CN107661765A - 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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CN107661765A
CN107661765A CN201610603025.XA CN201610603025A CN107661765A CN 107661765 A CN107661765 A CN 107661765A CN 201610603025 A CN201610603025 A CN 201610603025A CN 107661765 A CN107661765 A CN 107661765A
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nano
weight
carbon material
range
formed body
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CN107661765B (en
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史春风
荣峻峰
于鹏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds

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

Abstract

The invention discloses a kind of nano-carbon material formed body for 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 formed body contains nano-carbon material and for by the heat-resistant inorganic oxide of the nano-carbon material molding bonded, the nano-carbon material contains O elements and at least one metallic element, and the metallic element is selected from transition metal, group ia metal element and group iia metallic element.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 the heat-resistant inorganic oxide of the nano-carbon material molding bonded, the nano-carbon material to be contained into O Element and at least one metallic element, the metallic element are selected from transition metal, group ia metal element and group iia gold Belong to element.
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；
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 peroxide and at least one are dispersed with the aqueous dispersions Metallic compound, the metallic compound are selected from alkaline metal cpds and transistion metal compound, the alkalinous metal chemical combination Metallic element in thing is selected from group ia metal element and group iia metallic element, in course of reaction, the temperature of the aqueous dispersions Degree is in the range of 80-300 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, Determine that the surface treated nano-carbon material contains O elements and at least one metallic element, institute by x-ray photoelectron power spectrum State metallic element and be selected from transition metal, group ia metal element and group iia metallic element.
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, the surface treated nanometer is determined by x-ray photoelectron power spectrum Carbon material contains O elements and at least one metallic element, and the metallic element is selected from transition metal, group ia metal element With group iia metallic element.
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 contains O elements and at least one metal member Plain (hereinafter, otherwise referred to as nano-carbon material containing metallic atom).
The content of O elements and metallic element can be entered according to the source of the nano-carbon material in the nano-carbon material Row selection, can also be selected with the concrete application occasion of the nano-carbon material formed body.Usually, with the nano carbon material On the basis of the total amount of material and in terms of element, the contents of O elements can be 1-15 weight %, preferably 2-12 weight %, more preferably For 5-10 weight %；The content of the metallic element can be 0.2-20 weight %, preferably 0.5-18 weight %, be more preferably 1-9 weight %.Wherein, the content of each element is determined using X-ray photoelectron spectroscopy.Sample is before testing in 150 DEG C of temperature Dried 3 hours in helium atmosphere under degree.
In the present invention, 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.
According to the formed body of one side of the invention, the metallic element is selected from transition metal, group ia metal Element and group iia metallic element.
The instantiation of the group ia metal element and group iia metallic element can include but is not limited to lithium, sodium, It is more than one or both of potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, group ia metal element and group iia the metal member Element is more than one or both of sodium, potassium, magnesium, calcium and barium, and the nano-carbon material formed body so is being used as into hydrocarbon dehydrogenation During the catalyst of reaction, more preferable catalytic performance can be obtained.
The transition metal can in the periodic table of elements Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals element, V Group IIB metallic element, group VIII metallic element, I B-group metal member Element and group iib metallic element.The instantiation of the transition metal can include but is not limited to scandium, yttrium, rare earth metal Element (such as lanthanum, cerium, praseodymium), titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, Jin Hexin.It is excellent Selection of land, the transition metal are selected from group VIII metallic element, and it is anti-that nano-carbon material formed body now is used as into hydrocarbon dehydrogenation During the catalyst answered, higher catalytic activity can be obtained.The transition metal is more preferably selected from group VIII metallic element, Further preferably it is selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
According to the formed body of one side of the invention, the nano-carbon material can only contain transition metal, Group ia metal element and/or group iia metallic element can only be contained, transition metal and choosing can also be contained simultaneously From the metallic element of Group IA and HA.In one embodiment, the metallic element be group ia metal element and/ Or group iia metallic element (hereafter will be referred to as nano carbon material containing alkaline element according to the nano-carbon material of the embodiment Material).In another embodiment, the metallic element is transition metal (hereafter by the nanometer according to the embodiment Carbon material is referred to as nano-carbon material containing transition metal).As long as according to the nano-carbon material of the present invention although containing the gold Belong to element, but from the further nano-carbon material formed body that improves as the catalytic activity of the catalyst of hydrocarbon dehydrogenation reaction Angle is set out, the species of the metallic element preferably according to contained by nano-carbon material to the content of each element in nano-carbon material with And existence form optimizes, individually below to being described in detail according to the nano-carbon material of above two embodiment.
According to the present invention nano-carbon material containing alkaline element, on the basis of the total amount of the nano-carbon material and with Element meter, the contents of O elements can be 2-12 weight %, more preferably preferably 2.5-10 weight %, 5-8 weight %, C element Content can be 78-97.5 weight %, more preferably preferably 85-96.5 weight %, 88-94 weight %, the metal member The total amount of element can be 0.5-10 weight %, more preferably preferably 1-5 weight %, 1-4 weight %.
According to the present invention nano-carbon material containing alkaline element, the oxygen element determined by x-ray photoelectron power spectrum Total content is 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 tCan be in the range of 0.02-0.3, preferably in the range of 0.05-0.25, the scope more preferably in 0.08-0.2 It is interior.The content of the O elements determined by the peak in the range of 531.0-533.5eV in x-ray photoelectron power spectrum is IO nm, IO nm/IO tCan With in the range of 0.7-0.98, preferably in the range of 0.75-0.95, more preferably in the range of 0.8-0.92.
In the present invention, the area of the O1s spectral peaks in x-ray photoelectron power spectrum is designated as AO 1, O1s spectral peaks are divided into two groups Peak, the area of the spectral peak (corresponding to the oxygen species being connected with metallic atom) in the range of 529.5-530.8eV is designated as AO 2, will The area of spectral peak (corresponding to the oxygen species not being connected with metallic atom) in the range of 531.0-533.5eV is designated as AO 3, wherein, IO m/IO t=AO 2/AO 1, IO nm/IO t=AO 3/AO 1。
According to the nano-carbon material containing alkaline element of the present invention, by 531.0-532.5eV in x-ray photoelectron power spectrum In the range of the amount of O elements (that is, C=O) that determines of peak be IO c, in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount of O elements (that is, C-O) that determines of peak be IO e, IO c/IO eCan be in the range of 0.3-1.5, the model preferably in 0.3-1.2 In enclosing, more preferably in the range of 0.5-1, further preferably in the range of 0.6-0.9.
In the present invention, by x-ray photoelectron power spectrum in the range of 531.0-533.5eV spectral peak (correspond to not with gold The connected oxygen species of category atom) be further separated into two groups of peaks, i.e., the spectral peak in the range of 531.0-532.5eV (corresponds to C=O Species) and spectral peak (corresponding to C-O species) in the range of 532.6-533.5eV, by the range of 531.0-532.5eV The area of spectral peak 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。
According to the present invention nano-carbon material containing alkaline element, with the nano-carbon material by x-ray photoelectron On the basis of the total amount for the C element that power spectrum determines, the C that is determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum The content of element can be 65-95 weight %, preferably 75-85 weight %；By 286.0- in x-ray photoelectron power spectrum The total content for the C element that peak in the range of 288.8eV determines can be 5-35 weight %, preferably 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。
According to the nano-carbon material containing alkaline element of the present invention, in the nano-carbon material, by x-ray photoelectron energy The amount for the C element that peak in spectrum in the range of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron power spectrum The amount for the C element that peak in the range of 286.2eV determines is IC e, IC c/IC eCan be in the range of 0.4-2, preferably in 0.45-1.5 In the range of, more preferably in the range of 0.8-1.3, further preferably in the range of 0.9-1.2.
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。
According to the present invention the nano-carbon material containing transition metal, on the basis of the total amount of the nano-carbon material simultaneously In terms of element, the content of O elements can be 1-15 weight %, more preferably preferably 3-13 weight %, 5-10 weight %；Metal The total amount of element can be 0.4-20 weight %, more preferably preferably 2-18 weight %, 4-9 weight %；The content of C element can Think 65-98.6 weight %, preferably 69-95 weight %, more preferably 81-91 weight %.
According to the nano-carbon material containing transition metal of the present invention, in the nano-carbon material, by x-ray photoelectron The total content for the oxygen element that power spectrum determines is IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum The content of O elements is IO m, IO m/IO tCan more preferably it exist in the range of 0.01-0.6, preferably in the range of 0.02-0.5 In the range of 0.03-0.4, further preferably in the range of 0.09-0.18.By 531.0- in x-ray photoelectron power spectrum The content for the O elements that peak in the range of 533.5eV determines is IO nm, IO nm/IO tCan preferably it exist in the range of 0.4-0.99 In the range of 0.5-0.98, more preferably in the range of 0.6-0.97, further preferably in the range of 0.82-0.91.
According to the nano-carbon material containing transition metal of the present invention, by 531.0- in x-ray photoelectron power spectrum The amount for the O elements (that is, C=O) that peak in the range of 532.5eV determines is IO c, by 532.6- in x-ray photoelectron power spectrum The amount for the O elements (that is, C-O) that peak in the range of 533.5eV determines is IO e, IO c/IO eIn the range of 0.2-1, preferably exist In the range of 0.25-0.9, more preferably in the range of 0.4-0.75.
According to the present invention the nano-carbon material containing transition metal, with the nano-carbon material by X ray photoelectricity On the basis of the total amount for the C element that sub- power spectrum determines, determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum The content of C element can be 60-95 weight %, preferably 60-80 weight %；By 286.0- in x-ray photoelectron power spectrum The total content for the C element that peak in the range of 288.8eV determines can be 5-40 weight %, preferably 20-40 weight %.
According to the nano-carbon material containing transition metal of the present invention, in the nano-carbon material, by x-ray photoelectron The amount for the C element that peak in power spectrum in the range of 288.6-288.8eV determines is IC c, by 286.0- in x-ray photoelectron power spectrum The amount for the C element that peak in the range of 286.2eV determines is IC e, IC c/IC eCan be in the range of 0.3-2, preferably in 0.4-1.6 In the range of, more preferably in the range of 0.8-1.4.
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 288.6-288.8eV refers to that the combination corresponding to summit can be in 288.6- Whole peaks in the range of 288.8eV.
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, the specific surface area of the multi-walled carbon nanotube is preferably 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 90-300m2/ g, more preferably 120-180m2/ g.In the present invention, the specific surface area is determined by nitrogen adsorption BET method.
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.w500/w800More preferably in the range of 0.02-0.4, further preferably in the range of 0.05-0.15.This In invention, w800=W800- W400, w500=W500- W400, W400For the mass loss rate determined at a temperature of 400 DEG C, W800For 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 weightlessness Rate is determined using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, and heating rate is 10 DEG C/min；Sample exists Depress in 150 DEG C of temperature and 1 normal atmosphere before test and dried 3 hours in helium atmosphere.
According to the nano-carbon material formed body of the present invention, in the nano-carbon material, its outside oxygen atom and nitrogen-atoms Its nonmetallic heteroatoms, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, according to the nanometer of the present invention Carbon material formed body, in the nano-carbon material, other nonmetallic heteroatoms outside oxygen atom and nitrogen-atoms (such as sulphur atom and Phosphorus atoms) total amount can be below 0.5 weight %, preferably below 0.2 weight %, more preferably below 0.1 weight %, enter One step is preferably below 0.05 weight %.According to the nano-carbon material formed body of the present invention, in the nano-carbon material, except selected from Outside aforesaid metal elements, other metallic atoms can also be contained, other metallic atoms for example can be to be received from preparation The catalyst used during rice carbon material.The content of other metallic atoms is generally below 2.5 weight %, preferably 2 weights Below % is measured, is still more preferably below 0.5 weight %, particularly preferably 0.2 weight more 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.
The heat-resistant inorganic oxide is preferably more than one or both of aluminum oxide, silica and titanium oxide.One In individual example, the heat-resistant inorganic oxide is aluminum oxide, and it is higher to be molded physical efficiency acquisition according to the nano-carbon material of the example 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 It is dispersed with least one peroxide and at least one metallic compound, in course of reaction, the temperature of the aqueous dispersions exists In the range of 80-300 DEG C.
The peroxide refers to the compound for containing-O-O- keys in molecular structure.Specifically, the peroxide can be with Selected from the organic peroxide shown in hydrogen peroxide and Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl andAnd R1And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl.
In the present invention, C4-C12The instantiation of alkyl include but is not limited to normal-butyl, sec-butyl, isobutyl group, tertiary fourth Base, n-pentyl, neopentyl, isopentyl, tertiary pentyl, hexyl (the various isomers for including hexyl), cyclohexyl, octyl group are (including pungent The various isomers of base), nonyl (the various isomers for including nonyl), decyl (the various isomers for including decyl), hendecane Base (the various isomers for including undecyl) and dodecyl (the various isomers for including dodecyl).
In the present invention, C6-C12The instantiation of aryl include but is not limited to phenyl, naphthyl, aminomethyl phenyl and ethylo benzene Base.In the present invention, C7-C12Aralkyl instantiation include but is not limited to phenyl methyl, phenylethyl, phenyl n-propyl, Phenyl normal-butyl, phenyl t-butyl, propyloxy phenyl base, phenyl n-pentyl and phenyl normal-butyl.
The instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, TBHP, peroxidating Hydrogen isopropylbenzene, hydrogen peroxide ethylbenzene, cyclohexyl hydroperoxide, cumyl peroxide, dibenzoyl peroxide, the uncle of peroxidating two Butyl and dilauroyl peroxide.
The metallic compound is selected from alkaline metal cpds and transistion metal compound.
Metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, its Instantiation can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, the metallic element be selected from sodium, Potassium, magnesium, calcium and barium, so when the nano-carbon material formed body to be used as to the catalyst of hydrocarbon dehydrogenation reaction, it can obtain more preferable Catalytic performance.The alkaline metal cpds are preferably selected from hydroxide and basic salt.It is highly preferred that the alkalinous metal Compound is selected from the hydroxide containing metallic element, the carbonate containing the metallic element and the bicarbonate containing the metallic element Salt.The instantiation of the alkaline metal cpds can include but is not limited to：Lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen Beryllium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, bicarbonate It is more than one or both of sodium, calcium bicarbonate, saleratus and barium bicarbonate.From further improve the nano-carbon material into The angle of catalytic activity of the type body in hydrocarbon dehydrogenation reaction is set out, and the alkaline metal cpds are preferably sodium hydroxide, hydrogen-oxygen Change potassium, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, bicarbonate It is more than one or both of calcium, saleratus and barium bicarbonate.
Metallic element in the transistion metal compound is selected from transition metal, and (that is, described metallic compound is preferred Selected from the compound containing transition metal).Metallic element in the transistion metal compound can specifically be selected from, but not limited to, member Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals element, in plain periodic table VIIB races metallic element, group VIII metallic element, I B-group metal element and group iib metallic element.The transition metal The instantiation of metallic element in compound can include but is not limited to 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, Jin Hexin.Preferably, the transition metal Metallic element in compound is selected from group VIII metallic element, and now, the nano-carbon material formed body is as hydrocarbon dehydrogenation During the catalyst of reaction, higher catalytic activity can be obtained.It is highly preferred that the metallic element choosing in the transistion metal compound From iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The transistion metal compound can be selected from transition metal nitrate, transition metal acetate, transition metal carbonic acid Salt, transition metal sulfate, transition metal subcarbonate, transition metal gluconate, transition metal hydroxide, transition Metal chloride and transition metal complex, more preferably transition metal acetate, transition metal gluconate, mistake Cross metal carbonate, transition metal subcarbonate, transition metal hydroxide and transition metal complex (such as nitric acid ammonia palladium And palladium acetylacetonate).
The transistion metal compound can specifically be selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic carbonate Nickel, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, vinegar Sour ferrous iron, ferrous gluconate, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, alkali Formula zinc carbonate, zinc chloride, zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, nitric acid Lanthanum, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide Ruthenium, palladium nitrate, palladium bichloride, palladium dydroxide, platinum nitrate, platinum chloride, rhodium nitrate, nitric acid ammonia palladium (such as ammino palladium of nitric acid four), chlorination Rhodium and palladium acetylacetonate.
According to the formed body described in second aspect of the present invention, the metallic compound can be alkaline metal cpds, It can also be transistion metal compound, can also be the combination of alkaline metal cpds and transistion metal compound.A kind of real Apply in mode, the metallic compound is alkaline metal cpds.In another embodiment, the metallic compound was Cross metallic compound.Although in the presence of peroxide, raw material nano carbon material and metallic compound are subjected to hydro-thermal process, Catalytic activity during catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction can be improved, but is received from further raising The angle of the catalytic activity of rice carbon material formed body is set out, and preferably reaction condition is carried out according to the species of metallic compound excellent Change.
When the metallic compound is alkaline metal cpds, raw material nano carbon material：Peroxide：Alkalinous metal The weight ratio of compound is preferably 1：0.02-20：In the range of 0.01-10, the nano-carbon material containing metallic atom thus prepared exists The catalytic effect further improved can be obtained during catalyst as hydrocarbon dehydrogenation reaction.Raw material nano carbon material：Peroxide：Alkali The weight ratio of property metallic compound is more preferably 1：0.2-16：In the range of 0.02-5, further preferably 1：0.5-5：0.05- In the range of 1, still more preferably 1：1-2：In the range of 0.1-0.2.
When the metallic compound is alkaline metal cpds, raw material nano carbon material：H2O weight ratio is preferably 1： In the range of 2-500, when the dosage of water is within the scope of being somebody's turn to do, structural form of the nano-carbon material in processing procedure is kept Property is more preferable, such as：When raw material nano carbon material is CNT, it will not be cut off substantially in processing procedure.Raw material nano carbon Material：H2O weight ratio is more preferably 1：In the range of 10-400, further preferably 1：In the range of 50-200.
When the metallic compound is alkaline metal cpds, in a kind of preferable example, the peroxide is Hydrogen peroxide, the metallic element in the alkaline metal cpds are selected from magnesium, calcium and barium.In another preferable example, institute State peroxide and be selected from sodium and potassium for the organic peroxide shown in Formulas I, the metallic element of the alkaline metal cpds.According to The nano-carbon material formed body of above-mentioned two preferred embodiment can obtain higher catalysis in the catalyst as hydrocarbon dehydrogenation reaction Activity.
When the metallic compound is transistion metal compound, raw material nano carbon material：Peroxide：Metallic compound Weight ratio preferably 1：0.01-20：In the range of 0.01-10, the nano-carbon material containing metallic atom that thus prepares as The catalytic reaction effect further improved can be obtained during the catalyst of hydrocarbon dehydrogenation reaction.Raw material nano carbon material：Peroxide：Gold Belong to the weight ratio of compound more preferably 1：0.1-18：In the range of 0.02-5, further preferably 1：0.2-15：0.05-4's In the range of, still more preferably 1：0.5-2：In the range of 0.1-1.
When the metallic compound is transistion metal compound, raw material nano carbon material：H2O weight ratio is preferably 1： In the range of 2-500, when the dosage of water is within the scope of being somebody's turn to do, structural form of the nano-carbon material in processing procedure is kept Property is more preferable, such as：For CNT, it will not be cut off substantially in processing procedure.Raw material nano carbon material：H2O's Weight ratio is more preferably 1：In the range of 5-400, further preferably 1：In the range of 10-350, still more preferably 1： In the range of 25-100.
When the metallic compound is transistion metal compound, in a preferable example, the peroxide is Hydrogen peroxide, the metallic element in the metallic compound are selected from iron, cobalt and nickel.In another preferable example, the mistake Oxide is the organic peroxide shown in Formulas I, and the metallic element in the metallic compound is selected from ruthenium, rhodium, palladium and platinum.
According to the formed body described in second aspect of the present invention, in course of reaction, the temperature of the aqueous dispersions preferably exists In the range of 90-240 DEG C., will not be to raw material nano carbon material when the temperature of the aqueous dispersions is within above range Structural form produce significantly affect.In course of reaction, the temperature of the aqueous dispersions is more preferably in 120-220 DEG C of scope It is interior.
The duration of the reaction can be selected according to the temperature of reaction.Usually, the reaction it is lasting when Between can be in the range of 0.5-144 hours, preferably in the range of 0.5-96 hours, the scope more preferably in 2-72 hours It is interior, further preferably in the range of 10-60 hours, still more preferably in the range of 12-36 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 peroxide And metallic compound, so as to obtain the aqueous dispersions.In order to further improve the dispersion effect of raw material nano carbon material, simultaneously Shorten the scattered time, the method for sonic oscillation can be used to be dispersed in water raw material nano carbon material.The sonic oscillation Condition can be conventional selection, usually, the frequency of the sonic oscillation can be 10-200kHz, preferably 14- 140kHz；The duration of the sonic oscillation can be 0.1-6 hours, preferably 0.5-4 hours.The peroxide and gold Belong to compound can each to be provided in the form of solution (being preferably the aqueous solution) according to species, can also be each with the shape of pure material Formula provides, and is 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.The duration of the drying can root Selected according to dry temperature and mode.Usually, the duration of the drying can be no more than 48 hours, be preferably 4-24 hours, more preferably 6-12 hours.The drying can be carried out under normal pressure (that is, 1 standard atmospheric pressure), can also subtracted Carried out under conditions of pressure.From the further angle for improving dry efficiency, the drying is preferably entered at reduced pressure OK.Also spray drying etc. is without by solid matter is isolated in mixture the step of can be used, drying now can be Carried out at a temperature of 120-400 DEG C, carry out preferably at a temperature of 150-350 DEG C, more preferably enter at a temperature of 180-300 DEG C OK, the duration of the drying can be selected according to dry degree, be such as no 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 %, more preferably preferably 20-99 weight %, 50-99 weight %, deoxygenation The content of heat-resistant inorganic oxide outside SiClx can be 0-90 weight %, preferably 1-80 weight %, more preferably 1-50 Weight %.In the preferred embodiment, the instantiation of the heat-resistant inorganic oxide outside silicon can include but It is not limited to aluminum oxide and/or titanium oxide.As an example of the preferred embodiment, the heat resistant inorganic outside silicon Oxide 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 Formula II：
In Formula II, R4、R5、R6And R7Respectively C1-C4Alkyl.The C1-C4Alkyl include C1-C4Straight chained alkyl And C3-C4Branched alkyl, its instantiation can include but is not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary Butyl, isobutyl group and the tert-butyl group.Preferably, organic silicon source is selected from methyl silicate, tetraethyl orthosilicate, positive silicic acid positive third Ester, 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 hydrazine, urea, amine, hydramine and quaternary ammonium base in one kind or It is two or more.
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 III Alkali,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkyl, such as：R8、R9、R10And R11Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group or the tert-butyl group.
The amine can be the aliphatic amine and general formula R that formula IV represents15(NH2)2One kind in the material of expression or two More than kind,
In formula IV, R12、R13And R14Respectively H, C1-C6Alkyl or C6-C12Aryl, and R12、R13And R14When 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 R15(NH2)2In, R15Can 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 V represents,
In Formula V, R16、R17And R18Respectively-R16OH or hydrogen, and R16、R17And R18In it is at least one be-R19OH, R19 For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylidene, Its instantiation can include but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, isobutylidene With 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, hydrazine, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, n-propylamine, two positive third Amine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl Amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, di-iso-amylamine, three isoamyls Amine, tertiary amylamine, n-hexylamine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, dimethyl Base amine, n-tridecane base amine, n-tetradecane base amine, n-pentadecane base amine, n-hexadecyl amine, triethanolamine, triisopropanolamine, Diethanol amine, two n-propanolamines, three n-propanolamines, two n-butanol amine, three n-butanol amine, dodecyl-dimethyl amine, the tetradecane It is base dimethyl amine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, substituted or unsubstituted Pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substitution or Unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted EEDQ, take Generation or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin, substitution or unsubstituted Pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, m-toluidine, right Methylaniline, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,6- dimethylanilines, 3,4- diformazans Base aniline, 3,5- dimethylanilines, 2,4,6- trimethylanilines, o ethyl aniline, N- butylanilines, 2,6- diethylanilines, Cyclohexylamine, cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, TMAH, tetraethyl hydroxide Ammonium, TPAOH (including its various isomers, such as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), four fourths Base ammonium hydroxide (including its various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group hydrogen-oxygens Change ammonium and tetra-tert ammonium hydroxide) and one or both of four pentyl ammonium hydroxide (including its various isomers) more than.
In a preferred embodiment, the alkali is organic base, so can further improve the nanometer finally prepared Catalytic activity of the carbon material formed body as the catalyst of hydrocarbon dehydrogenation reaction.In the preferred embodiment, the alkali is conjunction Into HTS template, the quaternary ammonium base as shown in formula III, the nano-carbon material formed body thus prepared has higher Crushing strength, and the catalytic activity further improved is shown in the catalyst as hydrocarbon dehydrogenation reaction.
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 0.2-5：1, more preferably 0.3-2：1, 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 120-180 DEG C.The duration of the drying can root Selected according to dry temperature, typically can be preferably 3-24 hours, more preferably 5-15 hours no more than 48 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.Root According to the method described in third aspect of the present invention, the nano-carbon material in various sources can be handled, can be without table The nano-carbon material of face processing, or surface treated nano-carbon material.In the present invention, using x-ray photoelectron energy Spectrometry detects to the surface of nano-carbon material, if the member in nano-carbon material surface-element after testing in addition to C element The total content of element is below 2 weight %, then the nano-carbon material is considered as into not surface treated nano-carbon material, conversely, then The nano-carbon material is considered as 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 determines that the surface treated nano-carbon material contains O elements and at least one metallic element, described to be selected from transition Metallic element, group ia metal element and group iia metallic element.The transition metal, group ia metal element and Group IIA metal element is identical with the species of the metallic element described in one side of the invention, is no longer described in detail herein.The gold The content of category element can be selected according to the concrete application occasion of the nano-carbon material formed body finally prepared.Finally making During catalyst of the standby nano-carbon material formed body as hydrocarbon dehydrogenation reaction, on the basis of the total amount of the nano-carbon material and with Element meter, the content of O elements can be 1-15 weight %, more preferably preferably 2-12 weight %, 5-10 weight %；The gold The content for belonging to element can be 0.2-20 weight %, more preferably preferably 0.5-18 weight %, 1-9 weight %.
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.According to the nano carbon material described in the 4th aspect of the present invention Material formed body has higher porosity.Usually, the nano-carbon material formed body according to the 4th aspect of the present invention Porosity can be more than 5%, it might even be possible to it is more than 10%, such as can be in the range of 5-50%, preferably in 10-30% In the range of, 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 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 binding agent source and third aspect of the present invention institute It is identical to state the species in binding agent source, 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 selected from alkali, peroxide and metallic compound, and the alkali is different from the metallic compound.So can be further The crushing strength of the nano-carbon material formed body finally prepared is improved, while can also further improve the nano-sized carbon finally prepared Catalytic activity during catalyst of the material molded compact as hydrocarbon dehydrogenation reaction.It is without surface particularly in the nano-carbon material During the nano-carbon material of processing, the crushing strength and catalytic of the nano-carbon material formed body finally prepared can be significantly improved Energy.
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.The peroxide can be the peroxide being related in second aspect formed body of the present invention, no longer superfluous herein State.
The metallic compound can be alkaline metal cpds and/or transistion metal compound.
Metallic element in the alkaline metal cpds is selected from group ia metal element and group iia metallic element, its Instantiation can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium.Preferably, the metallic element be selected from sodium, Potassium, magnesium, calcium and barium, so when the nano-carbon material formed body to be used as to the catalyst of hydrocarbon dehydrogenation reaction, it can obtain more preferable Catalytic performance.The alkaline metal cpds are preferably selected from hydroxide and basic salt.It is highly preferred that the alkalinous metal Compound is selected from the hydroxide containing metallic element, the carbonate containing the metallic element and the bicarbonate containing the metallic element Salt.The instantiation of the alkaline metal cpds can include but is not limited to：Lithium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen Beryllium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, bicarbonate It is more than one or both of sodium, calcium bicarbonate, saleratus and barium bicarbonate.From further improve the nano-carbon material into The angle of catalytic activity of the type body in hydrocarbon dehydrogenation reaction is set out, and the alkaline metal cpds are preferably sodium hydroxide, hydrogen-oxygen Change potassium, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, bicarbonate It is more than one or both of calcium, saleratus and barium bicarbonate.
Metallic element in the transistion metal compound is selected from transition metal, and (that is, described metallic compound is preferred Selected from the compound containing transition metal).Metallic element in the transistion metal compound can specifically be selected from, but not limited to, member Group IIIB metallic element, group ivb metallic element, Group VB metallic element, vib metals element, in plain periodic table VIIB races metallic element, group VIII metallic element, I B-group metal element and group iib metallic element.The transition metal The instantiation of metallic element in compound can include but is not limited to 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, Jin Hexin.Preferably, the transition metal Metallic element in compound is selected from group VIII metallic element, and now, the nano-carbon material formed body is as hydrocarbon dehydrogenation During the catalyst of reaction, higher catalytic activity can be obtained.It is highly preferred that the metallic element choosing in the transistion metal compound From iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
The transistion metal compound can be selected from transition metal nitrate, transition metal acetate, transition metal carbonic acid Salt, transition metal sulfate, transition metal subcarbonate, transition metal gluconate, transition metal hydroxide, transition Metal chloride and transition metal complex, more preferably transition metal acetate, transition metal gluconate, mistake Cross metal carbonate, transition metal subcarbonate, transition metal hydroxide and transition metal complex (such as nitric acid ammonia palladium And palladium acetylacetonate).
The transistion metal compound can specifically be selected from, but not limited to, nickel nitrate, nickel acetate, nickel sulfate, basic carbonate Nickel, nickel chloride, nickel hydroxide, cobalt nitrate, cobalt acetate, cobaltous sulfate, basic cobaltous carbonate, cobalt chloride, cobalt hydroxide, ferric nitrate, vinegar Sour ferrous iron, ferrous gluconate, ferric sulfate, basic carbonate iron, iron chloride, iron hydroxide, zinc nitrate, zinc acetate, zinc sulfate, alkali Formula zinc carbonate, zinc chloride, zinc hydroxide, copper nitrate, copper acetate, copper sulphate, basic copper carbonate, copper chloride, Kocide SD, nitric acid Lanthanum, lanthanum carbonate, lanthanum chloride, lanthanum hydroxide, cerous nitrate, cerous carbonate, cerium chloride, cerium hydroxide, nitric acid ruthenium, ruthenic chloride, hydroxide Ruthenium, palladium nitrate, palladium bichloride, palladium dydroxide, platinum nitrate, platinum chloride, rhodium nitrate, nitric acid ammonia palladium (such as ammino palladium of nitric acid four), chlorination Rhodium and palladium acetylacetonate.
From the intensity and the catalysis in hydrocarbon dehydrogenation reaction for further improving the nano-carbon material formed body finally prepared The angle of performance is set out, and the inorganic agent is preferably alkali and selected from least one of peroxide and metallic compound.
In one embodiment, the inorganic agent is alkali, preferably organic base.From the further formed body for improving and preparing Intensity and the angle of the catalytic effect in hydrocarbon dehydrogenation reaction set out, the alkali is more preferably quaternary ammonium base, further preferably For synthesis of titanium silicon molecular sieve template, the quaternary ammonium base as shown in formula III.
In a kind of embodiment being more highly preferred to, the inorganic agent is alkali, peroxide and metallic compound.It is excellent at this In the embodiment of choosing, the alkali is preferably organic base, more preferably quaternary ammonium base, and more preferably synthesis of titanium silicon molecular sieve is used Template, the quaternary ammonium base as shown in formula III.By introducing quaternary ammonium base in hydrothermal treatment process, formed body can be effectively improved Intensity and catalytic performance.In the preferred embodiment, particularly preferred at least part alkali and at least part binding agent source is come From in molecular sieve preparation solution.
In the embodiment that this is more highly preferred to, metallic compound can be alkaline metal cpds and/or transition metal Compound.When the metallic compound is alkaline metal cpds, in a kind of preferable example, the peroxide was Hydrogen oxide, the metallic element in the alkaline metal cpds are selected from magnesium, calcium and barium；It is described in another preferable example Peroxide is the organic peroxide shown in Formulas I, and the metallic element of the alkaline metal cpds is selected from sodium and potassium.Described When metallic compound is transistion metal compound, in a preferable example, the peroxide is hydrogen peroxide, the gold Metallic element in category compound is selected from iron, cobalt and nickel；In another preferable example, the peroxide is shown in Formulas I Organic peroxide, the metallic element in the metallic compound is selected from ruthenium, rhodium, palladium and platinum.
With the nano-carbon material that is related to described in second aspect of the present invention (that is, first by raw material nano carbon material and peroxidating Thing and metallic compound carry out hydro-thermal process together, are then molded in the presence of base) compare, the preferred embodiment Not only the dosage of metallic compound is lower, and the formed body prepared is shown and first hydro-thermal process aftershaping and the shaping for preparing Body phase works as the intensity and catalytic performance of even more high.In the embodiment that this is more highly preferred to, alkali, peroxide and metal compound The mol ratio of thing can be 1：0.1-10：0.02-1.5, preferably 1：0.4-7：0.07-0.8.
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 0.1-8：1, more preferably 0.3-4：1, the binding agent Source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, the dosage of water with can by nano-carbon material and binding agent source and Optional alkali is well mixed to be defined.Water and the mol ratio in the binding agent source can be 1-150：1, preferably 4-120：1, it is described 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 % (such as below 94 weight %), excellent Elect as below 94 weight %, more preferably below 90 weight %.In an example, with the total of the nano-carbon material formed body On the basis of amount, the content of the nano-carbon material can be 5-95 weight % (such as 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 %, it is especially excellent Elect 70-90 weight % as, the content of the heat-resistant inorganic oxide can be 5-95 weight % (such as 6-94 weight %), be preferably 8-92 weight %, more preferably 10-90 weight %, more preferably 10-80 weight %, it is still more preferably 10-60 weights Measure %, particularly preferably 10-30 weight %.Nano-carbon material prepared by described according to the fifth aspect of the present invention method into Type body, under relatively low binder content, it can also obtain higher intensity.Usually, using the total amount of the formed body as Benchmark, the content of the nano-carbon material are preferably 75-95 weight %, more preferably 85-95 weight %, the heat resistant inorganic oxygen The content of compound is preferably 5-25 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.According to the nano-carbon material formed body of the present invention It can use directly as catalyst, be 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 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 2000-4500h-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 1-34 is used to prepare nano-carbon material containing metallic atom.
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, be dispersed under the conditions of sonic oscillation and carry out, sonic oscillation condition includes：Frequency is 140kHz, time are 1 hour.Then the hydrogen peroxide as peroxide and the hydroxide as alkaline metal cpds are added Barium, it is well mixed, so as to obtain aqueous dispersions, wherein, hydrogen peroxide and alkaline metal cpds are water-soluble with 25 weight % respectively The form of liquid provides, by raw material nano carbon material：Peroxide：Alkaline metal cpds：H2O weight ratio is 1：1：0.1： 100 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 120 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 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 Temperature is in 120 DEG C of oil bath, at ambient pressure back flow reaction 24 hours.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 3
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 1, unlike, in step (1), make What it is for 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 metallic atom is prepared using with the identical method of preparation example 1, unlike, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 90 DEG C, in self-generated pressure Lower reaction 24 hours.
Preparation example 5
20g is (limited purchased from Chinese Academy of Sciences's Chengdu organic chemistry as the multi-walled carbon nanotube C of raw material nano carbon material Company) 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 is 4 hours.Then, the hydrogen peroxide as peroxide and the calcium hydroxide as alkaline metal cpds are added, is mixed Close uniformly, so as to obtain aqueous dispersions, wherein, hydrogen peroxide is provided in the form of the 30 weight % aqueous solution, and calcium hydroxide is with 30 The form of weight % aqueous dispersions provides, by raw material nano carbon material：Peroxide：Alkaline metal cpds：H2O weight ratio For 1：2：0.1：200 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 180 DEG C of temperature Under, react 12 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, 150 DEG C At a temperature of dry 6 hours after, obtain nano-carbon material containing metallic atom, its composition, specific surface area and w500/w800In table 2 List.
Preparation example 6
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 5, unlike, in step (1), make What it is for 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 metallic atom is prepared using with the identical method of preparation example 5, unlike, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 240 DEG C, in self-generated pressure Lower reaction 12 hours.
Preparation example 8
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 5, unlike, in step (1), hydrogen Calcium oxide is replaced with the potassium hydroxide of equimolar amounts.
Preparation example 9
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 5, unlike, in step (1), mistake Hydrogen oxide is replaced with the TBHP of equimolar amounts.
Preparation example 10
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 5, unlike, in step (1), mistake Hydrogen oxide is replaced with the cumyl peroxide of equimolar amounts.
Preparation example 11
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 1, difference is as follows：
In step (1), after raw material nano carbon material is disperseed in deionized water, add containing the uncle as peroxide Butylhydroperoxide and the potassium hydroxide as alkaline metal cpds, it is well mixed, so as to obtain aqueous dispersions, wherein, uncle Butylhydroperoxide is provided in the form of the 10 weight % aqueous solution, and potassium hydroxide is provided in the form of the 20 weight % aqueous solution, is pressed Raw material nano carbon material：Peroxide：Alkaline metal cpds：H2O weight ratio is 1：2：0.2：120 ratio feeds intake；
In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 160 At a temperature of DEG C, react 36 hours at autogenous pressures.
Preparation example 12
It is equipped with being placed in the identical aqueous dispersions of preparation example 11 in the three-necked flask of condenser pipe, the three-necked flask is placed in Temperature is back flow reaction 36 hours at ambient pressure in the oil bath of 160 DEG C of temperature.After reaction terminates, the temperature in three-necked flask is treated After degree is down to room temperature, reactant mixture is filtered and washed, and collects solid matter.By the solid matter being collected into normal Pressure, after drying 12 hours at a temperature of 120 DEG C, obtain nano-carbon material containing metallic atom.
Preparation example 13
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 11, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, in spontaneous pressure Reacted 36 hours under power.
Preparation example 14
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 11, unlike, received as raw material Rice carbon material is multi-walled carbon nanotube B.
Preparation example 15
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 5, difference is as follows：Step (1) In, the aqueous solution for preparing aqueous dispersions contains the TBHP and conduct alkalinous metal chemical combination as peroxide The potassium hydroxide of thing, wherein, by raw material nano carbon material：Peroxide：Alkaline metal cpds：H2O weight ratio is 1：1： 0.1：50 ratio feeds intake；In step (2), obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining In, at a temperature of 120 DEG C, react 24 hours at autogenous pressures.
Preparation example 16
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 15, 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 24 hours under power.
Preparation example 17
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 15, unlike, t-butyl peroxy Change hydrogen to be replaced with the hydrogen peroxide of equimolar amounts.
Preparation example 18
(1) it is scattered in deionized water using 20g as the multi-walled carbon nanotube A of raw material nano carbon material, wherein, it is dispersed in Carried out under the conditions of sonic oscillation, sonic oscillation condition includes：Frequency is 14kHz, and the time is 0.5 hour, then adds peroxidating Hydrogen and the cobalt acetate as metallic compound, it is well mixed, so as to obtain aqueous dispersions, wherein, hydrogen peroxide is with 30 weight % The form of the aqueous solution provides, by raw material nano carbon material：Hydrogen peroxide：Metallic compound：H2O weight ratio is 1：1：0.5： 100 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 110 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, 120 DEG C At a temperature of dry 12 hours after, obtain nano-carbon material containing metallic atom, its composition, specific surface area and w500/w800In table 3 List.
Preparation example 19
It is equipped with being placed in the identical aqueous dispersions of preparation example 18 in the three-necked flask of condenser pipe, the three-necked flask is placed in In 110 DEG C of oil bath, back flow reaction 36 hours under normal 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 12 hours under degree, nano-carbon material containing metallic atom is obtained.
Preparation example 20
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 18, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube B.
Preparation example 21
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 18, 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 22
It is scattered in deionized water using 20g as the multi-walled carbon nanotube C of raw material nano carbon material, wherein, it is dispersed in super Carried out under the conditions of sound oscillation, sonic oscillation condition includes：Frequency is 90kHz, and the time is 2 hours, then add hydrogen peroxide and As the nickel acetate of metallic compound, it is well mixed, so as to obtain aqueous dispersions, wherein, hydrogen peroxide and metallic compound point There is provided not in the form of the 30 weight % aqueous solution, by raw material nano carbon material：Hydrogen peroxide：Metallic compound：H2O weight ratio For 1：2：1：50 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 180 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 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 23
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 22, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube D.
Preparation example 24
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 22, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 220 DEG C, in spontaneous pressure Reacted 24 hours under power.
Preparation example 25
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 22, unlike, in step (1), Hydrogen peroxide is replaced with the TBHP of equimolar amounts.
Preparation example 26
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 22, unlike, hydrogen peroxide is used The dibenzoyl peroxide of equimolar amounts replaces.
Preparation example 27
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 18, difference is as follows：Step (1) In, added to being dispersed with the deionized water of raw material nano carbon material as the TBHP of peroxide and as gold Belong to the palladium acetylacetonate of compound, be well mixed, so as to obtain aqueous dispersions, wherein, palladium acetylacetonate is water-soluble with 30 weight % The form of liquid is provided, and TBHP is provided in the form of 30 weight % aqueous dispersions, by raw material nano carbon material：Peroxide Compound：Metallic compound：H2O weight ratio is 1：0.5：0.1：25 ratio feeds intake；In step (2), obtained moisture is dissipated Liquid is placed in the autoclave with polytetrafluoroethyllining lining, and at a temperature of 120 DEG C, it is small to react 48 at autogenous pressures When.
Preparation example 28
It is equipped with being placed in the identical aqueous dispersions of preparation example 27 in the three-necked flask of condenser pipe, the three-necked flask is placed in Temperature is back flow reaction 48 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 29
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 27, 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 48 hours under power.
Preparation example 30
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 27, unlike, received as raw material Rice carbon material is multi-walled carbon nanotube B.
Preparation example 31
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 22, difference is as follows：Step (1) In, added to being dispersed with the deionized water of raw material nano carbon material as the cumyl hydroperoxide of peroxide and as gold Belong to the palladium of compound, so as to obtain aqueous dispersions, wherein, palladium is provided in the form of the 20 weight % aqueous solution, peroxide Change hydrogen isopropylbenzene to provide in the form of 30 weight % aqueous dispersions, by raw material nano carbon material：Peroxide：Metallic compound： H2O weight ratio is 1：1：0.2：50 ratio feeds intake；In step (2), obtained aqueous dispersions are placed in polytetrafluoroethyl-ne In the autoclave of alkene liner, at a temperature of 160 DEG C, react 24 hours at autogenous pressures.
Preparation example 32
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 31, unlike, in step (1), That as raw material nano carbon material is multi-walled carbon nanotube D.
Preparation example 33
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 31, unlike, in step (2), Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 210 DEG C, in spontaneous pressure Reacted 24 hours under power.
Preparation example 34
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 31, unlike, in step (1), Cumyl hydroperoxide is replaced with the hydrogen peroxide of equimolar amounts.
Embodiment 1-80 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 1-80.
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 weight %, with TiO2The content of the titanium elements of meter is 0.1 weight %, and the content of TPAOH is 4 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 0.504 Weight %, the content of TPAOH is 45 weight %.
Embodiment 1-44
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 and optional inorganic agent under environment temperature (25 DEG C) respectively, It will obtain after being dried and be optionally calcined in mixture feeding strip mould, it is (random to obtain nano-carbon material formed body Selected part formed body is polished, and is obtained the batten that length is 3-5mm and is used to determine crushing strength and porosity, as a result exists Listed in table 4), sieved after remaining formed body is crushed, obtain graininess formed body, its mean particle size (abbreviation grain Footpath) listed in table 4.
Table 4
1：The dosage of nano-carbon material is 10g2：TPAOH3：Tetraethyl ammonium hydroxide4：Dosage with Oxide meter
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Embodiment 45-76
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 77
Difference with embodiment 45 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 78
Difference with embodiment 45 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 45 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 45 Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Embodiment 79
Difference with embodiment 49 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 80
Difference with embodiment 49 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 49 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 49 Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Table 5
1：The dosage of nano-carbon material is 10g2：TPAOH3：TMAH4：Dosage with Oxide meter
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Testing example 1-80
The catalytic performance of the catalyst prepared using following methods successively testing example 1-80.
The graininess formed body respectively prepared by 0.5g embodiments 1-80 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 410 DEG C (concentration of normal butane is 2.18 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 3800h-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 1-80 identicals method. Experimental result is listed in table 6.
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 (43)

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, the nano-carbon material contain O elements and at least one metallic element, the metallic element choosing From transition metal, group ia metal element and group iia metallic element.
2. formed body according to claim 1, wherein, on the basis of the total amount of the nano-carbon material and in terms of element, O The content of element is 1-15 weight %, more preferably preferably 2-12 weight %, 5-10 weight %；The content of the metallic element For 0.2-20 weight %, preferably 0.5-18 weight %, more preferably 1-9 weight %.
3. formed body according to claim 1 or 2, wherein, the metallic element is selected from group VIII metallic element, I A One in race's metallic element and group iia metallic element, preferably iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, sodium, potassium, magnesium, barium and calcium Kind is two or more.
4. formed body according to claim 1, wherein, the metallic element is selected from transition metal, is preferably selected from It is more than one or both of group VIII metal element, more preferably iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum, the nano-carbon material In, the total content of the oxygen element determined by x-ray photoelectron power spectrum is IO t, by 529.5-530.8eV in x-ray photoelectron power spectrum In the range of the content of O elements that determines of peak be IO m, IO m/IO tIn the range of 0.01-0.6, the model preferably in 0.09-0.18 In enclosing；
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 0.2-1, preferably in the range of 0.25-0.9, more preferably in the range of 0.4-0.75.
5. formed body according to claim 4, 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 eIt is more excellent preferably in the range of 0.4-1.6 in the range of 0.3-2 It is selected in the range of 0.8-1.4.
6. the formed body according to claim 4 or 5, 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 60-80 weight %；In the range of 286.0-288.8eV in x-ray photoelectron power spectrum The total content for the C element that peak determines is 5-40 weight %, preferably 20-40 weight %.
7. according to the formed body described in any one in claim 4-6, wherein, on the basis of the total amount of the nano-carbon material And in terms of element, the content of O elements is 1-15 weight %, more preferably preferably 3-13 weight %, 5-10 weight %；Metal member The total amount of element is 0.4-20 weight %, more preferably preferably 2-18 weight %, 4-9 weight %；The content of C element is 65- 98.6 weight %, preferably 69-95 weight %, more preferably 81-91 weight %.
8. formed body according to claim 1, wherein, the metallic element is selected from group ia metal element and group iia More than one or both of metallic element, preferably sodium, potassium, magnesium, barium and calcium, in the nano-carbon material, by X ray photoelectricity The total content for the oxygen element that sub- power spectrum determines is IO t, determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum The contents of O elements be IO m, IO m/IO tIn the range of 0.02-0.3, preferably in the range of 0.05-0.25, more preferably exist In the range of 0.08-0.2；
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 0.3-1.5, preferably in the range of 0.3-1.2, more preferably in the range of 0.5-1, further preferably in 0.6- In the range of 0.9.
9. formed body according to claim 8, 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 eIt is more excellent preferably in the range of 0.45-1.5 in the range of 0.4-2 It is selected in the range of 0.8-1.3, further preferably in the range of 0.9-1.2.
10. formed body according to claim 8 or claim 9, wherein, with the nano-carbon material by x-ray photoelectron power spectrum On the basis of the total amount of the C element of determination, the C element that is determined by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum Content be 65-95 weight %, preferably 75-85 weight %；In the range of 286.0-288.8eV in x-ray photoelectron power spectrum The total content of C element that determines of peak be 5-35 weight %, preferably 15-25 weight %.
11. according to the formed body described in any one in claim 8-10, wherein, using the total amount of the nano-carbon material as base Accurate and in terms of element, the content of O elements be 2-12 weight %, more preferably preferably 2.5-10 weight %, 5-8 weight %, and C is first The content of element is 78-97.5 weight %, more preferably preferably 85-96.5 weight %, 88-94 weight %, the metallic element Total amount be 0.5-10 weight %, more preferably preferably 1-5 weight %, 1-4 weight %.
12. according to the formed body described in any one in claim 1-11, wherein, the nano-carbon material is CNT, Preferably multi-walled carbon nanotube；
Preferably, the specific surface area of the multi-walled carbon nanotube is in 50-500m2In the range of/g, preferably in 90-300m2/ g model In enclosing, more preferably in 120-180m2In the range of/g；
Preferably, weight-loss ratio of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C Weight-loss ratio in temperature range is w500, w500/w800It is more excellent preferably in the range of 0.02-0.4 in the range of 0.01-0.5 It is selected in the range of 0.05-0.15, the weight-loss ratio determines in air atmosphere.
13. 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；
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 peroxide and at least one metal are dispersed with the aqueous dispersions Compound, the metallic compound are selected from alkaline metal cpds and transistion metal compound, in the alkaline metal cpds Metallic element be selected from group ia metal element and group iia metallic element, in course of reaction, the temperature of the aqueous dispersions exists In the range of 80-300 DEG C.
14. formed body according to claim 13, wherein, the metallic element in the transistion metal compound is preferably selected from Group VIII metallic element, it is more preferably selected from iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum；
Preferably, the transistion metal compound is selected from metal acetate salt, metal gluconate hydrochlorate, metal carbonate, metal base Formula carbonate, metal hydroxides and metal complex；
The alkaline metal cpds are selected from hydroxide and basic salt, are preferably selected from hydroxide, carbonate and bicarbonate, More preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, calcium hydroxide, barium carbonate, carbon It is more than one or both of sour calcium, calcium bicarbonate, barium hydroxide and magnesium hydroxide.
15. the formed body according to claim 13 or 14, wherein, the metallic compound is transistion metal compound, former Expect nano-carbon material：Peroxide：The weight ratio of metallic compound is 1：0.01-20：In the range of 0.01-10, preferably exist 0.1-18：In the range of 0.02-5, more preferably 1：0.2-15：In the range of 0.05-4, further preferably 1：0.5-2： In the range of 0.1-1.
16. formed body according to claim 15, wherein, raw material nano carbon material：H2O weight ratio is 1：2-500 model In enclosing, preferably 1：In the range of 5-400, more preferably 1：In the range of 10-350, further preferably 1：25-100 model In enclosing.
17. the formed body according to claim 13 or 14, wherein, the metallic compound is alkaline metal cpds, former Expect nano-carbon material：Peroxide：The weight ratio of alkaline metal cpds is 1：0.02-20：In the range of 0.01-10, preferably 1：0.2-16：In the range of 0.02-5, more preferably 1：0.5-5：In the range of 0.05-1, further preferably 1：1-2： In the range of 0.1-0.2.
18. formed body according to claim 17, wherein, raw material nano carbon material：H2O weight ratio is 1：2-500 model In enclosing, preferably 1：In the range of 10-400, more preferably 1：In the range of 50-200.
19. according to the formed body described in any one in claim 13-18, wherein, the peroxide is selected from hydrogen peroxide With the organic peroxide shown in Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl andAnd R1 And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl.
20. according to the formed body described in any one in claim 13-19, wherein, in course of reaction, the aqueous dispersions Temperature is maintained in the range of 90-240 DEG C, preferably in the range of 120-220 DEG C；
Preferably, the duration of the reaction is more excellent preferably in the range of 2-72 hours in the range of 0.5-96 hours It is selected in the range of 12-36 hours.
21. according to the formed body described in any one in claim 13-20, 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 0.02 weight %；The content of O elements is not higher than 1.5 weights Measure %, preferably not higher than 0.3 weight %；The total amount of metallic element is below 2.5 weight %, preferably below 0.5 weight %.
22. according to the formed body described in any one in claim 13-21, 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 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.
23. according to the formed body described in any one in claim 13-22, 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；The drying Duration be preferably 4-24 hours, more preferably 6-12 hours no more than 48 hours.
24. according to the formed body described in any one in claim 1-23, wherein, on the basis of the total amount of the formed body, The content of the nano-carbon material is 6-94 weight %, more preferably preferably 10-90 weight %, 40-90 weight %, further Preferably 70-90 weight %, the content of the heat-resistant inorganic oxide are 6-94 weight %, preferably 10-90 weight %, more excellent Elect 10-60 weight %, more preferably 10-30 weight % as.
25. according to the formed body described in any one in claim 1-24, 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 %, more preferably 50-99 weight %.
26. 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, determined by x-ray photoelectron power spectrum described surface treated Nano-carbon material contains O elements and at least one metallic element, and the metallic element is selected from transition metal, group ia metal Element and group iia metallic element.
27. according to the method for claim 26, 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 III,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl；
The alkali and the mol ratio in the binding agent source are preferably 0.1-10：1, preferably 0.2-5：1, more preferably 0.3-2：1, The binding agent source is in terms of oxide.
28. the method according to claim 26 or 27, wherein, before the mixture is molded, this method also includes will The mixture carries out hydro-thermal process.
29. according to the method for claim 28, 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.
30. according to the method described in any one in claim 26-29, 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.
31. 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, Determine that the surface treated nano-carbon material contains O elements and at least one metallic element, institute by x-ray photoelectron power spectrum State metallic element and be selected from transition metal, group ia metal element and group iia metallic element.
32. forming method according to claim 31, wherein, the aqueous dispersions also contain at least one inorganic agent, institute State inorganic agent and be different from institute for the combination more than one or both of alkali, peroxide and metallic compound, the alkali State metallic compound；；
Preferably, the alkali is organic base, is preferably selected from quaternary ammonium base, aliphatic amine and aliphatic hydramine, is more preferably selected from synthesizing HTS template, the quaternary ammonium base shown in formula III is further preferably selected from,
In formula III, R8、R9、R10And R11It is identical or different, respectively C1-C4Alkyl；
Preferably, the peroxide is selected from hydrogen peroxide and the organic peroxide shown in Formulas I,
In Formulas I, R1And R2It each is selected from H, C4-C12Alkyl, C6-C12Aryl, C7-C12Aralkyl andAnd R1 And R2It is asynchronously H, R3For C4-C12Straight or branched alkyl or C6-C12Aryl；
The peroxide is preferably selected from hydrogen peroxide, TBHP and cumyl peroxide；
The inorganic agent is for alkali and selected from least one of peroxide and metallic compound, preferably alkali, peroxide And metallic compound, the mol ratio of alkali, peroxide and metallic compound is 1：0.1-10：0.02-1.5, preferably 1：0.4- 7：0.07-0.8.
33. according to the method for claim 32, wherein, the metallic compound is transition metal salt and/or alkalinous metal Compound, the metallic element in the alkaline metal cpds are selected from group ia metal element and group iia metallic element；
Preferably, the alkaline metal cpds are selected from the hydroxide containing the metallic element and the alkali containing the metallic element Property salt, is preferably selected from the hydroxide containing the metallic element, the carbonate containing the metallic element and containing the metallic element Bicarbonate, more preferably sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, carbonic acid It is more than one or both of potassium, calcium carbonate, barium carbonate, sodium acid carbonate, calcium bicarbonate, saleratus and barium bicarbonate；
Preferably, the transistion metal compound is selected from transition metal acetate, transition metal oxalates, transition metal alkali formula carbon Hydrochlorate and transition metal complex, the transition metal are preferably selected from group VIII metallic element, are more preferably selected from Iron, ruthenium, cobalt, rhodium, nickel, palladium and platinum.
34. the method according to claim 32 or 33, wherein, relative to 100 parts by weight binder sources, the inorganic agent with The mol ratio in the binding agent source is 0.1-10：1, preferably 0.1-8：1, more preferably 0.3-4：1, the binding agent source is with oxygen Compound meter.
35. according to the method described in any one in claim 31-34, 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.
36. according to the method described in any one in claim 26-35, 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 %, more preferably 50-99 weight %.
37. according to the method described in any one in claim 26-36, 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 75-95 weight %, more preferably 85-95 are heavy % is measured, the content of the heat-resistant inorganic oxide is 5-95 weight %, and preferably 5-25 weight %, more preferably 5-15 are heavy Measure %.
38. according to the method described in any one in claim 26-37, wherein, the surface treated nano-carbon material For the nano-carbon material described in any one in claim 2-12 and 13-25.
39. according to the method described in any one in claim 26-38, wherein, the drying is at a temperature of 50-200 DEG C Carry out, carried out preferably at a temperature of 120-180 DEG C；The duration of the drying is no more than 48 hours, preferably 3-24 Hour, 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 1-12 hours, preferably 2-4 hours.
40. nano-carbon material formed body prepared by a kind of method in 26-39 as claim described in any one.
41. catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction in claim 1-25 and 40 described in any one Application, the hydrocarbon is preferably alkane, more preferably C2-C12Alkane, more preferably normal butane.
42. 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 1-25 and 40.
43. according to the method for claim 42, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably Normal butane.
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