CN107661764A - The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material - Google Patents

The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material Download PDF

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CN107661764A
CN107661764A CN201610602827.9A CN201610602827A CN107661764A CN 107661764 A CN107661764 A CN 107661764A CN 201610602827 A CN201610602827 A CN 201610602827A CN 107661764 A CN107661764 A CN 107661764A
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weight
nano
carbon material
range
formed body
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CN107661764B (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/40—
    • B01J35/613—
    • B01J35/615—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

Abstract

The forming method and hydrocarbon dehydrogenation reaction method of nano-carbon material formed body and its preparation method and application and nano-carbon material.The invention discloses a kind of nano-carbon material formed body and its preparation method and application and using hydrocarbon dehydrogenation reaction method of the formed body as catalyst, the formed body contains nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded, on the basis of the total amount of the formed body, the content of the nano-carbon material is 6 94 weight %, and the content of the binding agent is 6 94 weight %.According to the nano-carbon material formed body of the present invention using heat-resistant inorganic oxide as binding agent by nano-carbon material molding bonded, not only there is higher crushing strength, and there is higher porosity, the catalyst for being adapted as catalyst, particularly hydrocarbon dehydrogenation reaction uses.

Description

Nano-carbon material formed body and its preparation method and application and nano-carbon material into Type method and hydrocarbon dehydrogenation reaction method
Technical field
The present invention relates to nano-carbon material field shaping technique, in particular it relates to which a kind of nano-carbon material is molded Body and preparation method thereof, the invention further relates to the application of catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction, The invention further relates to a kind of hydrocarbon dehydrogenation reaction method using the nano-carbon material formed body as catalyst.
Background technology
The dehydrogenation reaction of hydrocarbons is a kind of important reaction type, such as most of low-carbon olefine is to pass through low-carbon The dehydrogenation reaction of alkane and obtain.Whether dehydrogenation reaction participates in that direct dehydrogenation reaction (that is, oxygen can be divided into according to oxygen Gas is not involved in) and oxidative dehydrogenation (that is, oxygen participates in) two classes.
Polytype nano-carbon material has been demonstrated equal to the direct dehydrogenation reaction of hydrocarbons and oxidative dehydrogenation With catalytic effect.
Hydrocarbon oxidative dehydrogenation process using nano-carbon material as catalyst, need to be by nano-sized carbon as used fixed bed reaction technique Material is molded, and formed body needs the requirement for meeting following two aspects：(1) there is certain intensity, to avoid in course of reaction Middle formed body occurs to crush, and on the one hand broken the fine grained formed or powder can cause beds pressure drop to raise, so as to carry High production run cost, increase the danger of production；On the other hand if the broken fine grained formed or powder are by reaction product band Go out, catalyst loss and product can be caused to separate and complicate；(2) there is certain porosity, to improve the ratio table of formed body Area so that the nano-carbon material in formed body can be contacted more fully with reaction mass.
As an example for being molded nano-carbon material, researcher attempts CNT (CNT) being supported on SiC bubbles The surface of foam, form CNT/SiC foams.Although CNT can preferably be anchored on SiC foam surface, CNT load capacity compared with It is low, it is typically only capable to reach 0.5-4 weight %.
Therefore, how nano-carbon material is shaped in wide in range nano-carbon material content range still with higher The formed body of intensity is still a technical problem urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to provide a kind of nano-carbon material formed body and preparation method thereof, nano-carbon material shaping Body not only has higher intensity, and the content of nano-carbon material can be adjusted in wider scope.
According to an aspect of the present invention, the invention provides a kind of nano-carbon material formed body, the formed body, which contains, to be received Rice carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded, using the total amount of the formed body as Benchmark, the content of the nano-carbon material is 6-94 weight %, and the content of the binding agent is 6-94 weight %.
According to the second aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain Nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded, with the total amount of the formed body On the basis of, the content of the nano-carbon material is 6-94 weight %, and the content of the binding agent is 6-94 weight %；
The nano-carbon material is made using the method comprised the following steps：By a kind of raw material nano carbon material of being dispersed with Aqueous dispersions are reacted in closed container, and at least one modifying agent is dissolved with the aqueous dispersions, and the modifying agent is Nitrogen-containing compound, or the modifying agent are nitrogen-containing compound and nitric acid metal salt, and the nitrogen-containing compound is selected from NH3, hydrazine and Urea, in course of reaction, the temperature of the aqueous dispersions is in the range of 80-350 DEG C.
According to the third aspect of the present invention, should the invention provides a kind of preparation method of nano-carbon material formed body Method include nano-carbon material is mixed with binding agent source, obtained mixture is molded, obtains article shaped, by it is described into Type thing is dried and is optionally calcined, and the binding agent source is selected from heat-resistant inorganic oxide and/or heat-resistant inorganic oxide Precursor, the nano-carbon material is not surface treated nano-carbon material and/or surface treated nano-carbon material.
According to the fourth aspect of the present invention, the invention provides a kind of method system as described in third aspect of the present invention Standby nano-carbon material formed body.
According to the fifth aspect of the present invention, the invention provides a kind of forming method of nano-carbon material, this method bag Include and nano-carbon material is subjected to hydro-thermal process in a kind of aqueous dispersions, the sizing material forming that hydro-thermal process is obtained, be molded Thing, the article shaped is dried and is optionally calcined, the aqueous dispersions contain binding agent source, the binding agent source choosing From the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, the nano-carbon material is received to be not surface treated Rice carbon material and/or surface treated nano-carbon material.
According to the sixth aspect of the invention, the invention provides as the method preparation described in the 5th aspect of the present invention Nano-carbon material formed body.
According to the seventh aspect of the present invention, the invention provides according to the present invention nano-carbon material formed body as hydrocarbon The application of the catalyst of dehydrogenation reaction.
According to the eighth aspect of the present invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, deposits Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with the present invention the on one side, second aspect, Nano-carbon material formed body contact described in 4th aspect or the 6th aspect.
Nano-carbon material is glued using heat-resistant inorganic oxide as binding agent according to the nano-carbon material formed body of the present invention Form type, not only there is higher crushing strength, and there is higher porosity, be adapted as catalyst, particularly hydrocarbon The catalyst of dehydrogenation reaction uses.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.In the present invention, when representing number range, " ×-× in the range of " include two binary values.In the present invention, nano-carbon material refers to that dispersed phase yardstick is at least one-dimensional Carbon material less than 100nm.In the present invention, " at least one " represents one or more kinds of.
According to the first aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain Nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded.
According to the nano-carbon material formed body of the present invention, the nano-carbon material can be pure nano-carbon material, It can be the nano carbon material containing the modifying element more than one or both of oxygen atom, nitrogen-atoms and metallic atom Material.
From the further angle for improving nano-carbon material formed body as the catalyst of hydrocarbon dehydrogenation reaction, the nanometer Carbon material preferably comprises C element, O elements, N element and optional metallic element.It is highly preferred that with the nano-carbon material On the basis of total amount and in terms of element, the content of N element can be that the content of 0.5-12 weight %, O element can be 0.5-10 weights % is measured, the content of metallic element can be 0-10 weight %.
In the present invention, the content of each element is determined using X-ray photoelectron spectroscopy in nano-carbon material.Sample is being tested It is preceding to be dried 3 hours in helium atmosphere at a temperature of 150 DEG C.Wherein, X-ray photoelectron spectroscopic analysis are in Thermo The ESCALab250 type x-ray photoelectron power spectrums equipped with Thermo Avantage V5.926 softwares of Scientific companies Tested on instrument, excitaton source is monochromatization Al K α X ray, energy 1486.6eV, power 150W, is led to used in narrow scan Can be thoroughly 30eV, base vacuum when analysis is tested is 6.5 × 10-10Mbar, the C1s peaks of electron binding energy simple substance carbon (284.0eV) is corrected, and carries out data processing on Thermo Avantage softwares, sensitivity factor is used in analysis module Method carries out quantitative analysis.
According to the nano-carbon material formed body of the present invention, the nano-carbon material can contain the metallic element, also may be used Not contain the metallic element.
In one embodiment, the content of metallic element described in the nano-carbon material be less than 0.1 weight % ( Referred to as nano-carbon material containing hetero atom), the embodiment is referred to as the first embodiment below.In another embodiment In, the content of metallic element described in the nano-carbon material is more than 0.1 weight % (also referred to as nano carbon materials containing metallic atom Material), the embodiment is referred to as second of embodiment below.Compared with the first embodiment, in remaining condition identical Under the conditions of, according to the nano-carbon material formed body of second of embodiment in the catalyst as hydrocarbon dehydrogenation reaction, show Higher catalytic activity, higher feed stock conversion and selectivity of product can be obtained.Below to according to above two embodiment Nano-carbon material formed body in the composition of nano-carbon material illustrate respectively.
In the first embodiment, on the basis of the total amount of nano-carbon material and in terms of element, the content of N element can be with For 1-12 weight %, preferably 3-12 weight %, more preferably 3.5-10 weight %, more preferably 3.5-9.5 weight %； The content of O elements can be 0.5-10 weight %, more preferably preferably 1-10 weight %, 3-9 weight %, be more preferably 4.5-8 weight %；The content of C element can be 78-98.5 weight %, preferably 78-96 weight %, more preferably 81-93.5 Weight %, more preferably 82.5-92 weight %.
In the first embodiment, the total amount for the N element in nano-carbon material being determined by x-ray photoelectron power spectrum is IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tCan be In the range of 0.7-1, preferably in the range of 0.8-1, more preferably in the range of 0.8-0.95, further preferably in 0.85- In the range of 0.92.In the first embodiment, it is true by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum Fixed N element is substantially not present or content is relatively low.Usually, in the first embodiment, by x-ray photoelectron power spectrum The amount for the N element that peak in the range of 400.6-401.5eV determines is IN g, IN g/IN tGenerally in the range of 0-0.3, preferably exist In the range of 0.05-0.2, more preferably in the range of 0.08-0.15.
In the present invention, the total amount A of N element is determined by the area of the N1s spectral peaks in x-ray photoelectron power spectrumN 1, by X ray N1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak in the range of 400.6-401.5eV (corresponds to graphite mould nitrogen Species) and 398.5-400.1eV in the range of spectral peak (nitrogen species in addition to graphite mould nitrogen), determine this respective face in two groups of peaks Product, A is designated as by the area of the spectral peak in the range of 400.6-401.5eVN 2, by the spectral peak in the range of 398.5-400.1eV Area is designated as AN 3, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, when obtained ratio is less than 0.01, it is believed that without such Species, and the content of such species is designated as 0.
In the first embodiment, the O determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum The amount of element (that is, C=O) is IO c, the O elements that are determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount of (that is, C-O) is IO e, IO c/IO eGenerally in the range of 0.3-1.5, preferably in the range of 0.8-1.5, more preferably exist In the range of 0.85-1.2, further preferably in the range of 0.9-1.
In the present invention, by the area A of the O1s spectral peaks in x-ray photoelectron power spectrumO 1The total amount of O elements is determined, by X ray O1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak (corresponding to C=O species) in the range of 531.0-532.5eV And the spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, by the spectral peak in the range of 531.0-532.5eV Area be designated as AO 2, the area of the spectral peak in the range of 532.6-533.5eV is designated as AO 3, IO c/IO e=AO 2/AO 3。
In the first embodiment, on the basis of the total amount of C element in nano-carbon material, by x-ray photoelectron power spectrum The content for the C element that peak in the range of middle 284.7-284.9eV determines can be 60-98 weight %, preferably 65-95 weights Measure %, more preferably 75-85 weight %；The C members determined by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum The total content of element can be 2-40 weight %, more preferably preferably 5-35 weight %, 15-25 weight %.
In the present invention, by the area A of the C1s spectral peaks in x-ray photoelectron power spectrumC 1The total amount of C element is determined, by X ray C1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak in the range of 284.7-284.9eV (corresponds to graphite mould carbon Species) and spectral peak (corresponding to non-graphite type carbon species) in the range of 286.0-288.8eV, will be in 284.7-284.9eV In the range of the area of spectral peak be designated as AC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, by X ray light Content=the A for the C element that peak in electron spectrum in the range of 284.7-284.9eV determinesC 2/AC 1, by x-ray photoelectron power spectrum Total content=the A for the C element that peak in the range of middle 286.0-288.8eV determinesC 3/AC 1。
In nano-carbon material described in the first embodiment, by 288.6-288.8eV scopes in x-ray photoelectron power spectrum The amount for the C element that interior peak determines is IC c, the C members that are determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum The amount of element is IC e, IC c/IC eIn the range of 0.3-1.5, preferably in the range of 0.5-1.5, the model more preferably in 0.6-1.4 In enclosing.
In the present invention, the spectral peak in x-ray photoelectron power spectrum in the range of 286.0-288.8eV (is corresponded into non-graphite Carbon species) be further divided into two groups of peaks, i.e., the spectral peak in the range of 286.0-286.2eV (corresponds to hydroxyl and ether type carbon thing Kind) and spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, will be in 286.0- The area of spectral peak in the range of 286.2eV is designated as AC 4, the area of the spectral peak in the range of 288.6-288.8eV is designated as AC 5, IC c/IC e=AC 5/AC 4。
In second of embodiment, the metallic element is selected from the metallic element that can form nitric acid metal salt, such as selects Group ia metal element, group iia metallic element, Group IIIB metallic element, group ivb metal member from the periodic table of elements Element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, group ib gold Belong to element, group iib metallic element, group III A metallic element, group IVA metallic element and V A races metallic element.It is described The instantiation of metallic element can include but is not limited to lithium, sodium, potassium, magnesium, calcium, strontium, scandium, yttrium, thulium (such as lanthanum, Cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminium, germanium, tin, lead and Antimony.Preferably, the metallic element is selected from group ia metal element, group iia metallic element, group VIII metallic element, the IB races metallic element, group iib metallic element and group IVA metallic element, the carbon material containing metal nano is now used as hydrocarbon During the catalyst of dehydrogenation reaction, higher catalytic activity can be obtained.It is highly preferred that the metallic element is selected from group VIII metal Element.It is further preferred that the metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
In second of embodiment, on the basis of the total amount of nano-carbon material and in terms of element, the contents of O elements can be with For 1-8 weight %, preferably 2-8 weight %, more preferably 3.5-6 weight %；The content of N element can be 0.5-10 weights Measure %, more preferably preferably 1.5-5 weight %, 2-4 weight %；The total amount of metallic element can be 1-10 weight %, preferably For 2-5 weight %, more preferably 2-4.5 weight %；The content of C element can be 72-97.5 weight %, preferably 82-94.5 Weight %, more preferably 85.5-92.5 weight %.
In nano-carbon material described in second of embodiment, the oxygen element that is determined by x-ray photoelectron power spectrum always contains Measure as IO t, the content of the O elements determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum is IO m, IO m/IO t Can be in the range of 0.02-0.35, preferably in the range of 0.05-0.3, more preferably in the range of 0.06-0.2.According to The nano-carbon material containing metallic atom of the present invention, is determined by the peak in the range of 531.0-533.5eV in x-ray photoelectron power spectrum The content of O elements is IO nm, IO nm/IO tCan be in the range of 0.75-0.98, preferably in the range of 0.7-0.95, more preferably In the range of 0.8-0.94.
In nano-carbon material described in second of embodiment of the invention, by the O1s spectral peaks in x-ray photoelectron power spectrum Area is designated as AO 1, O1s spectral peaks are divided into two groups of peaks, the spectral peak in the range of 529.5-530.8eV (is corresponded to and metallic atom Connected oxygen species) area be designated as AO 2, by the range of 531.0-533.5eV spectral peak (correspond to not with metallic atom phase Even oxygen species) area be designated as AO 3, wherein, IO m/IO t=AO 2/AO 1, IO nm/IO t=AO 3/AO 1。
In nano-carbon material described in second of embodiment, by 531.0-532.5eV scopes in x-ray photoelectron power spectrum The amount for the O elements (that is, C=O) that interior peak determines is IO c, by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount of the O elements (that is, C-O) of determination is IO e, IO c/IO eCan be in the range of 0.1-0.8, the scope preferably in 0.2-0.8 It is interior, preferably in the range of 0.4-0.6.
It is in second of embodiment, the spectral peak in x-ray photoelectron power spectrum in the range of 531.0-533.5eV is (right The oxygen species that Ying Yu is not connected with metallic atom) it is further separated into two groups of peaks, i.e., the spectral peak in the range of 531.0-532.5eV (corresponding to C=O species) and the spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, will be in 531.0- The area of spectral peak in the range of 532.5eV is designated as AO 4, the area of the spectral peak in the range of 532.6-533.5eV is designated as AO 5, IO c/IO e=AO 4/AO 5。
In nano-carbon material described in second of embodiment, to be determined in nano-carbon material by x-ray photoelectron power spectrum C element total amount on the basis of, the C element that is determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum contains Amount can be 60-95 weight %, more preferably preferably 70-92 weight %, 75-90 weight %；By in x-ray photoelectron power spectrum The total content for the C element that peak in the range of 286.0-288.8eV determines can be 5-40 weight %, preferably 8-30 weight %, More preferably 10-25 weight %.
In nano-carbon material described in second of embodiment, by 288.6-288.8eV scopes in x-ray photoelectron power spectrum The amount for the C element that interior peak determines is IC c, the C members that are determined by the peak in the range of 286.0-286.2eV in x-ray photoelectron power spectrum The amount of element is IC e, IC c/IC eGenerally in the range of 0.2-1, preferably in the range of 0.3-0.8.
In nano-carbon material described in second of embodiment, the N in nano-carbon material is determined by x-ray photoelectron power spectrum The total amount of element is IN t, the amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tIn the range of 0.6-0.95, preferably in the range of 0.65-0.8.Nanometer is determined by x-ray photoelectron power spectrum The total amount of N element in carbon material is IN t, the N members that are determined by the peak in the range of 403.5-406.5eV in x-ray photoelectron power spectrum Element (that is ,-NO2Species) content be IN n, IN n/IN tIn the range of 0.05-0.35, preferably in the range of 0.06-0.25. It is true by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum in nano-carbon material described in second of embodiment Fixed N element content is relatively low not to be contained even.Usually, in the nano-carbon material, by 400.6- in x-ray photoelectron power spectrum The amount for the N element that peak in the range of 401.5eV determines is IN g, IN g/IN tFor not higher than 0.3, the scope typically in 0.02-0.2 It is interior, preferably in the range of 0.05-0.15.
In second of embodiment, the total amount of N element is determined by the area of the N1s spectral peaks in x-ray photoelectron power spectrum AN 1, the N1s spectral peaks in x-ray photoelectron power spectrum are divided into three groups of peaks, i.e., the spectral peak in the range of 403.5-406.5eV is (corresponding In-NO2Species), the spectral peak (corresponding to graphite mould nitrogen species) in the range of 400.6-401.5eV and 398.5-400.1eV In the range of spectral peak (remove graphite mould nitrogen and-NO2Nitrogen species outside type nitrogen), by the spectral peak in the range of 400.6-401.5eV Area be designated as AN 2, the area of the spectral peak in the range of 398.5-400.1eV is designated as AN 3, will be in 403.5-406.5eV scopes The area of interior spectral peak is designated as AN 4, IN c/IN t=AN 3/AN 1, IN g/IN t=AN 2/AN 1, IN n/IN t=AN 4/AN 1, in obtained ratio During for less than 0.01, it is believed that be designated as 0 without such species, and by the content of such species.
In the present invention, the position at each peak can determine that as the combination corresponding to the summit at the peak, and scope determines by mentioned earlier The peak combination that refers to corresponding to summit can be within that range peak, a peak can be included within the range, can also be wrapped Include more than two peaks.Such as：Peak in the range of 398.5-400.1eV refers to that the combination corresponding to summit can be in 398.5- Whole peaks in the range of 400.1eV.
According to the nano-carbon material formed body of the present invention, the nano-carbon material can by it is common it is various in the form of exist, Be specifically as follows but be not limited to CNT, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, Nano diamond and Combination more than one or both of fullerene.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and Combination more than one or both of multi-walled carbon nanotube.According to nano-carbon material formed body, the nano-carbon material is preferred For multi-walled carbon nanotube.
According to the nano-carbon material formed body of the present invention, it is preferable that the specific surface area of the multi-walled carbon nanotube is 50- 500m2/ g, the catalytic performance of the formed body so can be further improved, especially as the catalyst of hydrocarbons dehydrogenation reaction Catalytic performance.The specific surface area of the multi-walled carbon nanotube is more preferably 80-300m2/ g, more preferably 90-250m2/ g.The specific surface area of the multi-walled carbon nanotube can also whether the species containing surface-element and surface-element be entered according to it Row optimization.For example, the multi-walled carbon nanotube for nano-carbon material described in the first embodiment above when, more wall carbon are received The specific surface area of mitron is preferably 90-150m2/g；It is receiving described in second of embodiment above in the multi-walled carbon nanotube During rice carbon material, the ratio surface of multi-walled carbon nanotube is preferably 120-180m2/g.In the present invention, the specific surface area is by nitrogen Adsorb BET method measure.
According to the nano-carbon material formed body of the present invention, the multi-walled carbon nanotube is in 400-800 DEG C of temperature range Weight-loss ratio be w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that in 0.01-0.5 model In enclosing, more preferable catalytic effect can be so obtained, during catalyst particularly as hydrocarbons dehydrogenation reaction, can be obtained more Good catalytic effect.The w of the multi-walled carbon nanotube500/w800Whether surface-element and surface element can also be contained according to it The species of element optimizes.For example, it is the nano-carbon material described in the first embodiment above in the multi-walled carbon nanotube When, w500/w800More preferably in the range of 0.02-0.2；In the multi-walled carbon nanotube for described in second of embodiment above Nano-carbon material when, w500/w800More preferably in the range of 0.05-0.4, further preferably in the range of 0.05-0.15. In the present invention, w800=W800- W400, w500=W500- W400, W400For the mass loss rate determined at a temperature of 400 DEG C, W800 For the mass loss rate determined at a temperature of 800 DEG C, W500For the mass loss rate determined at a temperature of 500 DEG C；The mistake Rate is determined using thermogravimetric analyzer in air atmosphere again, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample Depress in 150 DEG C of temperature and 1 normal atmosphere and dried 3 hours in helium atmosphere before testing.
According to the nano-carbon material formed body of the present invention, in the nano-carbon material, for oxygen atom and nitrogen-atoms outside Other nonmetallic heteroatoms, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, the nano carbon material In material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be 0.5 weight Measure below %, preferably below 0.2 weight %, more preferably below 0.1 weight %, more preferably 0.05 weight % with Under.In the nano-carbon material, in addition to selected from aforesaid metal elements, other metallic atoms, other metals can also be contained Atom for example can be from the catalyst used when preparing nano-carbon material.The content of other metallic atoms is generally Below 1.5 weight %, it is still more preferably below 0.5 weight %, particularly preferably 0.2 weight preferably below 1 weight % Measure below %.
According to the nano-carbon material formed body of the present invention, also contain and be used for the heat-resisting of the nano-carbon material molding bonded Inorganic oxide.In the present invention, term " heat-resistant inorganic oxide " refers to that under oxygen or oxygen-containing atmosphere decomposition temperature is not less than 300 DEG C (such as：Decomposition temperature be 300-1000 DEG C) inorganic oxygen-containing compound.
According to the present invention nano-carbon material formed body, the heat-resistant inorganic oxide be preferably aluminum oxide, silica and It is more than one or both of titanium oxide.In an example, the heat-resistant inorganic oxide is aluminum oxide, according to the example Nano-carbon material shaping physical efficiency obtains higher feed stock conversion.
In a preferred embodiment, at least part heat-resistant inorganic oxide is silica, according to the preferable reality The nano-carbon material formed body of mode is applied in the catalyst as hydrocarbon dehydrogenation reaction, can be in feed stock conversion and selectivity of product Between obtain preferably balance.It is described on the basis of the total amount of the heat-resistant inorganic oxide in the preferred embodiment The content of silica can be 10-100 weight %, more preferably preferably 20-99 weight %, 50-99 weight %, silicon Outside the content of heat-resistant inorganic oxide can be 0-90 weight %, preferably 1-80 weight %, more preferably 1-50 weight Measure %.In the preferred embodiment, the instantiation of the heat-resistant inorganic oxide outside silicon can be included but not It is limited to aluminum oxide and/or titanium oxide.As an example of the preferred embodiment, the heat resistant inorganic oxygen outside silicon Compound is titanium oxide.
According to the nano-carbon material formed body of the present invention, the content of the nano-carbon material can become in wider scope It is dynamic, still such that the nano-carbon material formed body has higher intensity.Usually, with the nano-carbon material formed body On the basis of total amount, the content of the nano-carbon material can be 6-94 weight %, preferably 8-92 weight %, more preferably 10- 90 weight %, more preferably 20-90 weight %, it is still more preferably 40-90 weight %, particularly preferably 70-90 weight % is measured, the content of the heat-resistant inorganic oxide can be 6-94 weight %, preferably 8-92 weight %, more preferably 10-90 Weight %, more preferably 10-80 weight %, it is still more preferably 10-60 weight %, particularly preferably 10-30 weight Measure %.In embodiment disclosed by the invention, the formed body that is calculated by inventory forms and uses x ray fluorescence spectrometry The composition of the formed body of measure is basically identical, and error is within 5%.
According to the second aspect of the invention, the invention provides a kind of nano-carbon material formed body, the formed body to contain Nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded.
According to the formed body described in second aspect of the present invention, the nano-carbon material is using the method comprised the following steps It is made：A kind of aqueous dispersions for being dispersed with raw material nano carbon material are reacted in closed container, in the aqueous dispersions Dissolved with least one modifying agent, in course of reaction, the temperature of the aqueous dispersions preferably exists in the range of 80-350 DEG C In the range of 80-310 DEG C.The duration of the reaction can be in the range of 0.5-144 hours, preferably in 0.5-96 hours In the range of, more preferably in the range of 2-72 hours, further preferably in the range of 10-60 hours.
According to the formed body described in second aspect of the present invention, the modifying agent can be nitrogen-containing compound, or Nitrogen-containing compound and nitric acid metal salt.The nitrogen-containing compound is selected from NH3, hydrazine and urea.It is below nitrogenous chemical combination by modifying agent The embodiment of thing is referred to as the first preparation method, and the embodiment that modifying agent is nitrogen-containing compound and nitric acid metal salt is referred to as into the Two preparation methods.The first preparation method and the second preparation method are illustrated individually below.
In the first preparation method, raw material nano carbon material：The weight ratio of nitrogen-containing compound can be 1：0.05-50.It is former Expect nano-carbon material：The weight ratio preferably 1 of nitrogen-containing compound：0.1-20, more preferably 1：0.3-10, more preferably 1： 0.4-5。
In the first preparation method, raw material nano carbon material：H2O weight ratio can be 1：1-200, preferably 1：2- 100, more preferably 1：10-50.Furthermore it is also possible to the dosage of water is adjusted according to the species of nitrogen-containing compound, so that institute State nitrogen-containing compound and can be dissolved in water and be defined.
In the first preparation method, in course of reaction, the temperature of the aqueous dispersions such as exists in the range of 80-350 DEG C In the range of 80-310 DEG C, preferably in the range of 80-250 DEG C.It is in the temperature of the aqueous dispersions within above range When, the oxygen atom and nitrogen atom content in raw material nano carbon material can not only be effectively improved, and will not be to raw material nano carbon The structural form of material is produced and significantly affected.In course of reaction, the temperature of the aqueous dispersions is more preferably in 100-220 DEG C of model In enclosing, further preferably in the range of 110-200 DEG C, still more preferably in the range of 110-170 DEG C.
In the first preparation method, the duration of the reaction can be selected according to the temperature of reaction, with can Enough oxygen atoms are introduced in raw material nano carbon material and nitrogen-atoms is defined.Usually, the duration of the reaction can be with In the range of 0.5-144 hours, preferably in the range of 2-72 hours, more preferably in the range of 10-60 hours, further It is preferred that in the range of 20-40 hours.
In the second preparation method, the metallic element in the nitric acid metal salt is selected from the gold that can form nitric acid metal salt Belong to element, group ia metal element, group iia metallic element, Group IIIB metallic element, the such as in the periodic table of elements Group IVB metallic element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metal member Element, I B-group metal element, group iib metallic element, group III A metallic element, group IVA metallic element and V A races gold Belong to element.The instantiation of metallic element in the nitric acid metal salt can include but is not limited to lithium, sodium, potassium, magnesium, calcium, barium, Strontium, scandium, yttrium, thulium (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, Platinum, copper, silver, gold, zinc, aluminium, germanium, tin and antimony.Preferably, the metallic element in the nitric acid metal salt is selected from group ia metal member Element, group iia metallic element, group VIII metallic element, I B-group metal element, group iib metallic element and group IVA gold Belong to element, the nano-carbon material formed body thus prepared can obtain higher catalysis in the catalyst as hydrocarbon dehydrogenation reaction Activity.It is highly preferred that the metallic element in the nitric acid metal salt is selected from group VIII metallic element.It is further preferred that institute The metallic element stated in nitric acid metal salt is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
In the second preparation method, it is preferable that raw material nano carbon material：Nitrogen-containing compound：The weight ratio of nitric acid metal salt 1：0.01-10：In the range of 0.01-10, the nano-carbon material formed body thus prepared is in the catalysis as hydrocarbon dehydrogenation reaction The feed stock conversion further improved and selectivity of product can be obtained during agent.Raw material nano carbon material：Nitrogen-containing compound：Nitric acid gold Belong to the weight ratio of salt more preferably 1：0.05-8：In the range of 0.1-8, further preferably 1：0.2-5：In the range of 0.5-3.
In the second preparation method, the dosage of water can be selected according to the amount of raw material nano carbon material.Raw material is received Rice carbon material：H2O weight ratio is preferably 1：In the range of 2-500, more preferably 1：In the range of 5-300, further preferably 1：In the range of 10-50.
In the second preparation method, although by nitrogen-containing compound with together with nitric acid metal salt together with raw material nano carbon material The catalytic performance that hydro-thermal process is carried out when can improve nano-carbon material formed body as hydrocarbon dehydrogenation reaction catalyst, but this hair Bright inventor has found in research process, is optimized by the species of nitrogen-containing compound and nitric acid metal salt, can be further Catalytic performance when improving nano-carbon material formed body as hydrocarbon dehydrogenation reaction catalyst.It is described in a preferable example Nitrogen-containing compound is ammonia, and the metallic atom in the nitric acid metal salt is selected from iron, cobalt and nickel.In another preferable example, The nitrogen-containing compound is hydrazine, and the metallic atom in the nitric acid metal salt is selected from palladium and platinum.In another preferable example, The nitrogen-containing compound is urea, and the metallic atom in the nitric acid metal salt is selected from ruthenium and rhodium.
In the second preparation method, the condition of the reaction is to be enough to improve oxygen atom, nitrogen in raw material nano carbon material The content of atom and metallic atom is defined.In course of reaction, the temperature of the aqueous dispersions can in the range of 80-350 DEG C, It is preferred that in the range of 80-310 DEG C.When the temperature of the aqueous dispersions is within above range, can not only effectively carry Oxygen atom, nitrogen-atoms and metal atom content in high raw material nano-carbon material, and will not be to the knot of raw material nano carbon material Configuration state is produced and significantly affected.In course of reaction, the temperature of the aqueous dispersions enters one more preferably in the range of 90-300 DEG C Step is preferably in the range of 100-230 DEG C.
In the second preparation method, the duration of the reaction can be selected according to the temperature of reaction.Usually, The duration of the reaction can be in the range of 0.5-96 hours, preferably in the range of 2-72 hours, more preferably in 12- In the range of 48 hours.
According to the formed body described in second aspect of the present invention, the moisture can be formed using conventional various methods Dispersion liquid, such as raw material nano carbon material can be dispersed in water (being preferably deionized water), then add the nitrogenous chemical combination Thing and the optional nitric acid metal salt, so as to obtain the aqueous dispersions.In order to further improve raw material nano carbon material Dispersion effect, while shorten the scattered time, can use the method for sonic oscillation that raw material nano carbon material is dispersed in into water In.The condition of the sonic oscillation can be conventional selection, and usually, the frequency of the sonic oscillation can be 10-200kHz, Preferably 10-140kHz；The duration of the sonic oscillation can be 0.1-6 hours, preferably 0.5-4 hours.According to this The method of invention, the nitrogen-containing compound and the nitric acid metal salt each can be according to species with solution (being preferably the aqueous solution) Form provide, can also each in the form of pure material provide, be not particularly limited.
According to the formed body described in second aspect of the present invention, oxygen element and nitrogen in the raw material nano carbon material Content is not particularly limited, and can be conventional selection.Usually, the content of oxygen element is not high in the raw material nano carbon material In 1.5 weight %, preferably not higher than 0.5 weight %, more preferably not above 0.3 weight %；The content of nitrogen is not high In 0.2 weight %, preferably not higher than 0.1 weight %, more preferably not above 0.05 weight %, more preferably it is not higher than 0.02 weight %.Remaining nonmetallic heteroatoms (such as phosphorus atoms in the raw material nano carbon material outside oxygen atom and nitrogen-atoms And sulphur atom) total amount (in terms of element) can be customary amount.Usually, in the raw material nano carbon material except oxygen element and The total amount (in terms of element) of remaining nonmetallic heteroatoms outside nitrogen is not higher than 0.5 weight %, preferably not higher than 0.2 weight Measure %, more preferably not above 0.1 weight %, more preferably not higher than 0.05 weight %.The raw material nano carbon material According to the difference in source, some metallic elements may be contained, such as the catalysis used during from preparing raw material nano-carbon material Metallic atom in agent.In the raw material nano carbon material content of metallic atom be generally (in terms of element) 2.5 weight % with Under, preferably below 1.8 weight %, more preferably below 0.5 weight %.
According to the formed body described in second aspect of the present invention, raw material nano carbon material can use this area before use Conventional method is pre-processed (as washed), to remove some impurity of raw material nano carbon material surface；Can also be without Pretreatment, directly use.In preparation example disclosed by the invention, raw material nano carbon material is not pre-processed using preceding.
According to the formed body described in second aspect of the present invention, the raw material nano carbon material can be but be not limited to carbon and receive One or both of mitron, graphene, Nano diamond, thin layer graphite, nano carbon particle, Nano carbon fibers peacekeeping fullerene with On combination.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube in one kind or Two or more combinations.Preferably, the raw material nano carbon material is CNT, more preferably multi-walled carbon nanotube.
According to the formed body described in second aspect of the present invention, in a preferred embodiment, the raw material nano Carbon material is multi-walled carbon nanotube, and the specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, preferably 80- 300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g。
When the raw material nano carbon material is multi-walled carbon nanotube, temperature of the multi-walled carbon nanotube at 400-800 DEG C The weight-loss ratio spent in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800Can be in 0.01- In the range of 0.5, preferably in the range of 0.02-0.4.
According to the formed body described in second aspect of the present invention, the reaction is carried out in closed container.The reaction can To be carried out under self-generated pressure (that is, not applying pressure additionally), can also carry out under pressure.Preferably, it is described anti- It should carry out at autogenous pressures.The closed container can be the common reactor that can realize sealing and heating, as high pressure is anti- Answer kettle.
According to the formed body described in second aspect of the present invention, isolated in the mixture that can also include obtaining from reaction It is dried after solid matter, so as to obtain nano-carbon material.It can use what conventional solid-liquid separating method obtained from reaction Solid matter is isolated in mixture, such as combination more than one or both of centrifugation, filtering and decantation.The bar of the drying Part can be conventional selection, be defined by that can remove the volatile materials in the solid matter isolated.Usually, the drying can To be carried out at a temperature of 50-400 DEG C, carried out preferably at a temperature of 80-180 DEG C, more preferably at a temperature of 100-160 DEG C Carry out.The duration of the drying can be selected according to dry temperature and mode.Usually, the drying continues Time can be preferably 4-24 hours, more preferably 6-12 hours no more than 48 hours.The drying can be in normal pressure (i.e., 1 standard atmospheric pressure) under carry out, can also carry out at reduced pressure.The angle of the efficiency dry from further raising, The drying is preferably carried out at reduced pressure.Also spray drying etc. can be used without solids will be isolated in mixture The step of matter, drying now can be carried out at a temperature of 120-400 DEG C, carried out preferably at a temperature of 150-350 DEG C, more It is preferred that being carried out at a temperature of 180-300 DEG C, the duration of the drying can be selected according to dry degree, if not More than 0.5 hour, preferably no more than 0.2 hour, more preferably less than 0.1 hour.
According to the formed body described in second aspect of the present invention, also contain and be used for the nano-carbon material molding bonded Heat-resistant inorganic oxide.The species and its content of the heat-resistant inorganic oxide with it is heat-resisting described in one side of the invention The species and content of inorganic oxide are identical, are no longer described in detail herein.
Nano-carbon material formed body according to one side of the invention and second aspect can have as needed There is variously-shaped such as spherical, bar shaped.
There is nano-carbon material formed body according to one side of the invention and second aspect higher resisting to break Broken intensity.Usually, can be more than 4N/mm according to the radial direction crushing strength of the nano-carbon material formed body of the present invention, typically For more than 5N/mm.Specifically, the footpath of the nano-carbon material formed body according to one side of the invention and second aspect It is 5-25N/mm, preferably 6-25N/mm, more preferably 10-25N/mm to crushing strength.In the present invention, radial direction crushing strength is pressed According to《Petrochemical Engineering Analysis method》In RIPP 25-90 described in (Science Press, the nineteen ninety first edition, Yang Cui are waited and compiled surely) Defined method measure.
Nano-carbon material formed body according to one side of the invention and second aspect has higher hole Rate.Usually, according to the present invention nano-carbon material formed body porosity can be more than 5%, it might even be possible to for 10% with On, such as can be in the range of 5-50%, preferably in the range of 10-30%, more preferably in the range of 12-25%.This In invention, porosity refers to all interstitial space volume sums and the body of the nano-carbon material formed body in nano-carbon material formed body Long-pending ratio, the porosity of the nano-carbon material formed body is referred to as, is expressed as a percentage, using mercury injection method (with reference to text Offer《Graphite porosity of porous material study on determination method》,《Lubrication and sealing》, 2010,35 (10)：99-101) method determines.
According to the third aspect of the present invention, should the invention provides a kind of preparation method of nano-carbon material formed body Method include nano-carbon material is mixed with binding agent source, obtained mixture is molded, obtains article shaped, by it is described into Type thing is dried and is optionally calcined.
Method according to third aspect of the present invention, the binding agent source are selected from heat-resistant inorganic oxide and/or resistance to The precursor of hot inorganic oxide.The heat-resistant inorganic oxide be preferably one kind in aluminum oxide, silica and titanium oxide or It is two or more.In an example, the heat-resistant inorganic oxide is aluminum oxide, according to the nano-carbon material formed body of the example Higher feed stock conversion can be obtained.
In a preferred embodiment, at least part heat-resistant inorganic oxide is silica, according to the preferable reality Nano-carbon material formed body prepared by the mode of applying can select in the catalyst as hydrocarbon dehydrogenation reaction in feed stock conversion and product Preferably balance is obtained between selecting property.In the preferred embodiment, on the basis of the total amount of the heat-resistant inorganic oxide, The content of the silica can be 10-100 weight %, preferably 20-99 weight %, the heat resistant inorganic oxygen outside silicon The content of compound can be 0-90 weight %, preferably preferably 1-80 weight %, 0-80 weight %.In the preferable embodiment party In formula, the instantiation of the heat-resistant inorganic oxide outside silicon can include but is not limited to aluminum oxide and/or titanium oxide. As an example of the preferred embodiment, the heat-resistant inorganic oxide outside silicon is titanium oxide.
The heat-resistant inorganic oxide can by it is common it is various in the form of provide, such as (such as Ludox, titanium is molten with colloidal sol Glue, Alumina gel) form provide.The precursor of the heat-resistant inorganic oxide can be according to expected heat-resistant inorganic oxide Species is selected.
For example, when the heat-resistant inorganic oxide is aluminum oxide, the precursor of the heat-resistant inorganic oxide can be The material of aluminum oxide can be transformed into, the material of aluminum oxide can be such as formed by hydrolysis-condensation reaction and/or roasting, for example, it is organic Aluminium salt and inorganic aluminate, its instantiation can include but is not limited to hydrated alumina (such as boehmite), aluminium hydroxide, sulphur Sour aluminium, sodium metaaluminate, aluminium chloride, aluminum nitrate and C1-C10Organic aluminium salt (such as aluminium isopropoxide, isobutanol aluminum, three isopropoxies Aluminium, three tert-butoxy aluminium and isooctanol aluminium) one or both of more than.
For another example when the heat-resistant inorganic oxide is silica, the precursor of the heat-resistant inorganic oxide can be with For the material of silica can be transformed into, the material of silica can be such as formed by hydrolysis-condensation reaction and/or roasting, its is specific Example can include but is not limited to the organo-silicon compound that hydrolysis-condensation reaction can occur.It is described that hydrolysis-condensation reaction can occur Organo-silicon compound can be the common various materials that silica can be formed by hydrolysis-condensation reaction.As an example, The organo-silicon compound that hydrolysis-condensation reaction can occur can be more than one or both of compound shown in Formulas I：
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl.The C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4Branched alkyl, its instantiation can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group and the tert-butyl group.Preferably, organic silicon source be selected from methyl silicate, tetraethyl orthosilicate, positive n-propyl silicate, Positive isopropyl silicate and positive silicic acid N-butyl.
In another example when the heat-resistant inorganic oxide is titanium oxide, the precursor of the heat-resistant inorganic oxide can be with For organic titanate and/or inorganic titanium salt, its instantiation can include but is not limited to TiCl4、Ti(SO4)2、TiOCl2, hydrogen-oxygen Change titanium, nitric acid titanium salt, phosphoric acid titanium salt, fatty alcohol titanium and organic titanate (such as tetraisopropyl titanate, the n-propyl of metatitanic acid four, metatitanic acid One or more in four butyl esters and tetraethyl titanate) in one or more.
Method according to third aspect of the present invention, in one embodiment, the binding agent source are selected from heat-resisting Inorganic oxide, such as the heat-resistant inorganic oxide provided with solation.In this embodiment, by nano-carbon material with gluing It is molded after knot agent source is well mixed.In another embodiment, at least part binding agent source is heat resistant inorganic oxygen The precursor of compound.In this embodiment, after nano-carbon material is mixed with binding agent source, entered according to the species in binding agent source Row processing, is transformed into heat-resistant inorganic oxide by the precursor of the heat-resistant inorganic oxide in binding agent source.
Method according to third aspect of the present invention, the mixture preferably also contain at least one alkali, such energy Further improve catalytic activity of the nano-carbon material formed body finally prepared in the catalyst as hydrocarbon dehydrogenation reaction.It is described Alkali can be organic base and/or inorganic base.The inorganic base can be that ammonia, the alkali that cation is alkali metal and cation are alkaline earth It is more than one or both of alkali of metal.The organic base can be one or both of urea, amine, hydramine and quaternary ammonium base More than.
The quaternary ammonium base can be various organic level Four ammonium alkali, and the amine can be various NH3In at least one hydrogen quilt The compound formed after alkyl (being preferably alkyl) substitution, the hydramine can be various NH3In at least one hydrogen by containing hydroxyl The compound formed after alkyl (being preferably alkyl) substitution of base.Specifically, the quaternary ammonium base can be the quaternary ammonium shown in Formula II Alkali,
In Formula II, R5、R6、R7And R8It is identical or different, respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3- C4Branched alkyl, such as：R5、R6、R7And R8Each can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, Isobutyl group or the tert-butyl group.
The amine can be the aliphatic amine and general formula R that formula III represents12(NH2)2One kind in the material of expression or two More than kind,
In formula III, R9、R10And R11Respectively H, C1-C6Alkyl or C6-C12Aryl, and R9、R10And R11When different For H.In the present invention, C1-C6The instantiation of alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, just Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.In the present invention, C6-C12 The instantiation of aryl include but is not limited to phenyl, naphthyl, aminomethyl phenyl and ethylphenyl.
General formula R12(NH2)2In, R12Can be C1-C6Alkylidene or C6-C12Arlydene.In the present invention, C1-C6's Alkylidene includes C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation can include but is not limited to：Methylene Base, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene, the sub- tert-butyl group, sub- n-pentyl and sub- n-hexyl.This In invention, C6-C12The instantiation of arlydene include but is not limited to phenylene and naphthylene.
The hydramine can be the aliphatic hydramine that formula IV represents,
In formula IV, R13、R14And R15Respectively-R16OH or hydrogen, and R13、R14And R15In it is at least one be-R16OH, R16For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylen Base, its instantiation can include but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- isobutyl Base and the sub- tert-butyl group.
The instantiation of the alkali can include but is not limited to ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, Potassium carbonate, barium hydroxide, urea, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, three N-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, three Isobutylamine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, di-iso-amylamine, triisoamylamine, uncle Amylamine, n-hexylamine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, dodecyl-dimethyl amine, N-tridecane base amine, n-tetradecane base amine, n-pentadecane base amine, n-hexadecyl amine, triethanolamine, triisopropanolamine, diethyl Hydramine, two n-propanolamines, three n-propanolamines, two n-butanol amine, three n-butanol amine, dodecyl-dimethyl amine, myristyl two Methyl amine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, substituted or unsubstituted pyrrole Cough up, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substitution or not Substituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted EEDQ, substitution It is or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin, substituted or unsubstituted Pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, to first Base aniline, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,6- dimethylanilines, 3,4- dimethyl Aniline, 3,5- dimethylanilines, 2,4,6- trimethylanilines, o ethyl aniline, N- butylanilines, 2,6- diethylanilines, ring Hexylamine, cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, TMAH, tetraethyl ammonium hydroxide, TPAOH (including its various isomers, such as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), the tetrabutyl Ammonium hydroxide (including its various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group hydroxides Ammonium and tetra-tert ammonium hydroxide) and one or both of four pentyl ammonium hydroxide (including its various isomers) more than.
Preferably, the alkali is organic base, so can further improve the nano-carbon material formed body conduct finally prepared The catalytic activity of the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that the alkali is synthesis of titanium silicon molecular sieve template, such as Formula II institute The quaternary ammonium base shown, the nano-carbon material formed body thus prepared have higher crushing strength, and anti-as hydrocarbon dehydrogenation The catalytic activity further improved is shown during the catalyst answered.
The dosage of the alkali can be selected according to the dosage in binding agent source.Usually, the alkali and the binding agent The mol ratio in source can be 0.1-10：1, preferably 0.15-5：1, more preferably 0.15-3：1, the binding agent source is with oxide Meter.
Method according to third aspect of the present invention, various decentralized media can be used by nano-carbon material and bonding Agent source and optional alkali are well mixed.Preferably, the decentralized medium is water.The dosage of the decentralized medium is with can be by nanometer Carbon material, binding agent source and optional alkali are well mixed to be defined.As an example, when the decentralized medium is water, water Mol ratio with the binding agent source can be 1-150：1, preferably 4-120：1, the binding agent source is in terms of oxide.
The present inventor has found that molecular sieve preparation solution generally contains caused by molecular sieve preparation process in research process There are the required binding agent source of the present invention and alkali, while also contain water, above-mentioned molecular sieve preparation solution is mixed with nano-carbon material One of water, binding agent source and alkali, both or three are alternatively supplemented afterwards, nano-carbon material can not only be molded, and are made Standby nano-carbon material also shows higher crushing strength, while still shows preferable catalytic activity, also real in addition Recycling of the system with molecular sieve for preparing for process waste is showed.
The molecular sieve preparation solution can be the common various required binding agent sources of the present invention and optional of providing The molecular sieve preparation solution of alkali.Preferably, the molecular sieve preparation solution is the crystallization mother liquor and siliceous molecular sieve of siliceous molecular sieve Reset mixed liquor more than one or both of modified mother liquor.The siliceous molecular sieve can be silica zeolite, containing miscellaneous original It is more than one or both of sub- si molecular sieves (such as HTS) and Si-Al molecular sieve.The crystallization mother liquor refers to passing through When hydrothermal crystallizing prepares molecular sieve, the mixture obtained to hydrothermal crystallizing carries out the liquid that separation of solid and liquid obtains, i.e., brilliant from hydro-thermal Change and the liquid mixture remained after the molecular sieve to be formed is isolated in obtained mixture, also referred to as synthesis mother liquid, filtering waste liquid Or filter raw liquid.The rearrangement solution refers to when preparing modified molecular screen by hydrothermal modification rearrangement, after being reset to hydrothermal modification Obtained mixture carries out the liquid that separation of solid and liquid obtains, i.e., isolates molecular sieve in the mixture for resetting to obtain from hydrothermal modification The liquid mixture remained afterwards, also referred to as reset mother liquor, modified mother liquor, reset filtering waste liquid, modified filtering waste liquid, modified filtering Stoste resets filter raw liquid.The crystallization mother liquor and rearrangement solution can be mixed directly with nano-carbon material, also may be used as needed To be mixed with nano-carbon material after being concentrated or being diluted, so that the dosage of binding agent source, alkali and water can be enabled to meet It is required that proportion requirement as previously described is defined.
It is highly preferred that the siliceous molecular sieve preparation solution is the crystallization mother liquor (crystallization of such as silica zeolite of si molecular sieves Mother liquor), crystallization mother liquor (crystallization mother liquor of such as HTS), the crystallization mother liquor of Si-Al molecular sieve of the si molecular sieves containing hetero atom One or both of with the modification rearrangement solution (rearrangement solution of such as silica zeolite and HTS) of above-mentioned siliceous molecular sieve Mixed liquor above.
The concrete composition of the crystallization mother liquor and rearrangement solution is not particularly limited, as long as binding agent source and optional can be provided Alkali.As an example, in the crystallization mother liquor of siliceous molecular sieve, with SiO2The content of the element silicon of meter is generally 0.05-10 weight %, preferably 0.1-5 weight %, more preferably 1-4 weight %；The content of alkali is generally 0.05-15 weights Measure %, more preferably preferably 0.1-15 weight %, 1.5-14 weight %.As another example, the rearrangement of HTS In liquid, with SiO2The content of the element silicon of meter is generally 0.01-10 weight %, preferably 0.02-5 weight %, more preferably 0.5-2 weight %；With TiO2The content of the titanium elements of meter is generally 0.0001-0.2 weight %, preferably 0.001-0.1 weights Measure %, more preferably 0.01-0.08 weight %；The content of alkali is generally 0.01-10 weight %, preferably 0.05-5 weight %, More preferably 1-4 weight %.As there is an example, in the crystallization mother liquor of Si-Al molecular sieve, with SiO2The element silicon of meter contains Amount is generally 0.05-10 weight %, more preferably preferably 0.1-8 weight %, 1-4 weight %；With Al2O3The aluminium element of meter Content is generally 0.01-5 weight %, preferably 0.05-2 weight %, more preferably 0.1-0.5 weight %, and the content of alkali is general For 0.05-15 weight %, preferably 0.1-14 weight %, more preferably 8-13 weight %.
Method according to third aspect of the present invention, in a preferred embodiment, by the mixture Before being molded, the mixture is subjected to hydro-thermal process (that is, mixture hydro-thermal process obtained is molded), such energy Further improve catalytic activity during catalyst of the nano-carbon material formed body finally prepared as hydrocarbon dehydrogenation reaction.It is excellent at this In the embodiment of choosing, nano-carbon material, binding agent source and optional alkali can be dispersed in water, aqueous dispersions are carried out Hydro-thermal process.
In the preferred embodiment, the condition of hydro-thermal process is not particularly limited, as long as enter in closed environment Row high-temperature process.Specifically, the temperature of the hydro-thermal process can be 100-200 DEG C, preferably 120-180 DEG C.It is described The time of hydro-thermal process can be selected according to the temperature for carrying out hydro-thermal process, typically can be 0.5-24 hours, be preferably 6-12 hours.The hydro-thermal process can carry out (that is, in hydrothermal treatment process, not applying pressure additionally at autogenous pressures Power), it can also be carried out under conditions of pressure is additionally applied.Preferably, the hydro-thermal process is carried out at autogenous pressures.
Method according to third aspect of the present invention, the dosage in binding agent source can be according to expected nano-carbon material The content of binding agent is selected in formed body.Usually, the dosage in the binding agent source causes in the formed body that finally prepares, The content of nano-carbon material can be more than 5 weight % (such as more than 6 weight %), preferably more than 10 weight %, more preferably More than 50 weight %, it is still more preferably more than 70 weight %, still more preferably more preferably more than 60 weight % For more than 75 weight %, particularly preferably more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %, Preferably below 94 weight %, more preferably below 90 weight %.In an example, with the nano-carbon material formed body On the basis of total amount, the content of the nano-carbon material can be 5-95 weight %, preferably 6-94 weight %, more preferably 8-92 Weight %, more preferably 10-90 weight %, it is still more preferably 20-90 weight %, particularly preferably 40-90 weight % is measured, particularly preferably 70-90 weight %, the content of the heat-resistant inorganic oxide can be 5-95 weight %, be preferably 6-94 weight %, more preferably 8-92 weight %, more preferably 10-90 weight %, it is still more preferably 10-80 weights %, particularly preferably 10-60 weight % are measured, particularly preferably 10-30 weight %.When carrying out hydro-thermal process before the forming, i.e., Make under relatively low binder content, can also obtain higher intensity.Usually, when carrying out hydro-thermal process before the forming, with institute On the basis of the total amount for stating formed body, the content of the nano-carbon material is preferably 75-95 weight %, and more preferably 85-95 is heavy % is measured, the content of the heat-resistant inorganic oxide is preferably 5-25 weight %, more preferably 5-15 weight %.
Method according to third aspect of the present invention, conventional method can be used to contain nano-carbon material and bonding The mixture in agent source is molded, and obtains article shaped., can be by way of mediating and/or extruding by institute as an example State mixture shaping.The article shaped can have common variously-shaped such as spherical, bar shaped.
Method according to third aspect of the present invention, the article shaped can be dried under normal conditions, To remove the volatile materials in the article shaped.Usually, the drying can be carried out at a temperature of 50-200 DEG C, preferably Carry out at a temperature of 80-180 DEG C, carried out more preferably at a temperature of 100-175 DEG C, such as at a temperature of 120-175 DEG C Carry out.The duration of the drying can be selected according to dry temperature, typically can be no more than 48 hours, preferably For 3-24 hours, more preferably 5-15 hours.
It is able to can also be calcined without roasting through dry article shaped.The present invention does not have for the condition of roasting yet It is particularly limited to, can carries out under normal conditions.Usually, the roasting can 300-800 DEG C, preferably not higher than Carried out at a temperature of 650 DEG C.The roasting can be carried out in oxygen-containing atmosphere (such as air, oxygen), can also be non-oxygenous Carried out in atmosphere (such as nitrogen, group 0 element gas).When the roasting is carried out in oxygen-containing atmosphere, the roasting is preferably in 300- Carry out at a temperature of 500 DEG C, more preferably carried out at a temperature of not higher than 450 DEG C.Enter in the roasting in non-oxygen-containing atmosphere During row, the roasting is more preferably carried out preferably at 400-800 DEG C at a temperature of the temperature not higher than 750 DEG C.The roasting Duration can be 1-12 hours, preferably 2-4 hours.
Method according to third aspect of the present invention, the nano-carbon material in various sources can be handled, can Think not surface treated nano-carbon material, or surface treated nano-carbon material.In the present invention, penetrated using X Photoelectron Spectroscopy detects to the surface of nano-carbon material, if removing C in nano-carbon material surface-element after testing The total content of element outside element is below 2 weight %, then the nano-carbon material is considered as into not surface treated nano carbon material Material, conversely, the nano-carbon material then is considered as into surface treated nano-carbon material.
In one embodiment, the nano-carbon material is not surface treated nano-carbon material.In the embodiment party In formula, before the mixture is molded, the mixture is preferably subjected to hydro-thermal process in closed container, so not It is only capable of significantly improving the intensity of the formed body finally prepared, and the catalytic performance of the formed body finally prepared can be obviously improved. It is highly preferred that the binding agent source and optional alkali source come from molecular sieve preparation solution, by receiving for non-modified surface treatment Rice carbon material carries out hydro-thermal process in molecular sieve preparation solution can further improve the formed body finally prepared in hydrocarbon dehydrogenation reaction In catalytic performance.In this embodiment, the nano-carbon material can by it is common it is various in the form of exist, be specifically as follows But it is not limited in CNT, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, Nano diamond and fullerene One or more kinds of combinations.The CNT can be single-walled carbon nanotube, double-walled carbon nano-tube and multi-wall carbon nano-tube Combination more than one or both of pipe, preferably multi-walled carbon nanotube.The specific surface area of the multi-walled carbon nanotube can be with For 50-500m2/ g, preferably 80-300m2/ g, more preferably 90-250m2/g.The multi-walled carbon nanotube is at 400-800 DEG C Weight-loss ratio in temperature range is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that In the range of 0.01-0.5.As an example, described without surface treating nano carbon material can be second side of the invention Raw material nano carbon material in formed body described in face.
In another embodiment, the nano-carbon material is surface treated nano-carbon material, by X ray photoelectricity Sub- power spectrum determine the surface treated nano-carbon material contain one kind in O elements, N element and metallic element or Two or more modifying elements.In a preferred embodiment, the nano-carbon material preferably comprise O elements, N element with And optional metallic element.In a kind of embodiment being more highly preferred to, the nano-carbon material preferably comprises O elements, N element And metallic element.The metallic element is selected from group ia metal element and group iia metallic element, and its instantiation can wrap Include but be not limited to lithium, be more than one or both of sodium, potassium, beryllium, magnesium, calcium, barium and strontium.The metallic element be preferably sodium, potassium, More than one or both of magnesium, calcium and barium, more preferably more than one or both of magnesium, barium and calcium.
Specifically, the surface treated nano-carbon material can be in the present invention one side formed body Nano-carbon material in second aspect formed body of nano-carbon material and/or the present invention.
According to the fourth aspect of the present invention, the invention provides a kind of method system as described in third aspect of the present invention Standby nano-carbon material formed body.
Nano-carbon material formed body according to the 4th aspect of the present invention has higher crushing strength.Typically Ground, the radial direction crushing strength according to the nano-carbon material formed body of the present invention can be more than 4N/mm, generally more than 5N/mm. Specifically, the radial direction crushing strength of the nano-carbon material formed body according to one side of the invention and second aspect is 5-25N/mm, preferably 6-25N/mm, more preferably 10-25N/mm.
Nano-carbon material formed body according to the 4th aspect of the present invention has higher porosity.Usually, root Porosity according to the nano-carbon material formed body described in the 4th aspect of the present invention can be more than 5%, it might even be possible to be 10% More than, such as can be in the range of 5-50%, preferably in the range of 10-30%, more preferably in the range of 12-25%.
According to the fifth aspect of the present invention, the invention provides a kind of forming method of nano-carbon material, this method bag Include in closed container, nano-carbon material is subjected to hydro-thermal process in a kind of aqueous dispersions, the slurry that hydro-thermal process is obtained Shaping, obtains article shaped, the article shaped is dried and is optionally calcined, and the aqueous dispersions contain binding agent source, The binding agent source is selected from the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide.The binding agent source and this hair The species in the bright 3rd aspect binding agent source is identical, is no longer described in detail herein.
According to the method described in the 5th aspect of the present invention, the nano-carbon material in various sources can be handled, can Think not surface treated nano-carbon material, or surface treated nano-carbon material.The nano-carbon material tool Body can be the nano-carbon material described in third aspect of the present invention methods described, no longer be described in detail herein.
According to the method described in the 5th aspect of the present invention, the aqueous dispersions preferably also contain at least one inorganic agent, The inorganic agent is alkali and/or nitric acid metal salt.It so can further improve the anti-of the nano-carbon material formed body that finally prepares Breaking strength, while when can also further improve catalyst of the nano-carbon material formed body finally prepared as hydrocarbon dehydrogenation reaction Catalytic activity.Particularly when the nano-carbon material is not surface treated nano-carbon material, it can significantly improve final The crushing strength and catalytic performance of the nano-carbon material formed body of preparation.
The alkali is identical with the species of alkali and dosage that are related in third aspect of the present invention methods described, herein no longer It is described in detail.
Metallic element in the nitric acid metal salt is selected from the metallic element that can form nitric acid metal salt, is such as selected from element Group ia metal element, group iia metallic element, Group IIIB metallic element, group ivb metallic element, V B in periodic table Race's metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, I B-group metal element, Group iib metallic element, group III A metallic element, group IVA metallic element and V A races metallic element.The nitric acid metal The instantiation of metallic element in salt can include but is not limited to lithium, sodium, potassium, magnesium, calcium, barium, strontium, scandium, yttrium, rare earth metal member Plain (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminium, Germanium, tin and antimony.Preferably, the metallic element in the nitric acid metal salt is selected from group ia metal element, group iia metal member Element, group VIII metallic element, I B-group metal element, group iib metallic element and group IVA metallic element, are thus prepared Nano-carbon material formed body in the catalyst as hydrocarbon dehydrogenation reaction, higher catalytic activity can be obtained.It is highly preferred that institute The metallic element stated in nitric acid metal salt is selected from group VIII metallic element.It is further preferred that in the nitric acid metal salt Metallic element is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The dosage of the inorganic agent can carry out appropriate selection according to the amount in binding agent source.Preferably, the inorganic agent Mol ratio with the binding agent source can be 0.1-10：1, preferably 0.15-5：1, more preferably 0.15-3：1, the bonding Agent source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, when the inorganic agent is alkali and nitric acid metal salt, alkali and nitric acid Ratio between metal salt is not particularly limited.Preferably, the mol ratio between alkali and nitric acid metal salt can be 1：0.1-10, Preferably 1：0.2-5, more preferably 1：0.2-1, more preferably 1：0.2-0.5.
It is not surface treated nano-sized carbon in the nano-carbon material according to the method described in the 5th aspect of the present invention During material, the modifying agent is particularly preferably alkali and nitric acid metal salt.Handled with being individually used as using alkali or nitric acid metal salt Agent is compared, and not surface treated nano-carbon material is carried out hydro-thermal process and made as inorganic agent using alkali and nitric acid metal salt Standby nano-carbon material formed body has higher crushing strength, in the catalyst as hydrocarbon dehydrogenation reaction in use, also showing Higher catalytic activity is shown.
According to the method described in the 5th aspect of the present invention, the dosage of water with can by nano-carbon material and binding agent source and Optional alkali is well mixed to be defined.Usually, water and the mol ratio in the binding agent source can be 1-150：1, preferably 4- 120：1, the binding agent source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, the dosage in the binding agent source can be according to formed body expection group Into being selected.Usually, the dosage in the binding agent source make it that in the formed body that finally prepares that the content of nano-carbon material can Think more than 5 weight % (such as more than 6 weight %), preferably more than 10 weight %, more preferably more than 50 weight %, further It is still more preferably more than 70 weight % preferably more than 60 weight %, is still more preferably more than 75 weight %, especially Preferably more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %, preferably below 94 weight %, More preferably below 90 weight %.In an example, on the basis of the total amount of the nano-carbon material formed body, the nanometer The content of carbon material can be 5-95 weight % (such as 6-94 weight %), and preferably 8-92 weight %, more preferably 10-90 are heavy %, more preferably 20-90 weight % are measured, is still more preferably 40-90 weight %, particularly preferably 70-90 weight %, The content of the heat-resistant inorganic oxide can be 5-95 weight % (such as 6-94 weight %), preferably 8-92 weight %, more excellent Elect 10-90 weight %, more preferably 10-80 weight % as, be still more preferably 10-60 weight %, particularly preferably 10-30 weight %.Nano-carbon material formed body prepared by method described according to the fifth aspect of the present invention, even in relatively low Binder content under, can also obtain higher intensity.Usually, on the basis of the total amount of the formed body, the nano-sized carbon The content of material is preferably 80-95 weight %, more preferably 85-95 weight %, and the content of the heat-resistant inorganic oxide is preferred For 5-20 weight %, more preferably 5-15 weight %.
According to the method described in the 5th aspect of the present invention, the condition of hydro-thermal process is not particularly limited, as long as close High-temperature process is carried out in closed loop border.Specifically, the temperature of the hydro-thermal process can be 100-200 DEG C, preferably 120- 180℃.The time of the hydro-thermal process can be selected according to the temperature for carrying out hydro-thermal process, typically can be that 0.5-24 is small When, preferably 6-12 hours.The hydro-thermal process can be carried out (that is, in hydrothermal treatment process, not additionally at autogenous pressures Apply pressure), it can also be carried out under conditions of pressure is additionally applied.Preferably, the hydro-thermal process is entered at autogenous pressures OK.
According to the method described in the 5th aspect of the present invention, the shaping, the drying of article shaped and optionally it is calcined Method and condition are identical with the description in the method described in third aspect of the present invention, are no longer described in detail herein.
The sixth aspect of the invention, prepared the invention provides a kind of method as described in the 5th aspect of the present invention Nano-carbon material formed body.
Nano-carbon material formed body according to the 6th aspect of the present invention has higher crushing strength.Typically Ground, the radial direction crushing strength of the nano-carbon material formed body according to the 6th aspect of the present invention can be more than 7N/mm, excellent More than 10N/mm is elected as, typically in the range of 12-25N/mm.
Nano-carbon material formed body according to the 6th aspect of the present invention has higher porosity.Usually, root Porosity according to the nano-carbon material formed body described in the 6th aspect of the present invention can be more than 5%, it might even be possible to be 10% More than, such as can be in the range of 5-50%, preferably in the range of 10-30%, more preferably in the range of 12-25%.
According to the seventh aspect of the present invention, the invention provides according to the present invention the on one side, second aspect, the Application of the nano-carbon material formed body as the catalyst of hydrocarbon dehydrogenation reaction described in four aspects and the 6th aspect.It is described de- Hydrogen reaction can be carried out in the presence of oxygen, can not also be carried out in the presence of oxygen.Preferably, the dehydrogenation reaction is in oxygen In the presence of carry out, can so obtain more preferable catalytic effect.The species of the hydrocarbon and the actual conditions of dehydrogenation reaction will be under Text is described in detail, and is no longer described in detail herein.
According to the eighth aspect of the present invention, the invention provides a kind of hydrocarbon dehydrogenation reaction method, this method, which is included in, deposits Under conditions of oxygen, under hydrocarbon dehydrogenation reaction conditions, by hydrocarbon with the present invention the on one side, second aspect, Nano-carbon material formed body contact described in 4th aspect and the 6th aspect.Can according to nano-carbon material formed body of the present invention To be used directly as catalyst, used after can also crushing according to specific needs as catalyst.
Dehydrogenation can be carried out to polytype hydrocarbon according to the hydrocarbon dehydrogenation reaction method of the present invention, so as to obtain unsaturation Hydrocarbon, such as alkene.The method according to the invention to alkane particularly suitable for carrying out dehydrogenation, so as to obtain alkene.The hydrocarbon is preferably alkane Hydrocarbon, such as C2-C12Alkane.Specifically, the hydrocarbon can be but be not limited to ethane, propane, normal butane, iso-butane, pentane, different Pentane, neopentane, pentamethylene, n-hexane, 2- methylpentanes, 3- methylpentanes, 2,3- dimethylbutanes, hexamethylene, methyl ring Pentane, normal heptane, 2- methyl hexanes, 3- methyl hexanes, 2- ethylpentanes, 3- ethylpentanes, 2,3- dimethyl pentanes, 2,4- bis- Methylpentane, normal octane, 2- methyl heptanes, 3- methyl heptanes, 4- methyl heptanes, 2,3- dimethylhexanes, 2,4- dimethyl oneself Alkane, 2,5- dimethylhexanes, 3- ethyl hexanes, 2,2,3- trimethylpentanes, 2,3,3- trimethylpentanes, 2,4,4- trimethyls penta Alkane, 2- methyl -3- ethylpentanes, n -nonane, 2- methyloctanes, 3- methyloctanes, 4- methyloctanes, 2,3- dimethyl heptanes, 2,4- dimethyl heptanes, 3- ethyl heptanes, 4- ethyl heptanes, 2,3,4- trimethyl cyclohexanes, 2,3,5- trimethyl cyclohexanes, 2,4,5- Trimethyl cyclohexane, 2,2,3- trimethyl cyclohexanes, 2,2,4- trimethyl cyclohexanes, 2,2,5- trimethyl cyclohexanes, 2,3,3- trimethyls oneself Alkane, 2,4,4- trimethyl cyclohexanes, 2- methyl -3- ethyl hexanes, 2- methyl -4- ethyl hexanes, 3- methyl -3- ethyl hexanes, 3- Methyl -4- ethyl hexanes, 3,3- diethylpentanes, 1- methyl -2- ethyl cyclohexanes, 1- methyl -3- ethyl cyclohexanes, 1- first (including trimethyl-cyclohexane is various for base -4- ethyl cyclohexanes, n-propyl hexamethylene, isopropyl cyclohexane, trimethyl-cyclohexane Isomers, such as 1,2,3- trimethyl-cyclohexanes, 1,2,4- trimethyl-cyclohexanes, 1,2,5- trimethyl-cyclohexanes, 1,3,5- front threes Butylcyclohexane), n-decane, 2- methylnonanes, 3- methylnonanes, 4- methylnonanes, 5- methylnonanes, 2,3- dimethyl octane, 2,4- dimethyl octane, 3- ethyls octane, 4- ethyls octane, 2,3,4- trimethylheptanes, 2,3,5- trimethylheptanes, 2,3,6- Trimethylheptane, 2,4,5- trimethylheptanes, 2,4,6- trimethylheptanes, 2,2,3- trimethylheptanes, 2,2,4- trimethyls heptan Alkane, 2,2,5- trimethylheptanes, 2,2,6- trimethylheptanes, 2,3,3- trimethylheptanes, 2,4,4- trimethylheptanes, 2- first Base -3- ethyl heptanes, 2- methyl -4- ethyl heptanes, 2- methyl -5- ethyl heptanes, 3- methyl -3- ethyl heptanes, 4- methyl -3- Ethyl heptane, 5- methyl -3- ethyl heptanes, 4- methyl -4- ethyl heptanes, 4- propyl group heptane, 3,3- diethylhexanes, 3,4- bis- Ethyl hexane, 2- methyl -3,3- diethylpentanes, vinylbenzene, 1- phenyl-propanes, 2- phenyl-propanes, 1- phenyl butanes, 2- phenyl Combination more than one or both of butane, 1- phenyl pentanes, 2- phenyl pentanes and 3- phenyl pentanes.
The hydrocarbon is more preferably more than one or both of propane, normal butane, iso-butane and vinylbenzene, further preferably For normal butane.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the reaction can be carried out under conditions of it oxygen be present, can also Carried out under conditions of in the absence of oxygen.It is preferred that carried out under conditions of it oxygen be present.When being carried out under conditions of oxygen being present, The dosage of oxygen can be conventional selection.Usually, the mol ratio of hydrocarbon and oxygen can be 0.01-100：1, preferably 0.1- 10：1, more preferably 0.2-5：1, most preferably 0.5-2：1.
According to the hydrocarbon dehydrogenation reaction method of the present invention, can by carrier gas by hydrocarbon and optional oxygen be sent into reactor with The haptoreaction of nano-carbon material containing hetero atom.The carrier gas can be it is conventional at reaction conditions will not be with reactant and reaction Chemical interaction and the gas that will not be decomposed occur for product, such as nitrogen, carbon dioxide, rare gas and vapor One or both of more than combination.The dosage of the carrier gas can be conventional selection.Usually, the content of carrier gas can be with 30-99.5 volume %, preferably 50-99 volumes %, more preferably 70-98 volumes %.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the temperature of the contact can be conventional selection, to be enough to send out hydrocarbon Raw dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature Degree is lower to be carried out, and is carried out more preferably at a temperature of 350-550 DEG C, further preferably in 400-450 DEG C of temperature when such as hydrocarbon being butane Degree is lower to be carried out.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the contact is carried out preferably in fixed bed reactors.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the duration of the contact can be selected according to the temperature of contact Select, when such as described contact is carried out in fixed bed reactors, the duration of contact can be represented with the weight (hourly) space velocity (WHSV) of charging. Usually, the weight (hourly) space velocity (WHSV) of feed gas can be 1-50000h-1, preferably 10-20000h-1, more preferably 50-10000h-1, more preferably 100-8000h-1, such as 3000-5000h-1。
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following preparation example, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies equipped with Thermo Tested on the ESCALab250 type x-ray photoelectron spectroscopies of Avantage V5.926 softwares, excitaton source is monochromatization Al K α X ray, energy 1486.6eV, power 150W, the penetrating base vacuum that can be 30eV, analyze during test used in narrow scan For 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, in Thermo Avantage softwares Upper carry out data processing, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample is before testing at 150 DEG C Temperature and 1 normal atmosphere are depressed to be dried 3 hours in helium atmosphere.
In following preparation example, thermogravimetric analysis is carried out on TA5000 thermal analyzers, and test condition is air atmosphere, heating speed It is room temperature (25 DEG C) to 1000 DEG C to spend for 10 DEG C/min, temperature range.Sample is big in 150 DEG C of temperature and 1 standard before testing Dried 3 hours in helium atmosphere under air pressure.Using the ASAP2000 types N of Micromertrics companies of the U.S.2Physical adsorption appearance Measurement the specific area.
The property of multi-walled carbon nanotube in following preparation example as raw material nano carbon material is listed in table 1 below.
Table 1
In following examples and comparative example, the content of silicon, titanium and aluminium element in crystallization mother liquor and rearrangement solution and alkali Content is using the DV types of Perkin-Elmer 3300 sensing coupled plasma (ICP) spectroanalysis instrument measure.
In following examples and comparative example, radial direction crushing strength according to《Petrochemical Engineering Analysis method》(Science Press, The nineteen ninety first edition, Yang Cui surely wait compile) described in RIPP 25-90 specified in method measure；Porosity refers to nano-carbon material The ratio of all interstitial space volume sums and the volume of the nano-carbon material formed body, is referred to as the nanometer in formed body The porosity of carbon material formed body, is expressed as a percentage, using mercury injection method (reference literature《Graphite porosity of porous material determines Technique study》,《Lubrication and sealing》, 2010,35 (10)：99-101) method determines.
Preparation example 1-16 is used to prepare nano-carbon material containing hetero atom, and preparation example 17-42 is used to prepare to be received containing metallic atom Rice carbon material.
Preparation example 1
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube A of raw material nano carbon material Co., Ltd) it is scattered in deionized water, wherein, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes：Frequency For 14kHz, the time is 0.5 hour.Then, NH is added into aqueous dispersions3, stir, so as to obtain aqueous dispersions, its In, NH3There is provided in the form of the 25 weight % aqueous solution, by raw material nano carbon material：NH3：H2O weight ratio is 1：0.6：11.8 Ratio feed intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 170 DEG C of temperature Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), dry 6 hours at a temperature of 120 DEG C, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 2
It is equipped with being placed in the identical aqueous dispersions of preparation example 1 in the three-necked flask of condenser pipe, the three-necked flask is placed in In 170 DEG C of oil bath, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in three-necked flask is down to room temperature, Reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After being dried 6 hours under degree, nano-carbon material containing hetero atom is obtained.
Preparation example 3
Nitrogenous nano-carbon material is prepared using with the identical method of preparation example 1, unlike, in step (1), as raw material Nano-carbon material is multi-walled carbon nanotube B (being purchased from Shandong great Zhan nano materials Co., Ltd).
Preparation example 4
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, unlike, in step (1), by original Expect nano-carbon material：NH3：H2O weight ratio is 1：4：11.8 ratio feeds intake.
Preparation example 5
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube C of raw material nano carbon material Co., Ltd) it is scattered in deionized water, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes：Frequency is 90kHz, time are 2 hours, then add NH3, stir, so as to obtain aqueous dispersions, wherein, NH3It is water-soluble with 20 weight % The form of liquid provides, by raw material nano carbon material：NH3：H2O weight ratio is 1：0.4：19.6 ratio feeds intake.
(2) by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining, in 150 DEG C of temperature Under, react 36 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into normal pressure, 100 DEG C At a temperature of dry 12 hours after, obtain nano-carbon material containing hetero atom, its composition, specific surface area and w500/w800Arranged in table 2 Go out.
Preparation example 6
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 5, unlike, in step (1), as Raw material nano carbon material is multi-walled carbon nanotube D (being purchased from Shandong great Zhan nano materials Co., Ltd).
Preparation example 7
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 5, unlike, in step (1), by original Expect nano-carbon material：NH3：H2O weight ratio is 1：0.1：19.6 ratio feeds intake.
Preparation example 8
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, difference is as follows：
In step (1), raw material nano carbon material is disperseed in deionized water, then to add urea, stir, so as to Aqueous dispersions are obtained, wherein, urea is provided in the form of the 20 weight % aqueous solution, by raw material nano carbon material：Urea：H2O's Weight ratio is 1：2.5：22.5 ratio feeds intake；In step (2), by obtained aqueous dispersions with polytetrafluoroethyllining lining In autoclave, at a temperature of 140 DEG C, react 24 hours at autogenous pressures.
Preparation example 9
It is equipped with being placed in the identical aqueous dispersions of preparation example 8 in the three-necked flask of condenser pipe, the three-necked flask is placed in In 140 DEG C of oil bath, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in three-necked flask is down to room temperature, Reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After being dried 6 hours under degree, nano-carbon material containing hetero atom is obtained.
Preparation example 10
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 8, unlike, in step (1), as Raw material nano carbon material is multi-walled carbon nanotube B.
Preparation example 11
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 8, unlike, in step (1), by original Expect nano-carbon material：Urea：H2O weight ratio is 1：0.2：22.5 ratio feeds intake.
Preparation example 12
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 5, difference is as follows：
In step (1), raw material nano carbon material is disperseed in deionized water, then to add urea, stir, so as to Aqueous dispersions are obtained, wherein, urea is provided in the form of the 20 weight % aqueous solution, by raw material nano carbon material：Urea：H2O's Weight ratio is 1：1.5：28.5 ratio feeds intake；In step (2), by obtained aqueous dispersions with polytetrafluoroethyllining lining In autoclave, at a temperature of 110 DEG C, react 24 hours at autogenous pressures.
Preparation example 13
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 1, difference is as follows：
In step (1), raw material nano carbon material is disperseed in deionized water, then to add hydrazine, stir, so as to To aqueous dispersions, wherein, hydrazine is provided in the form of the 20 weight % aqueous solution, by raw material nano carbon material：Hydrazine：H2O weight ratio For 1：5：50 ratio feeds intake；In step (2), by obtained aqueous dispersions in the autoclave with polytetrafluoroethyllining lining In, at a temperature of 125 DEG C, react 24 hours at autogenous pressures.
Preparation example 14
It is equipped with being placed in the identical aqueous dispersions of preparation example 13 in the three-necked flask of condenser pipe, the three-necked flask is placed in In 125 DEG C of oil bath, back flow reaction 24 hours at ambient pressure.After reaction terminates, after the temperature in three-necked flask is down to room temperature, Reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 DEG C of temperature After being dried 6 hours under degree, nano-carbon material containing hetero atom is obtained.
Preparation example 15
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 13, unlike, in step (1), press Raw material nano carbon material：Hydrazine：H2O weight ratio is 1：15：50 ratio feeds intake.
Preparation example 16
Nano-carbon material containing hetero atom is prepared using with the identical method of preparation example 5, difference is as follows：
In step (1), raw material nano carbon material is disperseed in deionized water, then to add hydrazine, stir, so as to To aqueous dispersions, wherein, hydrazine is provided in the form of the 25 weight % aqueous solution, by raw material nano carbon material：Hydrazine：H2O weight ratio For 1：0.4：10 ratio feeds intake；In step (2), by obtained aqueous dispersions in the reaction under high pressure with polytetrafluoroethyllining lining In kettle, at a temperature of 165 DEG C, react 36 hours at autogenous pressures.
Preparation example 17
(1) deionized water is dispersed in using 20g as the multi-walled carbon nanotube A of raw material nano carbon material, is dispersed in ultrasound and shakes Carried out under the conditions of swinging, sonic oscillation condition includes：Frequency is 140kHz, and the time is 1 hour.Then, NH is added3And ferric nitrate, So as to obtain aqueous dispersions, wherein, by raw material nano carbon material：NH3：Ferric nitrate：H2O weight ratio is 1：1.6：1：17.4 Ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 100 DEG C of temperature Under, react 24 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into, in normal pressure, (1 standard is big Air pressure, similarly hereinafter), after drying 12 hours at a temperature of 120 DEG C, nano-carbon material containing metallic atom is obtained, its composition, specific surface area And w500/w800Listed in table 3.
Preparation example 18
It is equipped with being placed in the identical aqueous dispersions of preparation example 17 in the three-necked flask of condenser pipe, the three-necked flask is placed in Temperature is back flow reaction 24 hours under normal pressure in 100 DEG C of oil bath.After reaction terminates, treat that the temperature in three-necked flask is down to After room temperature, reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained
Preparation example 19
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 17, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube B.
Preparation example 20
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 17, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in spontaneous pressure Reacted 24 hours under power.
Preparation example 21
It is scattered in deionized water using 20g as the multi-walled carbon nanotube C of raw material nano carbon material, it is dispersed in sonic oscillation Under the conditions of carry out, sonic oscillation condition includes：Frequency is 90kHz, and the time is 4 hours.Then, NH is added3And palladium nitrate, so as to Aqueous dispersions are obtained, wherein, by raw material nano carbon material：NH3：Palladium nitrate：H2O weight ratio is 1：5：1：44 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 200 DEG C of temperature Under, react 48 hours at autogenous pressures.After reaction terminates, after the temperature in autoclave is down to room temperature, reaction is opened Kettle, reactant mixture is filtered and washed, and collect solid matter.By the solid matter being collected into normal pressure, 160 DEG C At a temperature of dry 10 hours after, obtain nano-carbon material containing metallic atom, its composition, specific surface area and w500/w800In table 3 List.
Preparation example 22
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube D.
Preparation example 23
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 310 DEG C, in spontaneous pressure Reacted 48 hours under power.
Preparation example 24
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, unlike, in step (1), Raw material nano carbon material：NH3：Palladium nitrate：H2O weight ratio is 1：0.2：1：44.
Preparation example 25
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, unlike, in step (1), Palladium nitrate is replaced with the nickel nitrate of equimolar amounts.
Preparation example 26
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 17, difference is as follows：Step (1) In, raw material nano carbon material is scattered in deionized water, hydrazine and palladium nitrate are then added, so as to obtain aqueous dispersions, wherein, By raw material nano carbon material：Hydrazine：Palladium nitrate：H2O weight ratio is 1：1：0.6：18.4 ratio feeds intake；In step (2), will To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 110 DEG C, at autogenous pressures Reaction 36 hours.
Preparation example 27
It is equipped with being placed in the identical aqueous dispersions of preparation example 26 in the three-necked flask of condenser pipe, the three-necked flask is placed in Temperature is back flow reaction 36 hours under normal pressure in 110 DEG C of oil bath.After reaction terminates, treat that the temperature in three-necked flask is down to After room temperature, reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.
Preparation example 28
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 26, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in spontaneous pressure Reacted 36 hours under power.
Preparation example 29
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 26, unlike, received as raw material Rice carbon material is multi-walled carbon nanotube B.
Preparation example 30
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, difference is as follows：Step (1) In, raw material nano carbon material is scattered in deionized water, hydrazine and platinum nitrate are then added, so as to obtain aqueous dispersions, wherein, By raw material nano carbon material：Hydrazine：Platinum nitrate：H2O weight ratio is 1：1：0.5：48.5 ratio feeds intake；In step (2), will To aqueous dispersions be placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 180 DEG C, at autogenous pressures Reaction 12 hours.
Preparation example 31
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 30, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 350 DEG C, in spontaneous pressure Reacted 12 hours under power.
Preparation example 32
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 30, unlike, in step (1), Platinum nitrate is replaced with the ferric nitrate of equimolar amounts.
Preparation example 33
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 30, unlike, in step (1), Platinum nitrate is replaced with the nitric acid ruthenium of equimolar amounts.
Preparation example 34
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 17, difference is as follows：Step (1) In, raw material nano carbon material is scattered in deionized water, urea and nitric acid ruthenium are then added, so as to obtain aqueous dispersions, its In, by raw material nano carbon material：Urea：Nitric acid ruthenium：H2O weight ratio is 1：3：1：16 ratio feeds intake；, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 120 DEG C, in self-generated pressure Lower reaction 12 hours.
Preparation example 35
It is equipped with being placed in the identical aqueous dispersions of preparation example 34 in the three-necked flask of condenser pipe, the three-necked flask is placed in Temperature is back flow reaction 12 hours under normal pressure in 120 DEG C of oil bath.After reaction terminates, treat that the temperature in three-necked flask is down to After room temperature, reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal pressure, 120 After being dried 12 hours at a temperature of DEG C, nano-carbon material containing metallic atom is obtained.
Preparation example 36
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 34, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 80 DEG C, in spontaneous pressure Reacted 12 hours under power.
Preparation example 37
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 34, unlike, received as raw material Rice carbon material is multi-walled carbon nanotube B.
Preparation example 38
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 21, difference is as follows：Step (1) In, raw material nano carbon material is scattered in deionized water, urea and rhodium nitrate are then added, so as to obtain aqueous dispersions, its In, by raw material nano carbon material：Urea：Rhodium nitrate：H2O weight ratio is 1：1：3：46 ratio feeds intake；, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 230 DEG C, in self-generated pressure Lower reaction 36 hours.
Preparation example 39
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 38, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube D.
Preparation example 40
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 38, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 310 DEG C, in spontaneous pressure Reacted 36 hours under power.
Preparation example 41
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 38, unlike, rhodium nitrate is used etc. The nickel nitrate of mole replaces.
Preparation example 42
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 38, unlike, rhodium nitrate is used etc. The platinum nitrate of mole replaces.
Embodiment 1-81 is used to illustrate according to nano-carbon material formed body of the present invention and preparation method thereof.
It is related to following binding agent source in embodiment 1-81.
Ludox：Purchased from Zhejiang Province Yuda Chemical Co., Ltd, dioxide-containing silica is 25 weight %
Tetraethyl orthosilicate：Purchased from Zhangjiagang new Asia Chemical Co., Ltd. (numbering TES)
Alumina gel：Purchased from Shandong, Chile reaches chemical inc, and alumina content is 12 weight %
Aluminium isopropoxide：Purchased from Beijing Deco Dao Jin Science and Technology Ltd.s (numbering IPOA)
Titanium oxide：Purchased from Shandong Origine Nanomaterial Engineering Co., Ltd., particle diameter 5-10nm
Tetraethyl titanate：Purchased from Jin Yu chemical industry Co., Ltd of Shouguang City (numbering TET)
(1) crystallization mother liquor of HTS
Method according to US4410501 embodiments 1 prepares titanium-silicon molecular sieve TS-1, and collects crystallization mother liquor.Concrete operations Process is：
455g tetraethyl orthosilicates are placed in equipped with agitating device and for without CO2In the reactor of atmosphere, Ran Houxian The TPAOH aqueous solution of 15g tetraethyl titanates and 800g concentration for 25 weight % is added afterwards., will after stirring 1 hour Temperature is increased to 80~90 DEG C, continues stirring 5 hours.Then deionized water is added into reaction solution, until the totality of reaction solution Product is 1.5L.Then, reaction solution is transferred to and be equipped with the autoclave of agitating device, the hydro-thermal under 175 DEG C, self-generated pressure After crystallization 10 days, obtained reactant mixture is filtered, crystallization mother liquor is collected, by the solid being filtrated to get in 550 DEG C of air gas It is calcined 6 hours in atmosphere, so as to obtain titanium-silicon molecular sieve TS-1.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 1.2 weight %, with TiO2 The content of the titanium elements of meter is 0.04 weight %, and the content of TPAOH is 3.1 weight %.The crystallization mother liquor is concentrated (concentrate numbering be TS-A) on the basis of the total amount of concentrate, with SiO2The content of the element silicon of meter is 3.6 weight %, with TiO2The content of the titanium elements of meter is 0.12 weight %, and the content of TPAOH is 9.3 weight %.
(2) crystallization mother liquor of HTS
Method according to US4410501 embodiments 2 prepares titanium-silicon molecular sieve TS-1, and collects crystallization mother liquor.Concrete operations Process is：
150g tetraethyl titanates are slowly added dropwise in 2.5L distilled water and hydrolyzed under agitation, obtain a white gum Suspension, this suspension is then cooled to 5 DEG C；Then it is 30% by the 1.8L mass concentrations for having cooled to 5 DEG C in advance Aqueous hydrogen peroxide solution is incorporated in wherein, and is kept for 2 hours at 5 DEG C under conditions of intermittent stirring, and it is molten to obtain an orange clarification Liquid；Then the TPAOH aqueous solution that the 2.4L mass concentrations for having cooled to 5 DEG C in advance are 25% is added to orange In settled solution, after 1 hour, 500g SiO are added2The Ludox that content is 40% carefully mixes, and obtained mixture is in normal temperature Left overnight；Most after 70-80 DEG C of heating stirring 6 hours.Obtained mixture is transferred to the high pressure for being equipped with agitating device In reactor, hydrothermal crystallizing filtered obtained reactant mixture after 10 days under 175 DEG C, self-generated pressure, and it is female to collect crystallization Liquid, the solid phase being filtrated to get is calcined 6 hours in 550 DEG C of air atmospheres, confirmed through X-ray diffraction analysis, obtain titanium silicon point Son sieve TS-1.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 2.8 weight %, with TiO2 The content of the titanium elements of meter is 0.04 weight %, and the content of TPAOH is 1.6 weight %.The crystallization mother liquor is concentrated (concentrate numbering be TS-B) on the basis of the total amount of concentrate, with SiO2The content of the element silicon of meter is 7.0 weight %, with TiO2The content of the titanium elements of meter is 0.1 weight %, and the content of TPAOH is 4.0 weight %.
(3) crystallization mother liquor of HTS
According to J.Chem.Soc.Chem.Commun., the method described in 1992,589-590 prepares HTS Ti-Beta, crystallization mother liquor is collected during separation of solid and liquid.Specifically preparation process is：
At room temperature, tetraethyl titanate and amorphous silica gel Aerosil 200 are added to tetraethyl hydrogen-oxygen under agitation Change in ammonium (TEAOH) aqueous solution, then add appropriate aluminum nitrate, the glue mole composition now formed is A12O3：TiO2： SiO2：H2O：TEAOH=1：12：388：6000：108, the glue of formation is transferred to the autoclave with polytetrafluoroethyllining lining Middle carry out dynamic crystallization, crystallization temperature are 130 DEG C, mixing speed 60rpm, crystallization time 3d.After cooling, consolidate what is obtained Liquid mixture is centrifuged, and obtains solid and crystallization mother liquor (numbering TS-C).The solid isolated is washed with water to pH=9 Left and right, 80 DEG C of dry 5h, the lower 580 DEG C of roastings 5h of air atmosphere, so as to obtain HTS Ti-Beta.
After testing, on the basis of the total amount of crystallization mother liquor, with SiO2The content of the element silicon of meter is 3.4 weight %, with TiO2 The content of the titanium elements of meter is 0.3 weight %, and the content of tetraethyl ammonium hydroxide is 13.1 weight %.
(4) rearrangement solution of HTS
Method according to the embodiment 9 of China's application 99126289.1 obtains the rearrangement solution of HTS, specific to prepare Process is：
According to TS-1 molecular sieves (gram)：Tetraethyl ammonium hydroxide (mole)：Water (mole)=100：0.25：60 ratio is mixed Close uniformly, mixture is placed in stainless steel sealing reactor, constant temperature is placed 3 days under 175 DEG C and self-generated pressure.Cool down release Afterwards, filtered, gained filtrate is the rearrangement solution of HTS.
After testing, on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 1.1 weight %, with TiO2Meter The contents of titanium elements be 0.02 weight %, the content of TPAOH is 3.6 weight %.Rearrangement solution is concentrated into (concentration Liquid numbering is TS-D) extremely on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 4.4 weight %, with TiO2Meter The contents of titanium elements be 0.08 weight %, the content of TPAOH is 14.4 weight %.
(5) crystallization mother liquor of Si-Al molecular sieve
With reference to the method for US4410501 embodiments 1 sial is prepared using silicon source aluminium isopropoxide replacement titanium source tetraethyl titanate Molecular sieve, and collect crystallization mother liquor.Specific operation process is：
Without CO2Atmosphere under, 455g tetraethyl orthosilicates are positioned in heatproof glass container, with stirring add 15g Aluminium isopropoxide, be subsequently added into by 800g mass concentrations be 25% the TPAOH aqueous solution, mix 4h after, in 80-90 DEG C heating stirring drives ethanol out of after 5 hours completely.Then 1.5L is added water to, obtained mixture is transferred to outfit stirring In the autoclave of device, hydrothermal crystallizing 10 days under 175 DEG C, self-generated pressure, obtained reactant mixture is filtered, collected Crystallization mother liquor.
After testing, on the basis of the total amount of crystallization mother liquor (being AS-F by crystallization mother liquor numbering), with SiO2The element silicon of meter Content be 2.3 weight %, with Al2O3The content of the aluminium element of meter is 0.14 weight %, and the content of TPAOH is 12.5 weight %.By crystallization mother liquor concentration (concentrate numbering is AS-E) extremely on the basis of the total amount of concentrate, with concentrate Total amount on the basis of, with SiO2The content of the element silicon of meter is 8.28 weight %, with Al2O3The content of the aluminium element of meter is 0.50 Weight %, the content of TPAOH is 45 weight %.
Embodiment 1-43
The condition provided according to table 4, nano-carbon material is molded respectively using following methods.
Nano-carbon material is well mixed with binding agent source under environment temperature (25 DEG C) respectively, mixture feeding will be obtained After being dried and be optionally calcined in strip mould, obtain nano-carbon material formed body and (randomly select part formed body to enter Row polishing, obtain the batten that length is 3-5mm and be used to determine crushing strength and porosity, as a result listed in table 4), will be surplus Sieved after remaining formed body is broken, obtain graininess formed body, its mean particle size (abbreviation particle diameter) is listed in table 4.
Table 4
1：The dosage of nano-carbon material is 10g2：TPAOH3：Tetraethyl ammonium hydroxide4：Dosage is to aoxidize Thing meter
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Embodiment 44-76
Using following methods, nano-carbon material is molded by the condition provided according to table 5 respectively：
Nano-carbon material is mixed with binding agent source and optional inorganic agent respectively, is then placed in obtained mixture In sealing autoclave with polytetrafluoroethyllining lining, hydro-thermal process is carried out under self-generated pressure.Treat in autoclave Temperature be down to environment temperature after, open reactor, obtained slurries be sent into strip mould and are dried and optionally After roasting, obtain nano-carbon material formed body and (randomly select part formed body to be polished, obtain the batten that length is 3-5mm For determining crushing strength and porosity, as a result listed in table 5), by remaining formed body it is broken after sieved, obtain Granular formed body, its mean particle size are listed in table 5.
Embodiment 78
Difference with embodiment 44 is, nano-carbon material is well mixed with binding agent source in environment temperature (25 DEG C) Afterwards, without hydro-thermal process, but directly it is molded.
Embodiment 79
Difference with embodiment 44 is, the mixture in nano-carbon material and binding agent source is placed in three-necked flask, With carrying out back flow reaction, time and the water in embodiment 44 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 44 Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Embodiment 80
Difference with embodiment 47 is, nano-carbon material is well mixed with binding agent source in environment temperature (25 DEG C) Afterwards, without hydro-thermal process, but directly it is molded.
Embodiment 81
Difference with embodiment 47 is, the mixture in nano-carbon material and binding agent source is placed in three-necked flask, With carrying out back flow reaction, time and the water in embodiment 47 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 47 Heat treatment time is identical, and the time of back flow reaction is identical with the hydrothermal conditions in embodiment 44, and back flow reaction is obtained Mixture is sent into mould.
Table 5
1：The dosage of nano-carbon material is 10g2：TPAOH3：TMAH4：Dosage is to aoxidize Thing meter
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Testing example 1-81
The catalytic performance of the catalyst prepared using following methods successively testing example 1-81.
The graininess formed body respectively prepared by 0.5g embodiments 1-81 is micro- in universal fixed bed as Catalyst packing In type quartz tube reactor, the end seal of miniature quartz pipe reactor two has quartz sand, will under the conditions of 0MPa (gauge pressure) and 450 DEG C (concentration of normal butane is 2.06 volume %, normal butane and oxygen molar ratio 0.5 to gas containing normal butane and oxygen：1, surplus For the nitrogen as carrier gas) with 4200h-1Weight (hourly) space velocity (WHSV) be passed through in reactor and reacted, continuous monitoring is defeated from reactor The composition of the reactant mixture gone out, and calculate n-butane conversion and total olefin selectivity, the result of reaction 3 hours and 24 hours Listed in table 6.
Test comparison example 1-4
Using the catalytic performance for testing multi-walled carbon nanotube A, B, C and D successively with testing example 1-81 identicals method.
Table 6
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment Each particular technique feature, in the case of reconcilable, can be combined by any suitable means, in order to avoid not Necessary repetition, the present invention no longer separately illustrate to various combinations of possible ways.In addition, a variety of implementations of the present invention It can also be combined between mode, as long as it without prejudice to the thought of the present invention, it is public that it should equally be considered as institute of the invention The content opened.

Claims (40)

1. a kind of nano-carbon material formed body, the formed body contains nano-carbon material and for the nano-carbon material to be bonded The heat-resistant inorganic oxide of shaping, on the basis of the total amount of the formed body, the content of the nano-carbon material is 6-94 weights % is measured, the content of the binding agent is 6-94 weight %.
2. formed body according to claim 1, wherein, the nano-carbon material contain C element, O elements, N element and Optional metallic element, on the basis of the total amount of the nano-carbon material and in terms of element, the content of N element is 0.5-12 weights % is measured, the content of O elements is 0.5-10 weight %, and the content of metallic element is 0-10 weight %.
3. formed body according to claim 2, wherein, the content of metallic element described in the nano-carbon material be less than 0.1 weight %, on the basis of the total amount of the nano-carbon material and in terms of element, the content of N element is 1-12 weight %, preferably For 3-12 weight %, more preferably 3.5-10 weight %, more preferably 3.5-9.5 weight %；The content of O elements is 0.5- 10 weight %, preferably 1-10 weight %, more preferably 3-9 weight %, more preferably 4.5-8 weight %；C element contains Measure as 78-98.5 weight %, preferably 78-96 weight %, more preferably 81-93.5 weight %, more preferably 82.5-92 Weight %；
Determine that the total amount of the N element in the nano-carbon material is I by x-ray photoelectron power spectrumN t, by x-ray photoelectron power spectrum The amount for the N element that peak in the range of middle 398.5-400.1eV determines is IN c, IN c/IN tIn the range of 0.7-1, preferably in 0.8- In the range of 1, more preferably in the range of 0.8-0.95, further preferably in the range of 0.85-0.92；
In the nano-carbon material, the O elements that are determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum Measure as IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO e In the range of 0.3-1.5, preferably in the range of 0.8-1.5, more preferably in the range of 0.85-1.2, further preferably exist In the range of 0.9-1.
4. formed body according to claim 3, wherein, in the nano-carbon material, by x-ray photoelectron power spectrum The amount for the C element that peak in the range of 288.6-288.8eV determines is IC c, by 286.0-286.2eV models in x-ray photoelectron power spectrum The amount for the C element that peak in enclosing determines is IC e, IC c/IC eIn the range of 0.3-1.5, preferably in the range of 0.5-1.5, more It is preferred that in the range of 0.6-1.4.
5. the formed body according to claim 3 or 4, wherein, with true by x-ray photoelectron power spectrum in the nano-carbon material On the basis of the total amount of fixed C element, the C element that is determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum Content is 60-98 weight %, more preferably preferably 65-95 weight %, 75-85 weight %；By in x-ray photoelectron power spectrum The content for the C element that peak in the range of 286.0-288.8eV determines is 2-40 weight %, preferably 5-35 weight %, more preferably For 15-25 weight %.
6. according to the formed body described in any one in claim 3-5, wherein, received as described in determining x-ray photoelectron power spectrum The total amount of N element in rice carbon material is IN t, the N that is determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum The amount of element is IN g, IN g/IN tFor not higher than 0.3, preferably in the range of 0.05-0.2, the scope more preferably in 0.08-0.15 It is interior.
7. formed body according to claim 2, wherein, in the nano-carbon material, with the total amount of the nano-carbon material On the basis of and in terms of element, the content of O elements is 1-8 weight %, more preferably preferably 2-8 weight %, 3.5-6 weight %；N The content of element is 0.5-10 weight %, more preferably preferably 1.5-5 weight %, 2-4 weight %；The total amount of metallic element is 1-10 weight %, preferably 2-5 weight %, more preferably 2-4.5 weight %；The content of C element is 72-97.5 weight %, excellent Elect 82-94.5 weight %, more preferably 85.5-92.5 weight % as；
In the nano-carbon material, the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, by x-ray photoelectron The content for the O elements that peak in power spectrum in the range of 529.5-530.8eV determines is IO m, IO m/IO tIn the range of 0.02-0.35, It is preferred that in the range of 0.05-0.3, preferably in the range of 0.06-0.2；
In the nano-carbon material, the O elements that are determined by the peak in the range of 531.0-532.5eV in x-ray photoelectron power spectrum Measure as IO c, the amount of the O elements determined by the peak in the range of 532.6-533.5eV in x-ray photoelectron power spectrum is IO e, IO c/IO e In the range of 0.1-0.8, preferably in the range of 0.2-0.8, preferably in the range of 0.4-0.6；
In the nano-carbon material, determine that the total amount of the N element in the nano-carbon material is I by x-ray photoelectron power spectrumN t, The amount of the N element determined by the peak in the range of 398.5-400.1eV in x-ray photoelectron power spectrum is IN c, IN c/IN tIn 0.6- In the range of 0.95, preferably in the range of 0.65-0.8；In the range of 403.5-406.5eV in x-ray photoelectron power spectrum The content for the N element that peak determines is IN n, IN n/IN tIn the range of 0.05-0.35, preferably in the range of 0.06-0.25.
8. formed body according to claim 7, wherein, in the nano-carbon material, by x-ray photoelectron power spectrum The amount for the C element that peak in the range of 288.6-288.8eV determines is IC c, by 286.0-286.2eV models in x-ray photoelectron power spectrum The amount for the C element that peak in enclosing determines is IC e, IC c/IC eIn the range of 0.2-1, preferably in the range of 0.3-0.8.
9. the formed body according to claim 7 or 8, wherein, with true by x-ray photoelectron power spectrum in the nano-carbon material On the basis of the total amount of fixed C element, the C element that is determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum Content is 60-95 weight %, preferably 70-92 weight %, more preferably 75-90 weight %, by x-ray photoelectron power spectrum The content for the C element that peak in the range of 286.0-288.8eV determines is 5-40 weight %, preferably 8-30 weight %, more preferably For 10-25 weight %.
10. according to the formed body described in any one in claim 7-9, wherein, received as described in determining x-ray photoelectron power spectrum The total amount of N element in rice carbon material is IN t, the N that is determined by the peak in the range of 400.6-401.5eV in x-ray photoelectron power spectrum The amount of element is IN g, IN g/IN tFor not higher than 0.3, preferably in the range of 0.02-0.2, the scope more preferably in 0.05-0.15 It is interior.
11. according to the formed body described in any one in claim 1-10, wherein, the nano-carbon material is CNT； Preferably, the nano-carbon material is multi-walled carbon nanotube；
Preferably, the specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 90- 250m2/g；
Preferably, total weight loss rate of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C Temperature range in total weight loss rate be w500, w500/w800In the range of 0.01-0.5, the weight-loss ratio is in air atmosphere Measure.
12. a kind of nano-carbon material formed body, the formed body contains nano-carbon material and for the nano-carbon material to be glued Form the heat-resistant inorganic oxide of type, on the basis of the total amount of the formed body, the content of the nano-carbon material is 6-94 weights % is measured, the content of the binding agent is 6-94 weight %；
The nano-carbon material is made using the method comprised the following steps：By a kind of moisture for being dispersed with raw material nano carbon material Dispersion liquid is reacted in closed container, and at least one modifying agent is dissolved with the aqueous dispersions, and the modifying agent is nitrogenous Compound, or the modifying agent are nitrogen-containing compound and nitric acid metal salt, and the nitrogen-containing compound is selected from NH3, hydrazine and urea, In course of reaction, the temperature of the aqueous dispersions is in the range of 80-350 DEG C.
13. formed body according to claim 12, wherein, the modifying agent is nitrogen-containing compound, raw material nano carbon material： The weight ratio of nitrogen-containing compound is 1：0.05-50, preferably 1：0.1-20, more preferably 1：0.3-10, more preferably 1： 0.4-5；Raw material nano carbon material：H2O weight ratio is 1：1-200, preferably 1：2-100, more preferably 1：10-50.
14. formed body according to claim 12, wherein, the modifying agent is nitrogen-containing compound and nitric acid metal salt, former Expect nano-carbon material：Nitrogen-containing compound：The weight ratio of nitric acid metal salt is 1：0.01-10：In the range of 0.01-10, preferably exist 1：0.05-8：In the range of 0.1-8, more preferably 1：0.2-5：In the range of 0.5-3；
Raw material nano carbon material：H2O weight ratio is 1：In the range of 2-500, preferably 1：In the range of 5-300, more preferably exist 1：In the range of 10-50.
15. formed body according to claim 12, wherein, the modifying agent is nitrogen-containing compound and nitric acid metal salt,
The nitrogen-containing compound is ammonia, and the metallic atom in the nitric acid metal salt is selected from iron, cobalt and nickel；Or
The nitrogen-containing compound is hydrazine, and the metallic atom in the nitric acid metal salt is selected from palladium and platinum；Or
The nitrogen-containing compound is urea, and the metallic atom in the nitric acid metal salt is selected from ruthenium and rhodium.
16. according to the formed body described in any one in claim 12-15, wherein, in course of reaction, the aqueous dispersions Temperature is in the range of 80-310 DEG C.
17. according to the formed body described in any one in claim 12-16, wherein, the duration of the reaction is in 0.5- In the range of 144 hours, preferably in the range of 0.5-96 hours, more preferably in the range of 2-72 hours, further preferably In the range of 10-60 hours.
18. according to the formed body described in any one in claim 12-17, wherein, in the raw material nano carbon material, N members The content of element is not higher than 0.2 weight %, preferably not higher than 0.1 weight %, more preferably not above 0.05 weight %, enters one Step is preferably not higher than 0.02 weight %；The content of O elements be not higher than 1.5 weight %, preferably not higher than 0.5 weight %, More preferably not above 0.3 weight %；The total amount of metallic element is below 2.5 weight %, preferably below 1.8 weight %, is entered One step is preferably below 0.5 weight %.
19. according to the formed body described in any one in claim 12-17, wherein, the raw material nano carbon material is received for carbon Mitron；Preferably, the raw material nano carbon material is multi-walled carbon nanotube；
Preferably, the specific surface area of the multi-walled carbon nanotube is 50-500m2/ g, preferably 80-300m2/ g, more preferably 100-260m2/ g, more preferably 120-190m2/g；
Preferably, total weight loss rate of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C Temperature range in total weight loss rate be w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.4, The weight-loss ratio determines in air atmosphere.
20. according to the formed body described in any one in claim 12-19, wherein, methods described also includes obtaining from reaction Mixture in isolate solid matter, and the solid matter isolated is dried；
Preferably, the drying is carried out at a temperature of 50-400 DEG C, is carried out preferably at a temperature of 80-180 DEG C, is more preferably existed Carried out at a temperature of 100-160 DEG C；The duration of the drying is preferably 4-24 hours no more than 48 hours, more preferably For 6-12 hours.
21. according to the formed body described in any one in claim 1-20, wherein, the metallic element is selected from period of element Group ia metal element, group iia metallic element, group VIII metallic element, I B-group metal element, group iib gold in table Belong to more than one or both of element and group IVA metallic element, the one kind being preferably selected from group VIII metallic element Or it is two or more, more preferably more than one or both of iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
22. according to the formed body described in any one in claim 1-21, wherein, on the basis of the total amount of the formed body, The content of the nano-carbon material is 8-92 weight %, more preferably preferably 10-90 weight %, 20-90 weight %, further Preferably 40-90 weight %, it is still more preferably 70-90 weight %, the content of the heat-resistant inorganic oxide is 8-92 weights %, more preferably preferably 10-90 weight %, more preferably 10-80 weight %, 10-60 weight % are measured, it is further excellent Elect 10-30 weight % as.
23. according to the formed body described in any one in claim 1-22, wherein, the heat-resistant inorganic oxide is oxidation It is more than one or both of aluminium, silica and titanium oxide；
Preferably, the heat-resistant inorganic oxide contains silica；
It is highly preferred that on the basis of the total amount of the heat-resistant inorganic oxide, the content of the silica is 10-100 weight %, Preferably 20-99 weight %.
24. a kind of preparation method of nano-carbon material formed body, this method includes mixing nano-carbon material with binding agent source, will Obtained mixture is molded, and obtains article shaped, and the article shaped is dried and is optionally calcined, the binding agent Source is selected from the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, and the nano-carbon material is non-surface treated Nano-carbon material and/or surface treated nano-carbon material.
25. according to the method for claim 24, wherein, the mixture also contains at least one alkali；
Preferably, the alkali is selected from organic base；
It is highly preferred that the organic base is selected from quaternary ammonium base, aliphatic amine and aliphatic hydramine；
It is further preferred that the organic base is selected from synthesis of titanium silicon molecular sieve template；
It is further preferred that the organic base is selected from the quaternary ammonium base shown in Formula II,
In Formula II, R5、R6、R7And R8It is identical or different, respectively C1-C4Alkyl；
The alkali and the mol ratio in the binding agent source are preferably 0.1-10：1, more preferably 0.15-5：1, more preferably 0.15-3：1, the binding agent source is in terms of oxide.
26. the method according to claim 24 or 25, wherein, before the mixture is molded, this method also includes will The mixture carries out hydro-thermal process.
27. according to the method for claim 26, wherein, the hydro-thermal process is at 100-200 DEG C, preferably 120-180 DEG C At a temperature of carry out, the duration of the hydro-thermal process is 0.5-24 hours, preferably 6-12 hours.
28. according to the method described in any one in claim 24-27, wherein, at least part binding agent source, at least partly may be used The organic base and at least part water of choosing come from molecular sieve preparation solution, and the molecular sieve preparation solution is the crystallization of siliceous molecular sieve Mixed liquor more than one or both of rearrangement solution of mother liquor and siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor and/or rearrangement solution, the crystallization of HTS of silica zeolite Mixing more than one or both of crystallization mother liquor and/or rearrangement solution of mother liquor and/or rearrangement solution and Si-Al molecular sieve Liquid.
29. a kind of forming method of nano-carbon material, this method includes nano-carbon material entering water-filling in a kind of aqueous dispersions Heat treatment, the sizing material forming that hydro-thermal process is obtained, obtains article shaped, the article shaped is dried and optionally roasted Burn, the aqueous dispersions contain binding agent source, and the binding agent source is selected from heat-resistant inorganic oxide and/or heat-resistant inorganic oxide Precursor, the nano-carbon material is not surface treated nano-carbon material and/or surface treated nano-carbon material.
30. forming method according to claim 29, wherein, the aqueous dispersions also contain at least one inorganic agent, institute It is alkali and/or nitric acid metal salt to state inorganic agent；
Preferably, the alkali is organic base；
It is highly preferred that the alkali is selected from quaternary ammonium base, aliphatic amine and aliphatic hydramine；
It is further preferred that the alkali is selected from synthesis of titanium silicon molecular sieve template；
It is further preferred that the organic base is selected from the quaternary ammonium base shown in Formula II,
In Formula II, R5、R6、R7And R8It is identical or different, respectively C1-C4Alkyl；
Preferably, group ia metal element, the group iia gold in the periodic table of elements of the metallic element in the nitric acid metal salt Belong to element, group VIII metallic element, I B-group metal element, group iib metallic element and group IVA metallic element, preferably Selected from group VIII metallic element, iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum are more preferably selected from,
Preferably, the inorganic agent is alkali and nitric acid metal salt, and the mol ratio of the alkali and the nitric acid metal salt is 1：0.1- 10, preferably 1：0.2-5, more preferably 1：0.2-1, more preferably 1：0.2-0.5.
31. according to the method for claim 30, wherein, relative to 100 parts by weight binder sources, the inorganic agent with it is described The mol ratio in binding agent source is 0.1-10：1, preferably 0.15-5：1, more preferably 0.15-3：1, the binding agent source is to aoxidize Thing meter.
32. according to the method described in any one in claim 29-31, wherein, at least part binding agent source, at least partly may be used The organic base and at least part water of choosing come from molecular sieve preparation solution, and the molecular sieve preparation solution is the crystallization of siliceous molecular sieve Mixed liquor more than one or both of rearrangement solution of mother liquor and siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor and/or rearrangement solution, the crystallization of HTS of silica zeolite Mixing more than one or both of crystallization mother liquor and/or rearrangement solution of mother liquor and/or rearrangement solution and Si-Al molecular sieve Liquid.
33. according to the method described in any one in claim 24-32, wherein, the heat-resistant inorganic oxide be aluminum oxide, It is more than one or both of silica and titanium oxide；
Preferably, the heat-resistant inorganic oxide contains silica；
It is highly preferred that on the basis of the total amount of the heat-resistant inorganic oxide, the content of the silica is 10-100 weight %, Preferably 20-99 weight %.
34. according to the method described in any one in claim 24-33, wherein, the dosage in the binding agent source causes finally In the formed body of preparation, the content of nano-carbon material is 5-95 weight %, and preferably 6-94 weight %, more preferably 8-92 are heavy %, more preferably 10-90 weight % are measured, is still more preferably 20-90 weight %, particularly preferably 40-90 weight %, It is preferably particularly 70-90 weight %, the content of the heat-resistant inorganic oxide can be 5-95 weight %, preferably 6-94 weights %, more preferably more preferably 8-92 weight %, 10-90 weight % are measured, is still more preferably 10-80 weight %, it is special You Xuanwei not 10-60 weight %, particularly preferably 10-30 weight %.
35. according to the method described in any one in claim 24-34, wherein, the surface treated nano-carbon material For the nano-carbon material described in any one in claim 2-11 and 12-21.
36. according to the method described in any one in claim 24-35, wherein, the drying is at a temperature of 50-200 DEG C Carry out, carried out preferably at a temperature of 80-180 DEG C；The duration of the drying is that preferably 3-24 was small no more than 48 hours When, more preferably 5-15 hours；
The roasting is carried out at a temperature of 300-800 DEG C, is carried out preferably at a temperature of 300-650 DEG C, the roasting is held The continuous time is 2-12 hours, preferably 2-4 hours.
37. nano-carbon material formed body prepared by a kind of method in 24-36 as claim described in any one.
38. catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction in claim 1-23 and 37 described in any one Application, the hydrocarbon is preferably alkane, more preferably C2-C12Alkane, more preferably normal butane.
39. a kind of hydrocarbon dehydrogenation reaction method, this method is included under conditions of existence or non-existence oxygen, in hydrocarbon dehydrogenation reaction bar Under part, hydrocarbon is contacted with the nano-carbon material formed body described in any one in claim 1-23 and 37.
40. according to the method for claim 39, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably Normal butane.
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