably in the range of 1: in the range of 0.02 to 2, more preferably in the range of 1: in the range of 0.02 to 1, more preferably in the range of 1: in the range of 0.02 to 0.5, particularly preferably in the range of 1: 0.1-0.3.
Raw material nano carbon material: h2The weight ratio of O is preferably in the range of 1: in the range of 2 to 100, the nanocarbon material has better structural morphology retention during treatment when the amount of water is within the range, for example: when the raw material nanocarbon material is a carbon nanotube, it is hardly cut off in the process of treatment. Raw material nano carbon material: h2The weight ratio of O is more preferably in the range of 1: 3 to 80, more preferably 1: in the range of 5 to 60, more preferably in the range of 1: 8-40.
The temperature of the aqueous dispersion during the reaction may be in the range of 80-310 ℃. When the temperature of the aqueous dispersion is within the above range, the content of oxygen atoms and metal atoms in the raw material nanocarbon material can be effectively increased, and the structural morphology of the raw material nanocarbon material is not significantly affected. During the reaction, the temperature of the aqueous dispersion is more preferably within the range of 100-300 ℃, still more preferably within the range of 120-250 ℃, and still more preferably within the range of 120-220 ℃.
In general, the duration of the reaction may be in the range of 0.5 to 144 hours, preferably in the range of 2 to 72 hours, more preferably in the range of 4 to 24 hours.
The aqueous dispersion can be formed by various methods commonly 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 basic metal compound. In order to further improve the dispersion effect of the raw material nanocarbon material and shorten the dispersion time, the raw material nanocarbon material may be dispersed in an aqueous solution in which the alkali metal compound is dissolved, by using 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 20 to 100kHz, preferably 40 to 60 kHz; the duration of the ultrasonic oscillation may be 0.1 to 12 hours, preferably 0.2 to 6 hours, more preferably 0.5 to 1 hour. The basic metal compound may be provided in the form of a solution (preferably an aqueous solution) or may be provided in the form of a pure substance, and is not particularly limited.
According to the molded body of the second aspect of the present invention, the content of the oxygen element and the nitrogen element in the raw material nanocarbon material is not particularly limited and may be selected conventionally. Generally, the content of the oxygen element in the raw material nanocarbon material is not more than 1.5% by weight, preferably not more than 0.5% by weight, more preferably not more than 0.3% by weight; the content of nitrogen element is not more than 0.2% by weight, preferably not more than 0.1% by weight, more preferably not more than 0.05% by weight, and further preferably not more than 0.02% by weight. The total amount (in terms of elements) of the non-metallic hetero atoms (such as phosphorus atoms and sulfur atoms) other than oxygen atoms and nitrogen atoms in the raw material nanocarbon material may be a conventional amount. Generally, the total amount (in terms of elements) of the non-metallic hetero atoms other than oxygen and nitrogen in the raw material nanocarbon material is not more than 0.5% by weight, preferably not more than 0.2% by weight, more preferably not more than 0.1% by weight, and further preferably not more than 0.05% by weight. The raw nanocarbon material may contain some metal elements depending on the source, for example, metal atoms derived from the catalyst used in the preparation of the raw nanocarbon material. The content (in terms of element) of the metal atom in the raw nanocarbon material is generally 2.5 wt% or less, preferably 1.8 wt% or less, and more preferably 0.5 wt% or less.
According to the molded body of the second aspect of the present invention, the raw material nanocarbon material may be pretreated (e.g., washed) by a method commonly used in the art before use to remove some impurities on the surface of the raw material nanocarbon material; or may be used without pretreatment. In the preparation examples disclosed in the present invention, the raw material nanocarbon material was not pretreated before use.
According to the molded body of the second aspect of the present invention, the raw material nanocarbon material may be, but is not limited to, one or a combination of two or more of carbon nanotubes, graphene, nanodiamonds, thin-layer graphites, nanocarbon particles, nanocarbon fibers, and fullerenes. The carbon nanotube can be one or the combination of more than two of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. Preferably, the raw material nanocarbon material is a carbon nanotube, more preferably a multiwall carbon nanotube.
In a preferred embodiment of the molded body according to the second aspect of the present invention, the raw nanocarbon material is multi-walled carbon nanotubes, and the specific surface area of the multi-walled carbon nanotubes may be 50 to 500m2A/g, preferably from 80 to 300m2(ii)/g, more preferably 100-260m2(ii)/g, more preferably 120-190m2/g。
When the raw material nano carbon material is the multi-walled carbon nanotube, the weight loss rate of the multi-walled carbon nanotube in the temperature range of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800May be in the range of 0.01 to 0.5, preferably in the range of 0.02 to 0.4.
According to the molded article of the second aspect of the present invention, the reaction is carried out in a closed vessel. The reaction may be carried out under autogenous pressure (i.e., without additional application of pressure) or under pressurized conditions. Preferably, the reaction is carried out under autogenous pressure. The closed container can be a common reactor capable of realizing sealing and heating, such as a high-pressure reaction kettle.
The molded body according to the second aspect of the present invention may further comprise separating solid matter from the mixture obtained by the reaction and drying the separated solid matter to obtain a nanocarbon material. The solid matter can be separated from the mixture obtained by the reaction by a conventional solid-liquid separation method such as one or a combination of two or more of centrifugation, filtration and decantation. The drying conditions may be chosen conventionally, so as to be able to remove volatile substances from the separated solid material. In general, the drying may be carried out at a temperature of from 50 to 400 ℃, preferably from 80 to 180 ℃. The duration of the drying may be selected according to the temperature and manner of drying. Generally, the duration of the drying may be no more than 48 hours, preferably 4 to 24 hours, more preferably 6 to 12 hours. The drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure. From the viewpoint of further improving the efficiency of drying, the drying is preferably performed under reduced pressure. Spray drying or the like can also be employed without a step of separating solid substances from the mixture, in which case the drying can be carried out at a temperature of 120-400 ℃, preferably at a temperature of 150-350 ℃, more preferably at a temperature of 180-300 ℃, and the duration of the drying can be selected according to the degree of drying, such as not more than 0.5 hour, preferably not more than 0.2 hour, more preferably not more than 0.1 hour.
The molded article according to the second aspect of the present invention further contains a heat-resistant inorganic oxide for binding and molding the nanocarbon material. The kind and content of the refractory inorganic oxide are the same as those of the refractory inorganic oxide described in the first aspect of the present invention, and are not described in detail herein.
The nanocarbon material molded body according to the first and second aspects of the present invention may have various shapes such as a spherical shape and a strip shape as needed.
The nanocarbon material molded body according to the first and second aspects of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm. In the present invention, the radial crush strength was measured by a method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (first edition, 1990, ed., Yankee edition, and edited by Yankee corporation).
The nanocarbon material molded body according to the first and second aspects of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the invention may be 5% or more, even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, more preferably in the range of 12 to 25%. In the present invention, the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (see document "research on porosity of graphite porous material", "lubrication and sealing", "2010, 35 (10): 99-101) in percentage).
According to a third aspect of the present invention, there is provided a method for producing a nanocarbon material shaped body, comprising mixing a nanocarbon material with a binder source, shaping the obtained mixture to obtain a shaped body, drying and optionally firing the shaped body.
According to the method of the third aspect of the invention, the binder source is selected from the group consisting of refractory inorganic oxides and/or precursors of refractory inorganic oxides. The heat-resistant inorganic oxide is preferably one or more of alumina, silica and titania. In one example, the heat-resistant inorganic oxide is alumina, and the nanocarbon material molding according to this example can achieve a higher conversion rate of raw materials.
In a preferred embodiment, at least a portion of the refractory inorganic oxide is silica, and the nanocarbon material shaped body prepared according to this preferred embodiment can achieve a better balance between feedstock conversion and product selectivity when used as a catalyst for a hydrocarbon dehydrogenation reaction. In the preferred embodiment, the content of the silicon oxide may be 10 to 100% by weight, preferably 20 to 99% by weight, and more preferably 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxides, and the content of the heat-resistant inorganic oxides other than silicon oxide may be 0 to 90% by weight, preferably 1 to 80% by weight, and more preferably 1 to 50% by weight. In the preferred embodiment, specific examples of the heat-resistant inorganic oxide other than silicon oxide may include, but are not limited to, aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide other than silicon oxide is titanium oxide.
The refractory inorganic oxide may be provided in various forms as is common, for example, in the form of a sol (e.g., silica sol, titanium sol, aluminum sol). The precursor of the heat-resistant inorganic oxide may be selected according to the kind of the intended heat-resistant inorganic oxide.
For example, when the refractory inorganic oxide is alumina, the precursor of the refractory inorganic oxide may be a substance capable of being converted into alumina, such as a substance capable of forming alumina by hydrolytic condensation reaction and/or calcination, for example, organic aluminum salts and inorganic aluminum salts, specific examples of which may include, but are not limited to, hydrated alumina (such as pseudo-boehmite), aluminum hydroxide, aluminum sulfate, sodium metaaluminate, aluminum chloride, aluminum nitrate and C1-C10And one or more of organic aluminum salts (e.g., aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate) of (a).
For another example, when the heat-resistant inorganic oxide is silicon oxide, the precursor of the heat-resistant inorganic oxide may be a substance that can be converted into silicon oxide, such as a substance that can form silicon oxide by a hydrolytic condensation reaction and/or firing, and specific examples thereof may include, but are not limited to, organosilicon compounds that can undergo a hydrolytic condensation reaction. The organosilicon compound capable of undergoing a hydrolytic condensation reaction may be any of various conventional substances capable of forming silicon oxide by a hydrolytic condensation reaction. As an example, the organosilicon compound capable of undergoing hydrolytic condensation reaction may be one or more than two of the compounds represented by formula I:
Figure BDA0001061583690000091
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 can be one or more of ammonia, alkali (such as sodium hydroxide and potassium hydroxide) with alkali metal as cation, and alkali (such as magnesium hydroxide, calcium hydroxide and barium hydroxide) with alkaline earth metal as cation. The organic base can be one or more than two of hydrazine, urea, amine and quaternary ammonium base.
The quaternary ammonium base may specifically be a compound of formula II:
Figure BDA0001061583690000101
in the formula II, R5、R6、R7And R8Each may be C1-C20Alkyl (including C)1-C20Straight chain alkyl of (2) and C3-C20Branched alkyl of) or C6-C12Aryl group of (1). Said C is1-C20Specific examples of the alkyl group of (a) may include, but are not limited to: one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, and n-eicosyl. Said C is6-C12Specific examples of the aryl group of (a) may include, but are not limited to, phenyl, naphthyl, 4-methylbenzeneA group and a 4-ethylphenyl group. R5、R6、R7And R8Preferably each is C1-C10Alkyl (including C)1-C10Straight chain alkyl of (2) and C3-C10Branched alkyl groups of) more preferably each C1-C6Alkyl (including C)1-C6Straight chain alkyl of (2) and C3-C6Branched alkyl groups of (a).
The amine refers to a substance in which one, two or three hydrogens in an ammonia molecule are replaced with an organic group, which may be bonded to a nitrogen atom to form a cyclic structure. The organic group may be a substituted (e.g., hydroxyl-substituted) or unsubstituted aliphatic hydrocarbon group and/or a substituted (e.g., hydroxyl-substituted) or unsubstituted aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic chain hydrocarbon group, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic hydrocarbon group, and a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic hydrocarbon group. Specifically, the amine may be one or two or more of a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated aliphatic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted saturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted unsaturated alicyclic amine, a substituted (e.g., hydroxyl-substituted) or unsubstituted heterocyclic amine, and a substituted (e.g., hydroxyl-substituted) or unsubstituted arylamine.
The saturated aliphatic amine is preferably a compound represented by formula III, a compound represented by formula IV, or a compound represented by general formula R16(NH2)2One or more of the substances shown,
Figure BDA0001061583690000102
in the formula III, R9、R10And R11Each is H or C1-C6And R is alkyl of9、R10And R11Not H at the same time. Book (I)In the invention, C1-C6Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.
In the formula IV, R12、R13And R14Each is-R15OH or hydrogen, and R12、R13And R14At least one of which is-R15OH，R15Is 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.
General formula R16(NH2)2In, R16Can be C1-C6An alkylene group of (a). In the present invention, C1-C6Alkylene of (A) includes C1-C6Linear alkylene of (A) and (C)3-C6Specific examples thereof may include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, and n-hexylene.
The unsaturated aliphatic amine refers to an aliphatic chain amine having an unsaturated group in a molecular structure, and the unsaturated group is preferably an alkenyl group (i.e., -C ═ C —). The number of the unsaturated group and the amino group may be one or two or more, and is not particularly limited.
Specific examples of the organic base may include, but are not limited to, 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, isoamylamine, diisopentylamine, triisopentylamine, tert-pentylamine, hexylamine, octylamine, nonylamine, decylamine, undecylamine, dodecyldimethylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, monoethanolamine, triethanolamine, triisopropanolamine, diethanolamine, dipropanolamine, tripropylamine, dibutanolamine, tributylamine, 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, o-tolylaniline, m-methylaniline, p-methylaniline, 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5-dimethylaniline, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, o-ethylaniline, N-butylaniline, 2, 6-diethylaniline, cyclohexylamine, cyclopentylamine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including its various isomers, such as tetra-N-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including its various isomers, such as tetra-N-butylammonium hydroxide, tetra-sec-butylammonium hydroxide, tetra-isobutyl ammonium hydroxide and tetra-tert-butylammonium hydroxide), and tetrapentylammonium hydroxide (including its various isomers).
Preferably, the base is an organic base, which can further improve the catalytic activity of the finally prepared nanocarbon material molding as a catalyst for dehydrogenation reaction of hydrocarbon. More preferably, the base is a template agent for synthesizing the titanium silicalite molecular sieve, such as 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 0.05 to 15: 1, preferably 0.1 to 12: 1, more preferably 0.12 to 6: 1, the binder source is calculated by oxide.
According to the method of the third aspect of the present invention, the nanocarbon material may be uniformly mixed with the binder source and optionally the alkali using various dispersion media. Preferably, the dispersion medium is water. The amount of the dispersion medium is such that the nanocarbon material, the binder source and optionally the alkali can be mixed uniformly. As an example, where the dispersing medium is water, the molar ratio of water to the binder source may be from 1 to 150: 1, preferably 4 to 120: 1, the binder source is calculated by oxide.
The inventor of the present invention finds in the research process that the molecular sieve preparation solution generated in the molecular sieve preparation process usually contains the binder source and the alkali required in the present invention, and also contains water, and after the molecular sieve preparation solution is mixed with the nanocarbon material, one, two or three of the water, the binder source and the alkali are optionally supplemented, so that not only can the nanocarbon material be molded, but also the prepared nanocarbon material shows higher crushing resistance strength, and simultaneously still shows better catalytic activity, and in addition, the reuse of the waste liquid in the molecular sieve preparation process is realized.
The molecular sieve preparation solution can be any common molecular sieve preparation solution capable of providing the binder source and optional base required by the invention. Preferably, the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid of a silicon-containing molecular sieve and a rearrangement modified mother liquid of the silicon-containing molecular sieve. The silicon-containing molecular sieve can be one or more than two of an all-silicon molecular sieve, a heteroatom-containing molecular sieve (such as a titanium-silicon molecular sieve) and a silicon-aluminum molecular sieve. The crystallization mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained by hydrothermal crystallization when a molecular sieve is prepared by hydrothermal crystallization, namely a liquid mixture remaining after a formed molecular sieve is separated from the mixture obtained by hydrothermal crystallization, and is also called as synthesis mother liquor, filtered waste liquor or filtered stock liquor. The rearrangement modified mother liquor refers to a liquid obtained by performing solid-liquid separation on a mixture obtained after hydrothermal modification rearrangement when the modified molecular sieve is prepared by hydrothermal modification rearrangement, namely a liquid mixture remaining after the molecular sieve is separated from the mixture obtained by hydrothermal modification rearrangement, and is also called as rearrangement mother liquor, modified mother liquor, rearrangement filtration waste liquor, modified filtration raw liquor or rearrangement filtration raw liquor. The crystallization mother liquor and the rearrangement liquor can be directly mixed with the nano-carbon material, and can also be mixed with the nano-carbon material after being concentrated or diluted according to the needs, so that the dosage of the binder source, the alkali and the water can meet the requirements, for example, the proportion requirements are met.
More preferably, the solution for preparing the silicon-containing molecular sieve is one or more than two of a crystallization mother liquor of the silicon molecular sieve (such as a crystallization mother liquor of the all-silicon molecular sieve), a crystallization mother liquor of the heteroatom-containing molecular sieve (such as 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 (such as 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 the silicon element is generally 0.05 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 1-4% 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 ℃, preferably at a temperature of from 80 to 180 ℃, more preferably at a temperature of 100 ℃ and 150 ℃. 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 sources can be treated, and the nanocarbon materials can be non-surface-treated nanocarbon materials or surface-treated nanocarbon materials. In the present invention, the surface of the nanocarbon material is detected by X-ray photoelectron spectroscopy, and if the total content of elements other than C in the surface elements of the nanocarbon material detected is 2 wt% or less, the nanocarbon material is regarded as a nanocarbon material without surface treatment, whereas the nanocarbon material is regarded as a nanocarbon material with surface treatment.
In one embodiment, the nanocarbon material is a nanocarbon material that has not been surface treated. In this embodiment, the mixture is preferably subjected to a hydrothermal treatment before the mixture is shaped, which not only significantly improves the strength of the finally produced shaped body, but also significantly improves the catalytic properties of the finally produced shaped body. More preferably, the binder source and the optional alkali source are from a molecular sieve preparation solution, and the catalytic performance of the finally prepared formed body in the hydrocarbon dehydrogenation reaction can be further improved by carrying out hydrothermal treatment on the nano carbon material without modified surface treatment in the molecular sieve preparation solution. In this embodiment, the nanocarbon material may exist in various forms, and specifically, may be, but not limited to, one or a combination of two or more of carbon nanotubes, graphene, thin graphite, nanocarbon particles, nanocarbon fibers, nanodiamonds, and fullerenes. The carbon nanotube can be one or more of single-walled carbon nanotube, double-walled carbon nanotube and multi-walled carbon nanotube, preferablyAnd is selected to be multi-wall carbon nano-tube. 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 surface-treated nanocarbon material, which contains an O element, an N element, and at least one metal element as determined by X-ray photoelectron spectroscopy. The metal element is selected from group IA metal elements and group IIA metal elements, and specific examples thereof may include, but are not limited to, one or two or more of lithium, sodium, potassium, beryllium, magnesium, calcium, barium, and strontium. The metal element is preferably one or two or more of sodium, potassium, magnesium, calcium, and barium, and more preferably one or two or more selected from magnesium, barium, and calcium.
Specifically, the surface-treated nanocarbon material may be a nanocarbon material in the molded body according to the first aspect of the present invention and/or a nanocarbon material in the molded body according to the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the third aspect of the present invention.
The nanocarbon material molded body according to the fourth aspect of the present invention has high crushing strength. Generally, the nanocarbon material shaped body according to the invention may have a radial crush strength of 4N/mm or more, typically 5N/mm or more. Specifically, the nanocarbon material shaped body according to the first and second aspects of the present invention has a radial crush strength of 5 to 25N/mm, preferably 6 to 25N/mm, and more preferably 10 to 25N/mm. The nanocarbon material molded body according to the fourth aspect of the present invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the fourth aspect of the present invention may be 5% or more, or even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, and more preferably in the range of 12 to 25%.
According to a fifth aspect of the present invention, there is provided a method of forming a nanocarbon material, comprising subjecting a nanocarbon material to hydrothermal treatment in an aqueous dispersion containing a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, forming the slurry obtained by the hydrothermal treatment to obtain a formed product, and drying and optionally firing the formed product. The binder source is of the same kind as the binder source of the third aspect of the invention and will not be described in detail here.
According to the method of the fifth aspect of the present invention, nanocarbon materials of various sources can be treated, and the nanocarbon materials can be non-surface-treated nanocarbon materials or surface-treated nanocarbon materials. The nano carbon material may be specifically the nano carbon material described in the method according to the third aspect of the present invention, and will not be described in detail herein.
According to the method of the fifth aspect of the present invention, the aqueous dispersion preferably further contains at least one treating agent which is an organic base and/or a basic metal compound. This can further improve the crushing strength of the finally produced nanocarbon material shaped body and can further improve the catalytic activity of the finally produced nanocarbon material shaped body when used as a catalyst for dehydrogenation reaction of hydrocarbons. Particularly, when the nano carbon material is a nano carbon material without surface treatment, the crushing resistance and the catalytic performance of the finally prepared nano carbon material forming body can be obviously improved.
The organic base can be one or more of amine and quaternary ammonium base (such as formula II, formula III, formula IV and general formula R)16(NH2)2Substances shown) in the specification, and specific examples of the organic base are described in the present inventionThe method of the third aspect has already been described in detail and will not be described in detail here. The organic base is preferably quaternary ammonium base (a compound shown as a formula II), and is particularly preferably a template agent for synthesizing the titanium silicalite molecular sieve.
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 dehydrogenation reaction of hydrocarbon. The metal element is more preferably selected from magnesium, barium and calcium from the viewpoint of further improving the catalytic performance of the produced nanocarbon material formed body as a catalyst for hydrocarbon dehydrogenation reaction.
Preferably, the basic metal compound is selected from a hydroxide containing the metal element and a basic salt containing the metal element. More preferably, 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. 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 two or more of calcium hydroxide, barium carbonate, calcium hydrogen carbonate, barium hydroxide, and magnesium hydroxide, and more preferably one or two or more of calcium hydroxide, magnesium hydroxide, and barium hydroxide, from the viewpoint of further improving the catalytic activity of the nanocarbon material molded body in the hydrocarbon dehydrogenation reaction.
According to the method of the fifth aspect of the invention, in one embodiment, the treating agent is an organic base or an alkali metal compound.
In a more preferred embodiment, the treating agent is an organic base and/or a basic metal compound. In this more preferred embodiment, the organic base may be contained in an amount of 20 to 100% by weight, based on the total amount of the treating agent. Preferably, the organic base is contained in an amount of 40 to 92 wt% based on the total amount of the treating agent.
Further preferably, the treating agent is at least one organic base and at least one basic metal compound (the basic metal compound is preferably selected from calcium hydroxide, magnesium hydroxide and barium hydroxide), and at least part of the organic base is a quaternary ammonium base (a compound shown in formula I). The nanocarbon material molded body prepared by subjecting a nanocarbon material (particularly, a nanocarbon material which is not surface-treated) to hydrothermal treatment using an organic base and a basic metal compound as treating agents has higher crushing strength than those using an organic base and a basic metal compound alone, and shows higher catalytic activity even when used as a catalyst for dehydrogenation reaction of hydrocarbons. Compared with the method that the nano carbon material without surface treatment is subjected to hydrothermal treatment by adopting an alkaline metal compound firstly, and then is subjected to hydrothermal treatment with a binder source in the presence of organic alkali for forming, the nano carbon material without surface treatment is mixed with the binder source and the organic alkali in the presence of the alkaline metal compound for forming after the hydrothermal treatment, so that the use amount of the alkaline metal compound can be obviously reduced, and the prepared nano carbon material forming body shows the strength and the catalytic activity which are equivalent to or even higher than those of the forming body prepared by modifying and forming firstly. The content of the organic base is preferably 20 to 95% by weight, preferably 40 to 92% by weight, based on the total amount of the treating agent. The quaternary ammonium hydroxide is preferably present in an amount of 40 to 100 wt%, more preferably 100 wt%, based on the total amount of the organic base. When part of the organic base is a quaternary ammonium base, the remaining part of the organic base may be an alcohol amine and/or an amine (specific examples thereof may be referred to the alcohol amine and the amine described in the molded article according to the second aspect of the present invention, and will not be described in detail here).
The amount of the treating agent to be used may be appropriately selected depending on the amount of the binder source. Preferably, the molar ratio of the treating agent to the binder source may be from 0.05 to 15: 1, preferably 0.1 to 8: 1, more preferably 0.5 to 5: 1, the binder source is calculated by oxide.
According to the method of the fifth aspect of the present invention, the amount of water is such that the nanocarbon material and the binder source, and optionally the base, can be mixed homogeneously. Generally, the molar ratio of water to the binder source may be from 1 to 150: 1, preferably 4 to 120: 1, the binder source is calculated by oxide.
According to the method of the fifth aspect of the invention, the amount of the binder source may be selected according to the desired composition of the shaped body. Generally, the binder source is used in an amount such that the nanocarbon material content in the finally produced molded article may be 5 wt% or more (e.g., 6 wt% or more), preferably 10 wt% or more, more preferably 50 wt% or more, further preferably 60 wt% or more, further preferably 70 wt% or more, further preferably 75 wt% or more, and particularly preferably 80 wt% or more, and the nanocarbon material content is generally 95 wt% or less, preferably 94 wt% or less, and more preferably 90 wt% or less. In one example, the nanocarbon material may be contained in an amount of 5 to 95 wt% (e.g., 6 to 94 wt%), preferably 8 to 92 wt%, more preferably 10 to 90 wt%, further preferably 20 to 90 wt%, further preferably 40 to 90 wt%, and particularly preferably 70 to 90 wt%, and the heat-resistant inorganic oxide may be contained in an amount of 5 to 95 wt% (e.g., 6 to 94 wt%), preferably 8 to 92 wt%, more preferably 10 to 90 wt%, further preferably 10 to 80 wt%, further preferably 10 to 60 wt%, and particularly preferably 10 to 30 wt%, based on the total amount of the nanocarbon material molded body. The nanocarbon material molded body produced by the method according to the fifth aspect of the present invention can obtain a high strength even at a low binder content. Generally, the content of the nanocarbon material is preferably 75 to 95 wt%, more preferably 85 to 95 wt%, and the content of the heat-resistant inorganic oxide is preferably 5 to 25 wt%, more preferably 5 to 15 wt%, based on the total amount of the molded body.
According to the method of the fifth aspect of the present invention, the conditions of the hydrothermal treatment are not particularly limited as long as the treatment is performed at a high temperature in a closed environment. Specifically, the temperature of the hydrothermal treatment may be 100-. The time for the hydrothermal treatment may be selected depending on the temperature at which the hydrothermal treatment is carried out, and may be generally 0.5 to 24 hours, preferably 6 to 12 hours. The hydrothermal treatment may be performed under autogenous pressure (i.e., no additional pressure is applied during the hydrothermal treatment), or may be performed under additional applied pressure. Preferably, the hydrothermal treatment is carried out under autogenous pressure.
The methods and conditions for the forming, drying of the formed article and optional firing according to the method of the fifth aspect of the present invention are the same as those described in the method of the third aspect of the present invention and will not be described in detail herein.
In a sixth aspect of the present invention, there is provided a nanocarbon material molded body produced by the method according to the fifth aspect of the present invention.
The nanocarbon material molded body according to the sixth aspect of the present invention has high crushing strength. In general, the nanocarbon material molded body according to the sixth aspect of the present invention may have a radial crush strength of 7N/mm or more, preferably 10N/mm or more, and generally in the range of 12 to 25N/mm. The nanocarbon material molded body according to the sixth aspect of the invention has a high porosity. Generally, the porosity of the nanocarbon material shaped body according to the sixth aspect of the present invention may be 5% or more, or even 10% or more, for example, may be in the range of 5 to 50%, preferably in the range of 10 to 30%, and more preferably in the range of 12 to 25%.
According to a seventh aspect of the present invention, there is provided a use of the nanocarbon material shaped body according to the first, second, fourth and sixth aspects of the present invention as a catalyst for dehydrogenation reaction of hydrocarbon. The dehydrogenation reaction may be carried out in the presence or absence of oxygen. Preferably, the dehydrogenation reaction is carried out in the presence of oxygen, which results in a better catalytic effect. The type of hydrocarbon and the specific conditions of the dehydrogenation reaction will be described in detail below and will not be described in detail here.
According to an eighth aspect of the present invention, there is provided a hydrocarbon dehydrogenation reaction method comprising contacting a hydrocarbon with the nanocarbon material shaped bodies according to the first, second, fourth and sixth aspects of the present invention under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen. The nanocarbon material molded body according to the present invention can be used as it is as a catalyst, or can be used as a catalyst after being crushed as needed.
The hydrocarbon dehydrogenation reaction process according to the present invention can dehydrogenate various types of hydrocarbons to obtain unsaturated hydrocarbons such as olefins. The 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)Alkanes, 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, 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-ethylheptane, 2-methyl-5-ethylheptane, 3-methyl-3-ethylheptane, 4-methyl-3-ethylheptane, 5-methyl-3-ethylheptane, 4-methyl-4-ethylheptane, 4-propylheptane, 3, 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. 3500-5500h-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 ℃. Samples were tested at 150 ℃ and 1 std before testingDried under pressure in a helium atmosphere for 3 hours. The method adopts ASAP2000 type N of Micromertrics corporation in America2The physical adsorption apparatus measures the specific surface area.
The properties of the multi-walled carbon nanotubes as the raw nanocarbon material in the following preparation examples are listed in table 1 below.
TABLE 1
Figure BDA0001061583690000181
In the following examples and comparative examples, the contents of silicon, titanium and aluminum elements and the alkali content in the crystallization mother liquor and the heavy liquid were measured by a Perkin-Elmer 3300DV type Inductively Coupled Plasma (ICP) spectrometer.
In the following examples and comparative examples, the radial crush strength was measured according to the method specified in RIPP 25-90 described in "analytical methods for petrochemical industry" (edited by scientific Press, first edition 1990, Yankee, et al); the porosity is a ratio of a sum of volumes of all pore spaces in the nanocarbon material molded body to a volume of the nanocarbon material molded body, and may be also referred to as a porosity of the nanocarbon material molded body, and is measured by a mercury intrusion method (refer to "research on porosity of graphite porous material", lubrication and sealing ", 2010, 35 (10): 99-101) in percentage).
Preparation examples 1 to 12 were used to prepare nanocarbon materials containing metal atoms.
Preparation example 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 40kHz and the time was 0.5 hour. Then, barium hydroxide as a basic metal compound was added and mixed uniformly to obtain an aqueous dispersion, wherein the barium hydroxide was provided in the form of a 20 wt% aqueous solution as a raw material nanocarbon material: basic metal compound: h2The weight ratio of O is 1: 0.2: and 9.8 of the ratio.
(2) Placing the obtained aqueous dispersion in a container with polytetrafluoroethyleneThe reaction was carried out in an olefin-lined autoclave at a temperature of 120 ℃ under autogenous pressure for 24 hours. After the reaction is finished, after the temperature in the high-pressure reaction kettle is reduced to room temperature, the reaction kettle is opened, the reaction mixture is filtered and washed, and solid substances are collected. Drying the collected solid substance at normal pressure (1 atm, the same below) and 120 deg.C for 6 hr to obtain nano carbon material containing metal atom, and its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 2
The same aqueous dispersion as in preparation example 1 was placed in a three-necked flask equipped with a condenser, and the three-necked flask was placed in an oil bath at a temperature of 120 ℃ and reacted under reflux at normal pressure for 24 hours. After the reaction was completed, after the temperature in the three-necked flask was lowered to room temperature, the reaction mixture was filtered and washed, and a solid matter was collected. And drying the collected solid substance at 120 ℃ for 6 hours under normal pressure to obtain the nano carbon material containing the metal atoms.
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 prepared in the same manner as in preparation example 1, except that the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene liner and reacted at a temperature of 100 ℃ under autogenous pressure for 24 hours.
Preparation example 5
A nanocarbon material containing metal atoms was produced in the same manner as in production example 1, except that, in step (1), the nanocarbon material was prepared as follows: basic metal compound: h2The weight ratio of O is 1: 0.02: and 9.8 of the ratio.
Preparation example 6
(1) 20g of multiwall carbon nanotube C (available from Chengdu organic chemistry Co., Ltd., China academy of sciences) as a raw nanocarbon material was dispersed inDispersing in ionized water under ultrasonic oscillation conditions, wherein the ultrasonic oscillation conditions comprise: the frequency was 60kHz and the time was 1 hour. Then adding calcium hydroxide as an alkaline metal compound, and uniformly mixing to obtain an aqueous dispersion, wherein the raw material nano carbon material: basic metal compound: h2The weight ratio of O is 1: 0.25: 24.75.
(2) the obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at a temperature of 220 ℃ under autogenous pressure for 12 hours. After the reaction is finished, opening the reaction kettle after the temperature in the high-pressure reaction kettle is reduced to room temperature, filtering the reaction mixture, and collecting solid substances. Drying the collected solid substance at 120 deg.C under normal pressure for 6 hr to obtain nano carbon material containing metal atoms, and its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 7
A nanocarbon material containing metal atoms was produced in the same manner as in production example 6, 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 270 ℃ under autogenous pressure for 12 hours.
Preparation example 8
A nanocarbon material containing metal atoms was prepared in the same manner as in preparation example 6, except that, in step (1), the nanocarbon material used was a multi-walled carbon nanotube D (available from Shandong Dazhan nanomaterial Co., Ltd.).
Preparation example 9
A nanocarbon material containing metal atoms was produced in the same manner as in production example 6, except that in the step (2), the obtained aqueous dispersion was placed in a high-pressure reaction vessel with a polytetrafluoroethylene inner liner and reacted at a temperature of 310 ℃ under autogenous pressure for 12 hours.
Preparation example 10
A nanocarbon material containing a metal atom was produced in the same manner as in production example 6, except that in step (1), calcium hydroxide was replaced with an equimolar amount of potassium hydroxide.
Preparation example 11
A nanocarbon material containing a metal atom was produced in the same manner as in production example 6, except that in step (1), calcium hydroxide was replaced with an equimolar amount of sodium hydroxide.
Preparation example 12
(1) 20g of multi-walled carbon nanotubes E (purchased from Chengdu organic chemistry, Inc., of Chinese academy of sciences) were dispersed in deionized water under ultrasonic oscillation conditions including: the frequency was 40kHz and the time was 0.5 hour. Then, magnesium hydroxide as a basic metal compound was added and uniformly mixed to obtain an aqueous dispersion, wherein the magnesium hydroxide was provided in the form of a 20 wt% aqueous solution as a raw material nanocarbon material: basic metal compound: h2The weight ratio of O is 1: 0.1: 40 of the total weight of the mixture.
(2) The obtained aqueous dispersion was placed in a high-pressure reactor with a polytetrafluoroethylene liner and reacted at a temperature of 200 ℃ under autogenous pressure for 24 hours. After the reaction is finished, opening the reaction kettle after the temperature in the high-pressure reaction kettle is reduced to room temperature, filtering the reaction mixture, and collecting solid substances. Drying the collected solid substance at 120 deg.C under normal pressure for 8 hr to obtain nano carbon material containing metal atoms, and its composition, specific surface area and w500/w800Listed in table 2.
Figure BDA0001061583690000211
Examples 1 to 69 are for illustrating the nanocarbon material molded body according to the present invention and the method for preparing the same.
Examples 1-69 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 to stir 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, carrying out hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, and roasting the filtered solid in 550 ℃ air atmosphere for 6 hours to obtain the titanium-silicon molecular sieve TS-1.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 1.2% by weight in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 3.1% by weight. Concentrating the crystallization mother liquor (concentrated solution number TS-A) to SiO based on the total amount of the concentrated solution2The content of silicon element was 3.6% by weight in terms of TiO2The content of titanium element was 0.12% by weight, and the content of tetrapropylammonium hydroxide was 9.3% by weight.
(2) Crystallization mother liquor of titanium silicon molecular sieve
The titanium silicalite TS-1 was prepared according to the method of US4410501, example 2, and the crystallization mother liquor was collected. The specific operation process is as follows:
150g tetraethyl titanate was slowly added dropwise to 2.5L distilled water and hydrolyzed under stirring to give a white colloidal suspension which was then suspendedCooling the suspension to 5 deg.C, adding 1.8L aqueous hydrogen peroxide solution with concentration of 30% by mass which had been previously cooled to 5 deg.C, and maintaining at 5 deg.C for 2 hr under intermittent stirring to obtain an orange clear solution, adding 2.4L aqueous tetrapropylammonium hydroxide solution with concentration of 25% by mass which had been previously cooled to 5 deg.C to the orange clear solution, and adding 500g SiO after 1 hr2Carefully mixing silica sol with the content of 40%, and standing the obtained mixture at normal temperature overnight; finally, the mixture is heated and stirred for 6 hours at 70-80 ℃. And transferring the obtained mixture into a high-pressure reaction kettle with a stirring device, carrying out hydrothermal crystallization at 175 ℃ under autogenous pressure for 10 days, filtering the obtained reaction mixture, collecting crystallization mother liquor, roasting the filtered solid phase for 6 hours in an air atmosphere at 550 ℃, and obtaining the titanium silicalite TS-1 through X-ray diffraction analysis.
Through detection, the total amount of the crystallization mother liquor is taken as a reference, and SiO is taken2The content of silicon element was 2.8 wt.% in terms of TiO2The content of titanium element was 0.04% by weight, and the content of tetrapropylammonium hydroxide was 1.6% by weight. Concentrating the crystallized mother liquor (concentrated solution number TS-B) to SiO based on the total amount of the concentrated solution2The content of silicon element is 7 wt% in terms of TiO2The content of titanium element was 0.1% by weight, and the content of tetrapropylammonium hydroxide was 4% by weight.
(3) Crystallization mother liquor of titanium silicon molecular sieve
The 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 is carried outThe time period 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.
The detection shows that the total amount of the crystallization mother liquor (with the number of TS-C) is taken as the reference, and SiO is taken as the reference2The content of silicon element was 3.4 wt% in terms of TiO2The content of titanium element was 0.3% by weight, and the content of tetraethylammonium hydroxide was 13.1% by weight.
(4) Rearrangement liquid of titanium-silicon molecular sieve
The method of embodiment 9 of the chinese application 99126289.1 is used to obtain the heavy liquid discharge of the titanium silicalite molecular sieve, and the specific preparation process is as follows:
according to TS-1 molecular sieve (g): tetraethylammonium hydroxide (mol): water (mole) ═ 100: 0.25: 60, placing the mixture into a stainless steel sealed reaction kettle, and placing the mixture for 3 days at a constant temperature of 175 ℃ and an autogenous pressure. Cooling, releasing pressure, and filtering to obtain filtrate, i.e. the heavy discharge liquid of the titanium-silicon molecular sieve.
Through detection, the total amount of the heavy discharge liquid is taken as a reference, and SiO is taken2The content of silicon element was 1.1% by weight in terms of TiO2The content of titanium element was 0.02% by weight, and the content of tetrapropylammonium hydroxide was 3.6% by weight. Concentrating the rearranged solution (the concentrated solution is numbered TS-D) to SiO based on the total amount of the rearranged solution2The content of elemental silicon was 4.4% by weight in terms of TiO2The content of titanium element was 0.08% by weight, and the content of tetrapropylammonium hydroxide was 14.4% by weight.
(5) Crystallization mother liquor of silicon-aluminum molecular sieve
Referring to US4410501, example 1, a silicon aluminum molecular sieve is prepared using aluminum isopropoxide as an aluminum source instead of tetraethyl titanate as a titanium source, and the crystallization mother liquor is collected. The specific operation process is as follows:
in the absence of CO2455g of tetraethyl silicate was placed in a heat-resistant glass vessel, 15g of aluminum isopropoxide was added with stirring, followed by 800g of an aqueous solution of tetrapropylammonium hydroxide having a mass concentration of 25%,mixing for 4h, heating at 80-90 deg.C, stirring for 5 hr, completely removing ethanol, adding water to 1.5L, transferring the obtained mixture into a high-pressure reaction kettle equipped with stirring device, performing hydrothermal crystallization at 175 deg.C under autogenous pressure for 10 days, filtering the obtained reaction mixture, and collecting crystallized mother liquor.
The detection shows that the total amount of the crystallization mother liquor (the crystallization mother liquor is numbered AS-F) is taken AS the reference, and SiO is taken AS the reference2The content of silicon element calculated as Al was 2.3 wt%2O3The content of aluminum element was 0.14% by weight, and the content of tetrapropylammonium hydroxide was 12.5% by weight. Concentrating the crystallization mother liquor (concentrated solution number is AS-E) to SiO based on the total amount of the concentrated solution2The content of silicon element calculated as Al was 8.28 wt%2O3The content of aluminum element was 0.50 wt%, and the content of tetrapropylammonium hydroxide was 45 wt%.
Examples 1 to 36
The nanocarbon materials were molded by the following methods, respectively, under the conditions given in table 3.
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 3), 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 3.
TABLE 3
Figure BDA0001061583690000241
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 37 to 65
The following methods were used to shape the nanocarbon materials according to the conditions given in table 4, 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 4), 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 4.
Example 66
The difference from example 37 is that the nanocarbon material and the binder source were uniformly mixed at ambient temperature (25 ℃ C.) and then molded without hydrothermal treatment.
Example 67
The difference from example 37 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 37 for the same time as the hydrothermal treatment time in example 37, and the mixture obtained by the reflux reaction was fed into a mold.
Example 68
The difference from example 38 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 69
The difference from example 38 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 38 for the same time as the hydrothermal treatment time in example 38, and the mixture obtained by the reflux reaction was fed into a mold.
TABLE 4
Figure BDA0001061583690000251
Figure BDA0001061583690000261
1: the amount of the nanocarbon material is 10g2: tetrapropylammonium hydroxide3: tetramethyl ammonium hydroxide4: tetraethyl ammonium hydroxide5: the amount is calculated by oxide
6: the kind and amount of the treating agent added in addition to the treating agent contained in the binder source
Test examples 1 to 69
The catalysts prepared in examples 1-69 were tested for catalytic performance in the following order.
0.25g of each of the granular molded bodies prepared in examples 1 to 69 was packed as a catalyst in a general-purpose fixed bed micro quartz tube reactor each having quartz sand sealed at both ends, and a gas containing n-butane and oxygen (n-butane concentration of 2.16% by volume, n-butane/oxygen molar ratio of 0.5: 1, and the balance nitrogen as a carrier gas) was fed at 4500 hours under conditions of 0MPa (gauge pressure) and 450 deg.C-1The reaction was carried out by passing into the reactor at a weight hourly space velocity of (g), continuously monitoring the composition of the reaction mixture output from the reactor, and calculating the n-butane conversion and the total olefin selectivity, the results of the reaction for 3 hours and 24 hours being shown in table 5.
Testing of comparative examples 1-5
The catalytic performance of the multi-walled carbon nanotubes A, B, C, D and E were tested in turn using the same method as in test examples 1-69.
TABLE 5
Figure BDA0001061583690000271
Figure BDA0001061583690000281
Figure BDA0001061583690000291
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 (114)

1. A nanocarbon material molded body comprising a nanocarbon material and a heat-resistant inorganic oxide for bonding and molding the nanocarbon material, the nanocarbon material containing a C element, an O element and at least one metal element selected from group IA metal elements and group IIA metal elements, the total amount of the O element being 1 to 10% by weight, the total amount of the metal elements being 0.1 to 10% by weight and the total amount of the C element being 80 to 98.9% by weight, based on the total amount of the nanocarbon material and in terms of the elements;
the amount of O element determined by a peak in the range of 531.0-532.5eV in an X-ray photoelectron spectrum is IO cThe amount of O element determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eIn the range of 1-3;
in the nanocarbon material, the amount of C element determined by a peak in the range of 288.6-288.8eV in an X-ray photoelectron spectrum is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eIn the range of 1-2.5;
the nano carbon material is prepared by adopting a method comprising the following steps: reacting an aqueous dispersion in which a raw material nanocarbon material and at least one basic metal compound, in which a metal element is selected from group IA metal elements and group IIA metal elements, are dispersed in a closed container, wherein the temperature of the aqueous dispersion is maintained within a range of 80-310 ℃ during the reaction, and the raw material nanocarbon material: the weight ratio of the alkali metal compound is 1: in the range of 0.01 to 5, the raw material nanocarbon material: h2The weight ratio of O is 1: 2-100, the duration of the reaction is in the range of 0.5-144 hours, and in the raw material nano carbon material, the content of N element is not higher than 0.2 wt%, the content of O element is not higher than 1.5 wt%, and the total amount of metal elements is less than 2.5 wt%;
the nano carbon material forming body is prepared by adopting a method comprising the following steps: mixing a nanocarbon material with a binder source, shaping the obtained mixture to obtain a shaped object, drying and optionally roasting the shaped object, wherein before shaping the mixture, the method further comprises subjecting the mixture to hydrothermal treatment, the binder source is selected from a heat-resistant inorganic oxide and/or a precursor of the heat-resistant inorganic oxide, the hydrothermal treatment is carried out at a 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 total amount of O element is 2 to 8 wt%, the total amount of the metal element is 0.2 to 8 wt%, and the total amount of C element is 84 to 97.8 wt%, based on the total amount of the nanocarbon material and calculated as an element.
3. The molded body according to claim 2, wherein the total amount of O element is 3 to 7% by weight, the total amount of the metal element is 0.5 to 5% by weight, and the total amount of C element is 88 to 96.5% by weight, based on the total amount of the nanocarbon material and calculated as an element.
4. The molded body according to claim 3, wherein the total amount of O element is 5 to 6% by weight, the total amount of the metal element is 1 to 4% by weight, and the total amount of C element is 90 to 94% by weight, based on the total amount of the nanocarbon material and calculated as an element.
5. Shaped body according to any one of claims 1 to 4, wherein the total content of oxygen, determined by X-ray photoelectron spectroscopy, is IO tThe content of O element determined by a peak in the range of 529.5-530.8eV in an X-ray photoelectron spectrum is IO m，IO m/IO tIn the range of 0.01-0.3.
6. Shaped body according to claim 5, wherein IO m/IO tIn the range of 0.02-0.25.
7. Shaped body according to claim 6, wherein IO m/IO tIn the range of 0.05-0.23.
8. Shaped body according to claim 7, wherein IO m/IO tIn the range of 0.09-0.18.
9. Shaped body according to any one of claims 1 to 4, wherein the amount of O element determined by a peak in the range of 531.0 to 532.5eV in the X-ray photoelectron spectrum is IO cThe amount of O element determined from a peak in the range of 532.6 to 533.5eV in the X-ray photoelectron spectrum is IO e，IO c/IO eIn the range of 1.2-2.5.
10. The shaped body as claimed in claim 9,wherein, IO c/IO eIn the range of 1.4-2.
11. Shaped body according to claim 10, wherein IO c/IO eIn the range of 1.5-1.8.
12. Shaped body according to any one of claims 1 to 4, wherein the amount of C element in the nanocarbon material, determined by a peak in the range of 288.6-288.8eV in the X-ray photoelectron spectrum, is IC cThe amount of C element determined from a peak in the range of 286.0-286.2eV in an X-ray photoelectron spectrum is IC e，IC c/IC eIn the range of 1.2-2.2.
13. The shaped body according to claim 12, wherein IC c/IC eIn the range of 1.5-2.
14. The shaped body according to claim 13, wherein IC c/IC eIn the range of 1.8-2.
15. The molded body according to any one of claims 1 to 4, wherein the content of C element determined from a peak in the range of 284.7 to 284.9eV in X-ray photoelectron spectrum is 60 to 98% by weight, and the content of C element determined from a peak in the range of 286.0 to 288.8eV in X-ray photoelectron spectrum is 2 to 40% by weight, based on the total amount of C element in the nanocarbon material determined by X-ray photoelectron spectrum.
16. The molded body according to claim 15, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum is 65-90% by weight and the content of C element determined from a peak in the range of 286.0-288.8eV in X-ray photoelectron spectrum is 10-35% by weight, based on the total amount of C element determined from X-ray photoelectron spectrum in the nanocarbon material.
17. The molded body according to claim 16, wherein the content of C element determined from a peak in the range of 284.7-284.9eV in X-ray photoelectron spectrum is 75-85% by weight, and the content of C element determined from a peak in the range of 286.0-288.8eV in X-ray photoelectron spectrum is 15-25% by weight, based on the total amount of C element determined from X-ray photoelectron spectrum in the nanocarbon material.
18. The molded body according to any one of claims 1 to 4, wherein the metal element is one or two or more of sodium, potassium, magnesium, calcium, and barium.
19. The molded body according to claim 18, wherein the metal element is one or two or more of magnesium, barium and calcium.
20. Shaped body according to any one of claims 1 to 4, wherein the nanocarbon material is carbon nanotubes.
21. The shaped body according to claim 20, wherein the nanocarbon material is a multiwall carbon nanotube.
22. The shaped body according to claim 21, wherein the multi-walled carbon nanotubes have a specific surface area of 50-500m2In the range of/g.
23. The shaped body according to claim 22, wherein the multi-walled carbon nanotubes have a specific surface area of 80-300m2In the range of/g.
24. The molded body as claimed in claim 23, wherein the specific surface area of the multi-walled carbon nanotubes is 100-250m2In the range of/g.
25. The molding of claim 24Wherein the specific surface area of the multi-walled carbon nanotube is 120-180m2In the range of/g.
26. The shaped body as claimed in claim 21, wherein the weight loss rate of the multi-walled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
27. The shaped body of claim 26, wherein w is500/w800In the range of 0.02-0.3.
28. The shaped body of claim 27, wherein w is500/w800In the range of 0.05-0.15.
29. The molded body according to claim 1, wherein the raw material nanocarbon material: the weight ratio of the alkali metal compound is 1: 0.02-2.
30. The shaped body according to claim 29, wherein the raw nanocarbon material: the weight ratio of the alkali metal compound is 1: 0.02-1.
31. The molded body according to claim 30, wherein the raw nanocarbon material: the weight ratio of the alkali metal compound is 1: 0.02-0.5.
32. The shaped body according to claim 31, wherein the raw nanocarbon material: the weight ratio of the alkali metal compound is 1: 0.1-0.3.
33. The molded body according to claim 1, wherein the raw material nanocarbon material: h2The weight ratio of O is 1: 3-80.
34. The shaped body according to claim 33, wherein the raw nanocarbon material: h2The weight ratio of O is 1: 5-60.
35. The shaped body according to claim 34, wherein the raw nanocarbon material: h2The weight ratio of O is 1: 8-40.
36. The shaped body according to any one of claims 1 and 29 to 32, wherein the basic metal compound is selected from the group consisting of a hydroxide containing the metal element and a basic salt containing the metal element.
37. The shaped body according to claim 36, wherein 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.
38. The molded body according to claim 37, wherein the basic metal compound is one or two or more of calcium hydroxide, barium carbonate, calcium hydrogen carbonate, barium hydroxide and magnesium hydroxide.
39. The molded body according to claim 38, wherein the basic metal compound is one or two or more of calcium hydroxide, magnesium hydroxide and barium hydroxide.
40. The shaped body according to any of claims 1 and 29 to 32, wherein the temperature of the aqueous dispersion is kept in the range of 100-300 ℃ during the reaction.
41. The shaped article according to claim 40, wherein the temperature of the aqueous dispersion is maintained in the range of 120-250 ℃ and the duration of the reaction is in the range of 2-72 hours during the reaction.
42. The shaped body according to claim 40, wherein the duration of the reaction is in the range of 4 to 24 hours.
43. The molded body according to claim 1, wherein the raw nanocarbon material contains not more than 0.02% by weight of an N element, not more than 0.3% by weight of an O element, and not more than 0.5% by weight of a total amount of metal elements.
44. The shaped body according to any one of claims 1 and 29 to 32, wherein the raw nanocarbon material is carbon nanotubes.
45. The shaped body according to claim 44, wherein the starting nanocarbon material is multi-walled carbon nanotubes.
46. The shaped body according to claim 45, wherein the multi-walled carbon nanotubes have a specific surface area of 50 to 500m2/g。
47. The shaped body as claimed in claim 46, wherein the multiwall carbon nanotubes have a specific surface area of 100-260m2/g。
48. The shaped body as claimed in claim 47, wherein the multi-walled carbon nanotubes have a specific surface area of 120-190m2/g。
49. The shaped body as claimed in claim 45, wherein the total weight loss of the multi-walled carbon nanotubes in the temperature interval of 400-800 ℃ is w800The total weight loss rate in the temperature range of 400-500 ℃ is w500，w500/w800The weight loss ratio is measured in an air atmosphere in the range of 0.01 to 0.5.
50. The shaped body of claim 49, wherein w is500/w800In the range of 0.02-0.4.
51. The shaped body according to any one of claims 1 and 29 to 32, wherein in the method for producing a nanocarbon material, the method further comprises separating solid matter from the mixture obtained by the reaction, and drying the separated solid matter.
52. The shaped body according to claim 51, wherein in the method for producing a nanocarbon material, the drying is carried out at a temperature of 50-400 ℃ and the duration of the drying is not more than 48 hours.
53. Shaped body according to claim 52, wherein in the method for the production of nanocarbon materials, the drying is carried out at a temperature of 80-180 ℃ and the duration of the drying is 4-24 hours.
54. The shaped body according to claim 53, wherein in the method for producing a nanocarbon material, the duration of the drying is 6 to 12 hours.
55. The shaped body according to any one of claims 1 to 4, 29 to 35 and 43, wherein the nanocarbon material is contained in an amount of 6 to 94% by weight and the heat-resistant inorganic oxide is contained in an amount of 6 to 94% by weight, based on the total amount of the shaped body.
56. The shaped body according to claim 55, wherein the nanocarbon material is contained in an amount of 10 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 90% by weight, based on the total amount of the shaped body.
57. The shaped body according to claim 56, wherein the nanocarbon material is contained in an amount of 40 to 90% by weight and the heat-resistant inorganic oxide is contained in an amount of 10 to 60% by weight, based on the total amount of the shaped body.
58. The shaped body according to claim 57, wherein the nanocarbon material is present in an amount of 70-90 wt.% and the heat-resistant inorganic oxide is present in an amount of 10-30 wt.%, based on the total amount of the shaped body.
59. The shaped body according to any one of claims 1 to 4, 29 to 35 and 43, wherein the heat-resistant inorganic oxide is one or two or more of alumina, silica and titania.
60. The shaped body according to claim 59, wherein the heat-resistant inorganic oxide comprises silicon oxide.
61. The shaped body according to claim 60, wherein the silicon oxide is contained in an amount of 10 to 100% by weight, based on the total amount of the heat-resistant inorganic oxide.
62. The shaped body according to claim 61, wherein the silicon oxide is contained in an amount of 20 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
63. The shaped body according to claim 62, wherein the silicon oxide is contained in an amount of 50 to 99% by weight, based on the total amount of the heat-resistant inorganic oxide.
64. A process for the preparation of a nanocarbon material shaped body, which process comprises mixing a nanocarbon material with a binder source, shaping the resulting mixture to give a shaped body, drying and optionally firing the shaped body, the binder source is selected from a refractory inorganic oxide and/or a precursor of a refractory inorganic oxide, the nano carbon material is a nano carbon material without surface treatment and a nano carbon material with surface treatment, or the nano carbon material is a nano carbon material with surface treatment, and the nano carbon material with the surface treatment contains C element, O element and at least one metal element determined by X-ray photoelectron spectroscopy, the metal element is selected from group IA metal elements and group IIA metal elements, and the surface-treated nanocarbon material is a nanocarbon material as claimed in any one of claims 1 to 54;
before the mixture is formed, the method further comprises the step of subjecting the mixture to hydrothermal treatment, wherein the hydrothermal treatment is carried out at the temperature of 100-200 ℃, and the duration of the hydrothermal treatment is 6-24 hours.
65. The method of claim 64, wherein the mixture further comprises at least one base that is one or more of ammonia, a base whose cation is an alkali metal, a base whose cation is an alkaline earth metal, urea, hydrazine, an amine, and a quaternary ammonium base.
66. A process according to claim 65, wherein the base is selected from quaternary ammonium bases.
67. The method of claim 66, wherein the base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
68. A process according to claim 67, wherein the base is selected from compounds of formula II:
Figure FDA0002457761440000071
in the formula II, R5、R6、R7And R8Each is C1-C20Alkyl group of (1).
69. The method of claim 68, wherein, in formula II, R5、R6、R7And R8Each is C1-C6Alkyl group of (1).
70. The method of any of claims 65-69, wherein the molar ratio of the base to the binder source is from 0.05-15: 1, the binder source is calculated by oxide.
71. The method of claim 70, wherein the molar ratio of the base to the binder source is from 0.1 to 12: 1, the binder source is calculated by oxide.
72. The method of claim 71, wherein the molar ratio of the base to the binder source is from 0.12-6: 1, the binder source is calculated by oxide.
73. The method as claimed in claim 64, wherein the hydrothermal treatment is carried out at a temperature of 100-200 ℃ and the duration of the hydrothermal treatment is 6-12 hours.
74. The method of any of claims 64-69, wherein at least a portion of the binder source, at least a portion of the optional base, and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor of a silicaceous molecular sieve and a rearrangement modification mother liquor of a silicaceous molecular sieve.
75. The method of claim 74, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a rearrangement modification liquid of an all-silicon molecular sieve, a crystallization mother liquid and/or a rearrangement modification liquid of a titanium-silicon molecular sieve, and a crystallization mother liquid and/or a rearrangement modification liquid of a silicon-aluminum molecular sieve.
76. A process for forming a nanocarbon material, which comprises subjecting a nanocarbon material to hydrothermal treatment in an aqueous dispersion, forming a slurry obtained by the hydrothermal treatment to obtain a formed article, drying and optionally calcining the formed article, the aqueous dispersion containing a binder source selected from a heat-resistant inorganic oxide and/or a precursor of a heat-resistant inorganic oxide, the nano carbon material is a nano carbon material without surface treatment and a nano carbon material with surface treatment, or the nano carbon material is a nano carbon material with surface treatment, and the nano carbon material with the surface treatment contains C element, O element and at least one metal element determined by X-ray photoelectron spectroscopy, the metal element is selected from group IA metal elements and group IIA metal elements, and the surface-treated nanocarbon material is a nanocarbon material according to any one of claims 1 to 54.
77. The method as claimed in claim 76, wherein the aqueous dispersion further comprises at least one treating agent, the treating agent being an organic base and/or a basic metal compound, the metal element of the basic metal compound being selected from group IA and IIA metal elements.
78. A process according to claim 77, wherein the organic base is selected from quaternary ammonium bases and amines.
79. The method of claim 78, wherein the organic base is selected from templating agents for synthesizing titanium silicalite molecular sieves.
80. A process according to claim 79, wherein the organic base is selected from compounds of formula II:
Figure FDA0002457761440000081
in the formula II, R5、R6、R7And R8Each is C1-C20Alkyl group of (1).
81. The method of claim 80, wherein, in formula II, R5、R6、R7And R8Each is C1-C6Alkyl group of (1).
82. A process as claimed in claim 77, wherein the treating agent is an organic base and/or a basic metal compound, the organic base being present in an amount of from 20 to 100% by weight, based on the total amount of the treating agent.
83. A process as claimed in claim 82, wherein the organic base is present in an amount of from 20 to 95% by weight, based on the total amount of treatment agent.
84. A process as claimed in claim 83, wherein the organic base is present in an amount of 40-92% by weight, based on the total amount of treatment agent.
85. The method of claim 77, wherein the treating agent is an organic base and/or a basic metal compound, and at least a portion of the organic base is a quaternary ammonium base, the organic base being present in an amount of 20 to 100 wt% and the quaternary ammonium base being present in an amount of 40 to 100 wt%, based on the total amount of the treating agent.
86. A process as claimed in claim 85, wherein the organic base is present in an amount of from 20 to 95% by weight, based on the total amount of treatment agent.
87. A process as claimed in claim 86, wherein the organic base is present in an amount of from 40 to 92% by weight, based on the total amount of treatment agent.
88. The method of any of claims 77-87, wherein the molar ratio of the treating agent to the binder source is from 0.05-15: 1, the binder source is calculated by oxide.
89. The method of claim 88, wherein the molar ratio of the treating agent to the binder source is from 0.1 to 8: 1, the binder source is calculated by oxide.
90. The method of claim 89, wherein the molar ratio of the treating agent to the binder source is from 0.5 to 5: 1, the binder source is calculated by oxide.
91. The method of any of claims 76-87, wherein at least a portion of the binder source, at least a portion of the optional organic base, and at least a portion of the water are from a molecular sieve preparation solution that is a mixture of one or more of a crystallization mother liquor of a silicaceous molecular sieve and a rearrangement-modified mother liquor of a silicaceous molecular sieve.
92. The method of claim 91, wherein the molecular sieve preparation liquid is a mixed liquid of one or more of a crystallization mother liquid and/or a rearrangement modification liquid of an all-silicon molecular sieve, a crystallization mother liquid and/or a rearrangement modification liquid of a titanium-silicon molecular sieve, and a crystallization mother liquid and/or a rearrangement modification liquid of a silicon-aluminum molecular sieve.
93. The process as set forth in any one of claims 76 to 87 wherein the hydrothermal treatment is carried out at a temperature of 100 ℃ and 200 ℃ for a duration of 0.5 to 24 hours.
94. The method of any of claims 64-69 and 76-87, wherein the refractory inorganic oxide is one or more of alumina, silica and titania.
95. The method of claim 94, wherein the refractory inorganic oxide comprises silicon oxide.
96. The method as claimed in claim 95, wherein the silicon oxide is present in an amount of 10-100% by weight, based on the total amount of the refractory inorganic oxide.
97. The method as claimed in claim 96, wherein the silica is present in an amount of 20-99 wt.% based on the total amount of the refractory inorganic oxide.
98. The method as claimed in claim 97, wherein the silicon oxide is present in an amount of 50-99 wt% based on the total amount of the refractory inorganic oxide.
99. The method of any of claims 64-69 and 76-87, 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%.
100. The method of claim 99, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 6-94% by weight and the refractory inorganic oxide content is 6-94% by weight.
101. The method as claimed in claim 100, 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 heat-resistant inorganic oxide is contained in an amount of 5-25 wt% in the finally prepared molded body.
102. The method of claim 101, wherein the binder source is used in an amount such that the nanocarbon material content in the finally prepared shaped body is 85-95 wt% and the refractory inorganic oxide content is 5-15 wt%.
103. The method of any of claims 64-69 and 76-87, wherein the drying is performed at a temperature of 50-200 ℃, for a duration of 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.
104. The method as recited in claim 103, wherein said drying is carried out at a temperature of 120-180 ℃, and the duration of said drying is 3-24 hours;
the calcination is carried out at a temperature of 350-650 ℃ and the duration of the calcination is 2-4 hours.
105. The method of claim 104, wherein the duration of drying is 5-15 hours.
106. A nanocarbon material shaped body prepared by the method of any one of claims 64-105.
107. Use of a nanocarbon material shaped body according to any one of claims 1 to 63 and 106 as a catalyst for dehydrogenation reactions of hydrocarbons.
108. The use of claim 107, wherein the hydrocarbon is an alkane.
109. The use of claim 108, wherein the hydrocarbon is C2-C12Of (a) an alkane.
110. The use of claim 109, wherein the hydrocarbon is n-butane.
111. A hydrocarbon dehydrogenation reaction process comprising contacting a hydrocarbon with the nanocarbon material shaped body of any one of claims 1-63 and 106 under hydrocarbon dehydrogenation reaction conditions in the presence or absence of oxygen.
112. The method of claim 111, wherein the hydrocarbon is an alkane.
113. The method of claim 112, wherein the hydrocarbon is C2-C12Of (a) an alkane.
114. The method of claim 113, wherein the hydrocarbon is n-butane.
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