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

Abstract

The invention discloses a kind of nano-carbon material formed body, 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 C element, O elements and at least one metallic element, and the metallic element is selected from 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 C Element, O elements and at least one metallic element, the metallic element are selected from group ia metal element and group iia metallic 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 one kind be dispersed with raw material nano carbon material and The aqueous dispersions of at least one alkaline metal cpds are reacted in closed container, the gold in the alkaline metal cpds Category element is selected from group ia metal element and group iia metallic element, and in course of reaction, the temperature of the aqueous dispersions is maintained at In the range of 100-300 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 C element, O elements and at least one metal by x-ray photoelectron power spectrum Element, the metallic element are selected from 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 C element, O elements and at least one metallic element, and the metallic element is selected from group ia metal element and II A Race's 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, nano-carbon material refers to disperse The phase yardstick at least one-dimensional carbon material less than 100nm.In the present invention, " at least one " represents one or more kinds of.This hair In bright, when representing number range, " ×-× in the range of " include two binary values.
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 C element, O elements and at least one Metallic element (hereinafter, otherwise referred to as nano-carbon material containing metallic atom).
According to the formed body described in one side of the invention, in the nano-carbon material, metallic element is selected from group ia Metallic element and group iia metallic element, its instantiation can include but is not limited to lithium, sodium, potassium, beryllium, magnesium, calcium, barium and strontium One or both of more than.Preferably, the metallic element is more than one or both of sodium, potassium, magnesium, calcium and barium, is incited somebody to action When this contains catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction, more preferable catalytic performance can be obtained.From entering one The angle that step improves catalytic performance when being used as the catalyst of hydrocarbon dehydrogenation reaction containing the nano-carbon material formed body is set out, described Metallic element is more preferably more than one or both of magnesium, barium and calcium.
The content of C element, O elements and metallic element can be according to the source of the nano-carbon material in the nano-carbon material Selected, can also be selected with the concrete application occasion of nano-carbon material formed body.Usually, with nano-carbon material On the basis of total amount and in terms of element, the content of O elements can be 1-10 weight %, preferably 2-8 weight %, more preferably 3-7 Weight %, more preferably 5-6 weight %；The content of the metallic element can be 0.1-10 weight %, preferably 0.2-8 Weight %, more preferably 0.5-5 weight %, more preferably 1-4 weight %；The content of C element can be 80-98.9 weights Measure %, more preferably preferably 84-97.8 weight %, more preferably 88-96.5 weight %, 90-94 weight %.
In the present invention, the content of each element is determined using X-ray photoelectron spectroscopy.Sample is before testing at 150 DEG C At a temperature of in helium atmosphere dry 3 hours.Wherein, X-ray photoelectron spectroscopic analysis are in Thermo Scientific companies Equipped with being tested on the ESCALab250 type x-ray photoelectron spectroscopies of Thermo Avantage V5.926 softwares, swash Rise for monochromatization Al K α X ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analyze Base vacuum during test is 6.5 × 10-10Mbar, C1s peaks (284.0eV) correction of electron binding energy simple substance carbon, Data processing is carried out on Thermo Avantage softwares, quantitative analysis is carried out using sensitivity factor method in analysis module.
According to the formed body of one side of the invention, in the nano-carbon material, determined by x-ray photoelectron power spectrum The total content of oxygen element is IO t, the O elements that are determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum contain Measure as IO m, IO m/IO tTypically in the range of 0.01-0.3, preferably in the range of 0.02-0.25, more preferably in 0.05-0.23 In the range of, further preferably in the range of 0.09-0.18.According to the formed body of the present invention, in the nano-carbon material, by The content for the O elements that peak in x-ray photoelectron power spectrum in the range of 531.0-533.5eV determines is IO nm, IO nm/IO tTypically exist In the range of 0.7-0.99, preferably in the range of 0.75-0.98, more preferably in the range of 0.77-0.95, further preferably In the range of 0.82-0.91.
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 formed body of one side of the invention, in the nano-carbon material, by x-ray photoelectron power spectrum The amount for the O elements (that is, C=O) that peak in the range of 531.0-532.5eV 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 eTypically in the range of 0.1-3, preferably exist In the range of 1-3, more preferably in the range of 1.2-2.5, the scope further preferably in 1.4-2, still more preferably exist In the range of 1.5-1.8.
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 formed body of one side of the invention, on the basis of the total amount of C element in nano-carbon material, by X ray The content for the C element that peak in photoelectron spectroscopy in the range of 284.7-284.9eV determines can be 60-98 weight %, be preferably 65-90 weight %, more preferably 75-85 weight %；It is true by the peak in the range of 286.0-288.8eV in x-ray photoelectron power spectrum The total content of fixed C element can be 2-40 weight %, more preferably preferably 10-35 weight %, 15-25 weight %.
In the present invention, by the area A of the C1s spectral peaks in x-ray photoelectron power spectrumC 1The total amount of C element is determined, by X ray C1s spectral peaks in photoelectron spectroscopy are divided into two groups of peaks, i.e., the spectral peak in the range of 284.7-284.9eV (corresponds to graphite mould carbon Species) and spectral peak (corresponding to non-graphite type carbon species) in the range of 286.0-288.8eV, will be in 284.7-284.9eV In the range of the area of spectral peak be designated as AC 2, the area of the spectral peak in the range of 286.0-288.8eV is designated as AC 3, by X ray light Content=the A for the C element that peak in electron spectrum in the range of 284.7-284.9eV determinesC 2/AC 1, by x-ray photoelectron power spectrum Total content=the A for the C element that peak in the range of middle 286.0-288.8eV determinesC 3/AC 1。
According to the formed body of one side of the invention, 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 eTypically in the range of 0.4-2.5, preferably in the range of 1-2.5, More preferably in the range of 1.2-2.2, further preferably in the range of 1.5-2, the scope still more preferably in 1.8-2 It is interior.
In the present invention, the spectral peak in x-ray photoelectron power spectrum in the range of 286.0-288.8eV (is corresponded into non-graphite Carbon species) be further divided into two groups of peaks, i.e., the spectral peak in the range of 286.0-286.2eV (corresponds to hydroxyl and ether type carbon thing Kind) and spectral peak (corresponding to carboxyl, acid anhydride and ester type carbon species) in the range of 288.6-288.8eV, will be in 286.0- The area of spectral peak in the range of 286.2eV is designated as AC 4, the area of the spectral peak in the range of 288.6-288.8eV is designated as AC 5, IC c/IC e=AC 5/AC 4。
In 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 286.0-288.8eV refers to that the combination corresponding to summit can be in 286.0- Whole peaks in the range of 288.8eV.
According to the formed body described in one side of the invention, the nano-carbon material can by it is common it is various in the form of deposit It is being specifically as follows but is being not limited to CNT, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, nanometer Buddha's warrior attendant Combination more than one or both of stone and fullerene.The CNT can be single-walled carbon nanotube, double wall carbon nano-tubes Combination more than one or both of pipe and multi-walled carbon nanotube.According to nano-carbon material formed body, the nano-carbon material Preferably multi-walled carbon nanotube.
According to the formed body described in one side of the invention, the specific surface area of the multi-walled carbon nanotube is preferably 50- 500m2/ g, the catalytic performance of formed body so can be further improved, especially as the catalyst of hydrocarbons dehydrogenation reaction Catalytic performance.The specific surface area of the multi-walled carbon nanotube is more preferably 80-300m2/ g, more preferably 100-250m2/ g, Still more preferably it is 120-180m2/g.In the present invention, the specific surface area is determined by nitrogen adsorption BET method.
Formed body described according to the first aspect of the invention, temperature of the multi-walled carbon nanotube at 400-800 DEG C Weight-loss ratio in section is w800, the weight-loss ratio in 400-500 DEG C of temperature range is w500, w500/w800It is preferred that in 0.01- In the range of 0.5, more preferable catalytic effect can be so obtained, during catalyst particularly as hydrocarbons dehydrogenation reaction, More preferable catalytic effect can be obtained.w500/w800More preferably in the range of 0.02-0.4, further preferably 0.05-0.15's In the range of.In the present invention, w800=W800- W400, w500=W500- W400, W400For the quality damage determined at a temperature of 400 DEG C Mistake rate, W800For the mass loss rate determined at a temperature of 800 DEG C, W500For the mass loss determined at a temperature of 500 DEG C Rate；The weight-loss ratio is determined using thermogravimetric analyzer in air atmosphere, and test initial temperature is 25 DEG C, heating rate 10 ℃/min；Sample is depressed in 150 DEG C of temperature and 1 normal atmosphere dried 3 hours in helium atmosphere before testing.
According to the formed body described in one side of the invention, in the nano-carbon material, outside oxygen atom and nitrogen-atoms Other nonmetallic heteroatoms, such as sulphur atom and phosphorus atoms, its content can be customary amount.Usually, the nano carbon material In material, the total amount of other nonmetallic heteroatoms (such as sulphur atom and phosphorus atoms) outside oxygen atom and nitrogen-atoms can be 0.5 weight Measure below %, preferably below 0.2 weight %, more preferably below 0.1 weight %, more preferably 0.05 weight % with Under.In the nano-carbon material, in addition to selected from aforesaid metal elements, other metallic atoms, other metals can also be contained Atom for example can be from the catalyst used when preparing nano-carbon material.The content of other metallic atoms is generally Below 2.5 weight %, it is still more preferably 0.5 weight more preferably below 1 weight % preferably below 2 weight % Below % is measured, particularly preferably below 0.2 weight %.
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 %.The composition of formed body can use x-ray fluorescence spectrometry.In embodiment disclosed by the invention, by the gauge that feeds intake The composition of the composition and the formed body using x-ray fluorescence spectrometry of obtained formed body is basically identical, and error is 1% Within.
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：By a kind of aqueous dispersions for being dispersed with raw material nano carbon material and at least one alkaline metal cpds in closed container Reacted.
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 nano-carbon material formed body to be used as to the catalyst of hydrocarbon dehydrogenation reaction, it can obtain and preferably urge Change performance.From the angle of the catalytic performance of further catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction for improving and preparing Degree sets out, and the metallic element is more preferably selected from magnesium, barium and calcium.
The alkaline metal cpds are preferably selected from hydroxide containing the metallic element and containing the metallic elements Basic salt.The alkaline metal cpds are more preferably selected from the hydroxide containing the metallic element, containing the metallic element Carbonate and the bicarbonate containing the metallic element.The instantiation of the alkaline metal cpds can include but unlimited In：Lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, carbon One or both of sour sodium, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, calcium bicarbonate, saleratus and barium bicarbonate More than.From the angle of catalytic activity of the further raising nano-carbon material formed body in hydrocarbon dehydrogenation reaction, the alkalescence Metallic compound be preferably one kind in calcium hydroxide, barium carbonate, calcium carbonate, calcium bicarbonate, barium hydroxide and magnesium hydroxide or It is two or more, more preferably more than one or both of calcium hydroxide, magnesium hydroxide and barium hydroxide.
The solids content of the aqueous dispersions is can be defined raw material nano carbon material is dispersed.Preferably, raw material Nano-carbon material：The weight ratio of alkaline metal cpds is 1：In the range of 0.01-5.Raw material nano carbon material：Alkalinous metal The weight ratio of compound is more preferably 1：In the range of 0.02-2, further preferably 1：It is further excellent in the range of 0.02-1 It is selected in 1：In the range of 0.02-0.5, particularly preferably 1：In the range of 0.1-0.3.
Raw material nano carbon material：H2O weight ratio is preferably 1：In the range of 2-100, the scope is in the dosage of water Within when, structural form retentivity of the nano-carbon material in processing procedure is more preferable, such as：Raw material nano carbon material is carbon nanometer Guan Shi, it will not be cut off substantially in processing procedure.Raw material nano carbon material：H2O weight ratio is more preferably 1：3-80 model In enclosing, further preferably 1：In the range of 5-60, still more preferably 1：In the range of 8-40.
In course of reaction, the temperature of the aqueous dispersions can be in the range of 80-310 DEG C.In the aqueous dispersions When temperature is within above range, the oxygen atom in raw material nano carbon material can not only be effectively improved and metallic atom contains Amount, and the structural form of raw material nano carbon material will not be produced and significantly affected.In course of reaction, the temperature of the aqueous dispersions Degree is more preferably in the range of 100-300 DEG C, further preferably in the range of 120-250 DEG C, still more preferably in 120- In the range of 220 DEG C.
Usually, the duration of the reaction can be in the range of 0.5-144 hours, the model preferably in 2-72 hours In enclosing, more preferably in the range of 4-24 hours.
The aqueous dispersions can be formed using conventional various methods, such as raw material nano carbon material can be disperseed In water (being preferably deionized water), the alkaline metal cpds are then added, so as to obtain the aqueous dispersions.In order to enter one Step improves the dispersion effect of raw material nano carbon material, while shortens the scattered time, can use the method for sonic oscillation by original Material nano-carbon material is dispersed in the aqueous solution dissolved with the alkaline metal cpds.The condition of the sonic oscillation can be Conventional selection, usually, the frequency of the sonic oscillation can be 20-100kHz, preferably 40-60kHz；The sonic oscillation Duration can be 0.1-12 hours, preferably 0.2-6 hours, more preferably 0.5-1 hours.The alkalinous metal chemical combination Thing can be provided in the form of solution (being preferably the aqueous solution), can also be provided, be not particularly limited in the form of pure material.
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 Formulas I：
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl.The C1-C4Alkyl include C1-C4Straight chained alkyl and C3-C4Branched alkyl, its instantiation can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group and the tert-butyl group.Preferably, organic silicon source be selected from methyl silicate, tetraethyl orthosilicate, positive n-propyl silicate, Positive isopropyl silicate and positive silicic acid N-butyl.
In another example when the heat-resistant inorganic oxide is titanium oxide, the precursor of the heat-resistant inorganic oxide can be with For organic titanate and/or inorganic titanium salt, its instantiation can include but is not limited to TiCl4、Ti(SO4)2、TiOCl2, hydrogen-oxygen Change titanium, nitric acid titanium salt, phosphoric acid titanium salt, fatty alcohol titanium and organic titanate (such as tetraisopropyl titanate, the n-propyl of metatitanic acid four, metatitanic acid One or more in four butyl esters and tetraethyl titanate) in one or more.
Method according to third aspect of the present invention, in one embodiment, the binding agent source are selected from heat-resisting Inorganic oxide, such as the heat-resistant inorganic oxide provided with solation.In this embodiment, by nano-carbon material with gluing It is molded after knot agent source is well mixed.In another embodiment, at least part binding agent source is heat resistant inorganic oxygen The precursor of compound.In this embodiment, after nano-carbon material is mixed with binding agent source, entered according to the species in binding agent source Row processing, is transformed into heat-resistant inorganic oxide by the precursor of the heat-resistant inorganic oxide in binding agent source.
Method according to third aspect of the present invention, the mixture preferably also contain at least one alkali, such energy Further improve catalytic activity of the nano-carbon material formed body finally prepared in the catalyst as hydrocarbon dehydrogenation reaction.It is described Alkali can be organic base and/or inorganic base.Alkali (such as sodium hydroxide, hydrogen that the inorganic base can be ammonia, cation is alkali metal Potassium oxide) and cation for alkaline-earth metal one or both of alkali (such as magnesium hydroxide, calcium hydroxide, barium hydroxide) with On.The organic base can be more than one or both of hydrazine, urea, amine and quaternary ammonium base.
The quaternary ammonium base is specifically as follows the compound shown in Formula II：
In Formula II, R5、R6、R7And R8Can be each C1-C20Alkyl (including C1-C20Straight chained alkyl and C3-C20's Branched alkyl) or C6-C12Aryl.The C1-C20The instantiation of alkyl can include but is not limited to：Methyl, ethyl, N-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl, n-hexyl, N-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, One or more in n-hexadecyl, n-octadecane base and n-eicosane base.The C6-C12The instantiation of aryl can be with Including but not limited to phenyl, naphthyl, 4- aminomethyl phenyls and 4- ethylphenyls.R5、R6、R7And R8It is preferred that it is respectively C1-C10Alkyl (including C1-C10Straight chained alkyl and C3-C10Branched alkyl), more preferably respectively C1-C6Alkyl (including C1-C6Straight chain Alkyl and C3-C6Branched alkyl).
The amine refers to the material that the one, two or three hydrogen in amino molecule is substituted and formed by organic group, described Organic group can form cyclic structure with nitrogen atom bonding.The organic group can be substitution (such as hydroxyl substitution) or not take The aliphatic alkyl in generation and/or substitution (such as hydroxyl substitution) or unsubstituted aromatic hydrocarbyl, the aliphatic alkyl can be Substitute (such as hydroxyl substitution) or unsubstituted representative examples of saturated aliphatic chain alkylene, substitution (such as hydroxyl substitution) or unsubstituted unsaturated lipid Fat race chain alkylene, substitution (such as hydroxyl substitution) or unsubstituted saturated alicyclic hydrocarbon base and substitution (such as hydroxyl substitution) do not take It is more than one or both of the unsaturated lipid cyclic hydrocarbon radical in generation.Specifically, the amine can be substitution (such as hydroxyl substitution) or not Substituted representative examples of saturated aliphatic amine, substitution (such as hydroxyl substitution) or unsubstituted unsaturated aliphatic amine, substitution (such as hydroxyl substitution) Or unsubstituted saturation aliphatic cyclic amine, substitution (such as hydroxyl substitution) or unsubstituted unsaturated lipid cyclammonium, substitution (such as hydroxyl substitution) Or more than unsubstituted heterocyclic amine and substitution one or both of (such as hydroxyl substitution) or unsubstituted arylamine.
The representative examples of saturated aliphatic amine is preferably the compound shown in formula III, the compound shown in formula IV and general formula R16 (NH2)2It is more than one or both of material of expression,
In formula III, R9、R10And R11Respectively H or C1-C6Alkyl, and R9、R10And R11It is asynchronously H.The present invention In, C1-C6The instantiation of alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl and n-hexyl.
In formula IV, R12、R13And R14Respectively-R15OH or hydrogen, and R12、R13And R14In it is at least one be-R15OH, R15For C1-C4Alkylidene.In the present invention, C1-C4Alkylidene include C1-C4Straight-chain alkyl-sub and C3-C4Branched alkylen Base, its instantiation can include but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- isobutyl Base and the sub- tert-butyl group.
General formula R16(NH2)2In, R16Can be C1-C6Alkylidene.In the present invention, C1-C6Alkylidene include C1-C6's Straight-chain alkyl-sub and C3-C6Branched alkylidene, its instantiation can include but is not limited to：Methylene, ethylidene, Asia positive third Base, isopropylidene, sub- normal-butyl, isobutylidene, the sub- tert-butyl group, sub- n-pentyl and sub- n-hexyl.
The unsaturated aliphatic amine refers to the aliphatic streptamine containing unsaturated group, the unsaturation in molecular structure Group is preferably alkenyl (that is ,-C=C-).The quantity of the unsaturated group and amino can be one or more, not have It is particularly limited to.
The instantiation of the organic base can include but is not limited to urea, hydrazine, methylamine, dimethylamine, trimethylamine, ethamine, Diethylamine, triethylamine, n-propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, three It is n-butylamine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, new Amylamine, iso-amylamine, di-iso-amylamine, triisoamylamine, tertiary amylamine, hexylamine, octylame, nonyl amine, decyl amine, undecyl amine, dodecyl Amine, dodecyl-dimethyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, monoethanolamine, three second Hydramine, triisopropanolamine, diethanol amine, dipropanolamine, tripropanol amine, two butanolamines, three butanolamines, dodecyl dimethyl Amine, tetradecyldimethylamine, hexadecyldimethyl benzyl ammonium amine, ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, substitution Or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydro pyrrole Pyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted two Hydrogen quinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinolin, take Generation or unsubstituted pyrimidine, aniline, diphenylamines, benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, o-toluidine, Methylaniline, open-chain crown ether, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines, 2,6- dimethyl benzenes Amine, 3,4- dimethylanilines, 3,5- dimethylanilines, 2,4,6- trimethylanilines, o ethyl aniline, N- butylanilines, 2,6- Diethylaniline, cyclohexylamine, cyclopentamine, hexamethylenetetramine, diethylenetriamine, triethylene tetramine, TMAH, four Ethyl ammonium hydroxide, TPAOH (including its various isomers, such as four n-propyl ammonium hydroxide and tetra isopropyl hydrogen-oxygen Change ammonium), TBAH (including its various isomers, such as 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four Isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and one kind in four pentyl ammonium hydroxide (including its various isomers) or It is two or more.
Preferably, the alkali is organic base, so can further improve the nano-carbon material formed body conduct finally prepared The catalytic activity of the catalyst of hydrocarbon dehydrogenation reaction.It is highly preferred that the alkali is synthesis of titanium silicon molecular sieve template, such as Formula II institute The quaternary ammonium base shown, the nano-carbon material formed body thus prepared have higher crushing strength, and anti-as hydrocarbon dehydrogenation The catalytic activity further improved is shown during the catalyst answered.
The dosage of the alkali can be selected according to the dosage in binding agent source.Usually, the alkali and the binding agent The mol ratio in source can be 0.05-15：1, preferably 0.1-12：1, more preferably 0.12-6：1, the binding agent source is to aoxidize Thing 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- molecular sieve (such as HTS) and Si-Al molecular sieve.The crystallization mother liquor refers to passing through water When thermal crystallisation prepares molecular sieve, the mixture obtained to hydrothermal crystallizing carries out the liquid that separation of solid and liquid obtains, i.e., from hydrothermal crystallizing Isolate the liquid mixture remained after the molecular sieve to be formed in obtained mixture, also referred to as synthesis mother liquid, filtering waste liquid or Filter raw liquid.The rearrangement modified mother liquor refers to when preparing modified molecular screen by hydrothermal modification rearrangement, to hydrothermal modification weight The mixture that is obtained after row carries out the liquid that separation of solid and liquid obtains, i.e., is isolated in the mixture for resetting to obtain from hydrothermal modification point The liquid mixture remained after son sieve, also referred to as reset mother liquor, modified mother liquor, reset filtering waste liquid, modified filtering waste liquid, modification Filter raw liquid resets filter raw liquid.The crystallization mother liquor and rearrangement solution can be mixed directly with nano-carbon material, as needed It can also be concentrated or be mixed after being diluted with nano-carbon material, can enable binding agent source, alkali and the dosage of water Meet to require, 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), the crystallization mother liquor (crystallization mother liquor of such as HTS) of molecular screen containing heteroatom, Si-Al molecular sieve crystallization mother liquor and One or both of modification rearrangement solution (rearrangement solution of such as silica zeolite and HTS) of above-mentioned siliceous molecular sieve with On mixed liquor.
The concrete composition of the crystallization mother liquor and rearrangement solution is not particularly limited, as long as binding agent source and optional can be provided Alkali.As an example, in the crystallization mother liquor of siliceous molecular sieve, with SiO2The content of the element silicon of meter is generally 0.05-10 weight %, preferably 0.1-5 weight %, more preferably 1-4 weight %；The content of alkali is generally 0.05-15 weights Measure %, more preferably preferably 0.1-15 weight %, 1.5-14 weight %.As another example, the rearrangement of HTS In liquid, with SiO2The content of the element silicon of meter is generally 0.01-10 weight %, preferably 0.02-5 weight %, more preferably 0.5-2 weight %；With TiO2The content of the titanium elements of meter is generally 0.0001-0.2 weight %, preferably 0.001-0.1 weights Measure %, more preferably 0.01-0.08 weight %；The content of alkali is generally 0.01-10 weight %, preferably 0.05-5 weight %, More preferably 1-4 weight %.As there is an example, in the crystallization mother liquor of Si-Al molecular sieve, with SiO2The element silicon of meter contains Amount is generally 0.05-10 weight %, more preferably preferably 0.1-8 weight %, 1-4 weight %；With Al2O3The aluminium element of meter Content is generally 0.01-5 weight %, preferably 0.05-2 weight %, more preferably 0.1-0.5 weight %, and the content of alkali is general For 0.05-15 weight %, preferably 0.1-14 weight %, more preferably 8-13 weight %.
Method according to third aspect of the present invention, in a preferred embodiment, by the mixture Before being molded, the mixture is subjected to hydro-thermal process (that is, mixture hydro-thermal process obtained is molded), such energy Further improve catalytic activity during catalyst of the nano-carbon material formed body finally prepared as hydrocarbon dehydrogenation reaction.It is excellent at this In the embodiment of choosing, nano-carbon material, binding agent source and optional alkali can be dispersed in water, aqueous dispersions are carried out Hydro-thermal process.
In the preferred embodiment, the condition of hydro-thermal process is not particularly limited, as long as enter in closed environment Row high-temperature process.Specifically, the temperature of the hydro-thermal process can be 100-200 DEG C, preferably 120-180 DEG C.It is described The time of hydro-thermal process can be selected according to the temperature for carrying out hydro-thermal process, typically can be 0.5-24 hours, be preferably 6-12 hours.The hydro-thermal process can carry out (that is, in hydrothermal treatment process, not applying pressure additionally at autogenous pressures Power), it can also be carried out under conditions of pressure is additionally applied.Preferably, the hydro-thermal process is carried out at autogenous pressures.
Method according to third aspect of the present invention, the dosage in binding agent source can be according to expected nano-carbon material The content of binding agent is selected in formed body.Usually, the dosage in the binding agent source causes in the formed body that finally prepares, The content of nano-carbon material can be more than 5 weight % (such as more than 6 weight %), preferably more than 10 weight %, more preferably More than 50 weight %, it is still more preferably more than 70 weight %, still more preferably more preferably more than 60 weight % For more than 75 weight %, particularly preferably more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %, Preferably below 94 weight %, more preferably below 90 weight %.In an example, with the nano-carbon material formed body On the basis of total amount, the content of the nano-carbon material can be 5-95 weight %, preferably 6-94 weight %, more preferably 8-92 Weight %, more preferably 10-90 weight %, it is still more preferably 20-90 weight %, particularly preferably 40-90 weight % is measured, particularly preferably 70-90 weight %, the content of the heat-resistant inorganic oxide can be 5-95 weight %, be preferably 6-94 weight %, more preferably 8-92 weight %, more preferably 10-90 weight %, it is still more preferably 10-80 weights %, particularly preferably 10-60 weight % are measured, particularly preferably 10-30 weight %.When carrying out hydro-thermal process before the forming, i.e., Make under relatively low binder content, can also obtain higher intensity.Usually, when carrying out hydro-thermal process before the forming, with institute On the basis of the total amount for stating formed body, the content of the nano-carbon material is preferably 75-95 weight %, and more preferably 85-95 is heavy % is measured, the content of the heat-resistant inorganic oxide is preferably 5-25 weight %, more preferably 5-15 weight %.
Method according to third aspect of the present invention, conventional method can be used to contain nano-carbon material and bonding The mixture in agent source is molded, and obtains article shaped., can be by way of mediating and/or extruding by institute as an example State mixture shaping.The article shaped can have common variously-shaped such as spherical, bar shaped.
Method according to third aspect of the present invention, the article shaped can be dried under normal conditions, To remove the volatile materials in the article shaped.Usually, the drying can be carried out at a temperature of 50-200 DEG C, preferably Carry out at a temperature of 80-180 DEG C, carried out more preferably at a temperature of 100-150 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, can Think not surface treated nano-carbon material, or surface treated nano-carbon material.In the present invention, penetrated using X Photoelectron Spectroscopy detects to the surface of nano-carbon material, if removing C in nano-carbon material surface-element after testing The total content of element outside element is below 2 weight %, then the nano-carbon material is considered as into not surface treated nano carbon material Material, conversely, the nano-carbon material then is considered as into surface treated nano-carbon material.
In one embodiment, the nano-carbon material is not surface treated nano-carbon material.In the embodiment party In formula, before the mixture is molded, the mixture is preferably subjected to hydro-thermal process, can not only so be significantly improved The intensity of the formed body finally prepared, and the catalytic performance of the formed body finally prepared can be obviously improved.It is it is highly preferred that described Binding agent source and optional alkali source come from molecular sieve preparation solution, by the nano-carbon material of non-modified surface treatment in molecule Catalytic performance of the formed body finally prepared in hydrocarbon dehydrogenation reaction can further be improved by carrying out hydro-thermal process in sieve preparation solution. In the embodiment, 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 carbon nanometer It is more than one or both of pipe, graphene, thin layer graphite, nano carbon particle, carbon nano-fiber, Nano diamond and fullerene Combination.The CNT can be one kind or two in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube The combination of the kind above, preferably multi-walled carbon nanotube.The specific surface area of the multi-walled carbon nanotube can be 50-500m2/ g, it is excellent Elect 80-300m as2/ g, more preferably 100-250m2/ g, more preferably 120-180m2/g.The multi-walled carbon nanotube exists Weight-loss ratio in 400-800 DEG C of 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, more preferably in the range of 0.02-0.3, the model further preferably in 0.05-0.15 In enclosing.As an example, described without surface treating nano carbon material can be second aspect formed body of the present invention In raw material nano carbon material.
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, N element and at least one metallic element.It is described Metallic element is selected from group ia metal element and group iia metallic element, its instantiation can include but is not limited to lithium, sodium, It is more than one or both of potassium, beryllium, magnesium, calcium, barium and strontium.The metallic element is preferably one in sodium, potassium, magnesium, calcium and barium Kind is two or more, more preferably more than one or both of magnesium, barium and calcium.
Specifically, the surface treated nano-carbon material can be in the present invention one side formed body Nano-carbon material in second aspect formed body of nano-carbon material and/or the present invention.
According to the fourth aspect of the present invention, the invention provides a kind of method system as described in third aspect of the present invention Standby nano-carbon material formed body.
Nano-carbon material formed body according to the 4th aspect of the present invention has higher crushing strength.Typically Ground, the radial direction crushing strength according to the nano-carbon material formed body of the present invention can be more than 4N/mm, generally more than 5N/mm. Specifically, the radial direction crushing strength of the nano-carbon material formed body according to one side of the invention and second aspect is 5-25N/mm, preferably 6-25N/mm, more preferably 10-25N/mm.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 organic base and/or alkaline metal cpds.So can further improve the nano-carbon material that finally prepares into The crushing strength of type body, while the nano-carbon material formed body finally prepared can also be further improved as hydrocarbon dehydrogenation reaction Catalytic activity during catalyst., can be obvious particularly when the nano-carbon material is not surface treated nano-carbon material Improve the crushing strength and catalytic performance of the nano-carbon material formed body finally prepared.
The organic base can be more than one or both of amine and quaternary ammonium base (such as Formula II, formula III, formula IV and logical Formula R16(NH2)2The material of expression), the organic base instantiation has been carried out in third aspect of the present invention methods described Detailed description, is herein no longer described in detail.The organic base is preferably quaternary ammonium base (compound as shown in Formula II), particularly preferably For synthesis of titanium silicon molecular sieve template.
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 nano-carbon material formed body to be used as to the catalyst of hydrocarbon dehydrogenation reaction, it can obtain and preferably urge Change performance.From the angle of the catalytic performance of further catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction for improving and preparing Degree sets out, and the metallic element is more preferably selected from magnesium, barium and calcium.
Preferably, the alkaline metal cpds are selected from the hydroxide containing the metallic element and containing the metallic element Basic salt.It is highly preferred that the alkaline metal cpds are selected from the hydroxide containing the metallic element, containing metal member The carbonate of element and the bicarbonate containing the metallic element.The instantiation of the alkaline metal cpds can be included but not It is limited to：Lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, One kind in sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium acid carbonate, calcium bicarbonate, saleratus and barium bicarbonate or two More than kind.From the angle of catalytic activity of the further raising nano-carbon material formed body in hydrocarbon dehydrogenation reaction, the alkali Property metallic compound is preferably one kind in calcium hydroxide, barium carbonate, calcium carbonate, calcium bicarbonate, barium hydroxide and magnesium hydroxide Or it is two or more, more preferably more than one or both of calcium hydroxide, magnesium hydroxide and barium hydroxide.
According to the present invention the 5th aspect described in method, in one embodiment, the inorganic agent be organic base or Person's alkaline metal cpds.
In a kind of embodiment being more highly preferred to, the inorganic agent is organic base and/or alkaline metal cpds.At this In the embodiment being more highly preferred to, on the basis of the total amount of the inorganic agent, the content of the organic base can be 20-100 weights Measure %.Preferably, on the basis of the total amount of the inorganic agent, the content of the organic base is 40-92 weight %.
It is further preferred that the inorganic agent is that at least one organic base and at least one alkaline metal cpds are (described Alkaline metal cpds are preferably selected from calcium hydroxide, magnesium hydroxide and barium hydroxide), and at least part organic base is quaternary ammonium base (compound shown in formula I).Compared with individually using organic base and alkaline metal cpds as inorganic agent, using organic base And alkaline metal cpds are carried out nano-carbon material (particularly not surface treated nano-carbon material) as inorganic agent Hydro-thermal process and the nano-carbon material formed body for preparing has higher crushing strength, in the catalyst as hydrocarbon dehydrogenation reaction In use, also show that higher catalytic activity.With first will not surface treated nano carbon material using alkaline metal cpds Material carries out hydro-thermal process, compared with then carrying out hydro-thermal process aftershaping with binding agent source in the presence of organic base, in alkaline gold In the presence of belonging to compound, not surface treated nano-carbon material is mixed into water-filling heat treatment with binding agent source and organic base Aftershaping, can not only substantially reduce the dosage of alkaline metal cpds, and the nano-carbon material formed body prepared show with The intensity and catalytic activity for the suitable even more high of formed body for being first modified aftershaping and preparing.Using the total amount of the inorganic agent as base Standard, the content of the organic base is preferably 20-95 weight %, preferably 40-92 weight %.Using the total amount of the organic base as base Standard, the content of the quaternary ammonium base is preferably 40-100 weight %, more preferably 100 weight %.In part, organic base is quaternary ammonium base When, remainder organic base can be that (its instantiation may refer to second aspect shaping of the present invention for hydramine and/or amine Hydramine and amine described in body, no longer it is described in detail herein).
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 0.05-15：1, preferably 0.1-8：1, more preferably 0.5-5：1, the bonding 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.Usually, water and the mol ratio in the binding agent source can be 1-150：1, preferably 4- 120：1, the binding agent source is in terms of oxide.
According to the method described in the 5th aspect of the present invention, the dosage in the binding agent source can be according to formed body expection group Into being selected.Usually, the dosage in the binding agent source make it that in the formed body that finally prepares that the content of nano-carbon material can Think more than 5 weight % (such as more than 6 weight %), preferably more than 10 weight %, more preferably more than 50 weight %, further It is still more preferably more than 70 weight % preferably more than 60 weight %, is still more preferably more than 75 weight %, especially Preferably more than 80 weight %, the content of the nano-carbon material is generally below 95 weight %, preferably below 94 weight %, More preferably below 90 weight %.In an example, on the basis of the total amount of the nano-carbon material formed body, the nanometer The content of carbon material can be 5-95 weight % (such as 6-94 weight %), and preferably 8-92 weight %, more preferably 10-90 are heavy %, more preferably 20-90 weight % are measured, is still more preferably 40-90 weight %, particularly preferably 70-90 weight %, The content of the heat-resistant inorganic oxide can be 5-95 weight % (such as 6-94 weight %), preferably 8-92 weight %, more excellent Elect 10-90 weight %, more preferably 10-80 weight % as, be still more preferably 10-60 weight %, particularly preferably 10-30 weight %.Nano-carbon material formed body prepared by method described according to the fifth aspect of the present invention, even in relatively low Binder content under, can also obtain higher intensity.Usually, on the basis of the total amount of the formed body, the nano-sized carbon The content of material is preferably 75-95 weight %, more preferably 85-95 weight %, and the content of the heat-resistant inorganic oxide is preferred For 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.According to the present invention the 6th aspect described in nano-carbon material into Type body has higher porosity.Usually, the hole of the nano-carbon material formed body according to the 6th aspect of the present invention Rate 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%, the model preferably in 10-30% In enclosing, 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 with 30-99.5 volume %, preferably 50-99 volumes %, more preferably 70-98 volumes %.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the temperature of the contact can be conventional selection, to be enough to send out hydrocarbon Raw dehydrogenation reaction is defined.Usually, the contact can be carried out at a temperature of 200-650 DEG C, preferably in 300-600 DEG C of temperature Degree is lower to be carried out, and is carried out more preferably at a temperature of 350-550 DEG C, further preferably in 400-450 DEG C of temperature when such as hydrocarbon being butane Degree is lower to be carried out.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the contact is carried out preferably in fixed bed reactors.
According to the hydrocarbon dehydrogenation reaction method of the present invention, the duration of the contact can be selected according to the temperature of contact Select, when such as described contact is carried out in fixed bed reactors, the duration of contact can be represented with the weight (hourly) space velocity (WHSV) of charging. Usually, the weight (hourly) space velocity (WHSV) of feed gas can be 1-50000h-1, preferably 10-20000h-1, more preferably 50-10000h-1, more preferably 100-8000h-1, such as 3500-5500h-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 Perkin-Elmer 3300DV types 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 1-12 is used to prepare nano-carbon material containing metallic atom.
Preparation example 1
20g is (limited purchased from Chinese Academy of Sciences's Chengdu organic chemistry as the multi-walled carbon nanotube A 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 40kHz, Time is 0.5 hour.Then, add and be well mixed as the barium hydroxide of alkaline metal cpds, so as to obtain aqueous dispersions, Wherein, barium hydroxide is provided in the form of the 20 weight % aqueous solution, by raw material nano carbon material：Alkaline metal cpds：H2O's Weight ratio is 1：0.2：9.8 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), dry 6 hours at a temperature of 120 DEG C, obtain nano-carbon material containing metallic atom, its composition, specific surface area with 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 back flow reaction 24 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 Dried 6 hours at a temperature of DEG C, obtain nano-carbon material containing metallic atom.
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, the moisture that will be obtained Dispersion liquid is placed in the autoclave with polytetrafluoroethyllining lining, and at a temperature of 100 DEG C, it is small to react 24 at autogenous pressures When.
Preparation example 5
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 1, unlike, in step (1), press Raw material nano carbon material：Alkaline metal cpds：H2O weight ratio is 1：0.02：9.8 ratio feeds intake.
Preparation example 6
(1) (it is purchased from Chinese Academy of Sciences's Chengdu organic chemistry using 20g as the multi-walled carbon nanotube C of raw material nano carbon material Co., Ltd) it is scattered in deionized water, it is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is 60kHz, time are 1 hour.Then the calcium hydroxide as alkaline metal cpds is added, is well mixed, so as to obtain moisture Dispersion liquid, wherein, raw material nano carbon material：Alkaline metal cpds：H2O weight ratio is 1：0.25：24.75.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 220 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 collect solid matter.By the solid matter being collected at a temperature of normal pressure, 120 DEG C Dry 6 hours, obtain nano-carbon material containing metallic atom, its composition, specific surface area and w500/w800Listed in table 2.
Preparation example 7
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 6, unlike, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 270 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 6, 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 9
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 6, unlike, will in step (2) Obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, at a temperature of 310 DEG C, in self-generated pressure Lower reaction 12 hours.
Preparation example 10
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 6, unlike, in step (1), hydrogen Calcium oxide is replaced with the potassium hydroxide of equimolar amounts.
Preparation example 11
Nano-carbon material containing metallic atom is prepared using with the identical method of preparation example 6, unlike, in step (1), hydrogen Calcium oxide is replaced with the sodium hydroxide of equimolar amounts.
Preparation example 12
(1) 20g multi-walled carbon nanotubes E (being purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) is dispersed in deionization In water, it is dispersed under the conditions of sonic oscillation and carries out, sonic oscillation condition includes：Frequency is 40kHz, and the time is 0.5 hour.So Afterwards, add and be well mixed as the magnesium hydroxides of alkaline metal cpds, so as to obtain aqueous dispersions, wherein, magnesium hydroxide with The form of the 20 weight % aqueous solution provides, by raw material nano carbon material：Alkaline metal cpds：H2O weight ratio is 1：0.1： 40 ratio feeds intake.
(2) obtained aqueous dispersions are placed in the autoclave with polytetrafluoroethyllining lining, in 200 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 collect solid matter.By the solid matter being collected at a temperature of normal pressure, 120 DEG C Dry 8 hours, obtain nano-carbon material containing metallic atom, its composition, specific surface area and w500/w800Listed in table 2.
Embodiment 1-69 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 1-69.
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 (numbering TS-C), with SiO2The content of the element silicon of meter is 3.4 Weight %, with TiO2The content of the titanium elements of meter is 0.3 weight %, and the content of tetraethyl ammonium hydroxide is 13.1 weight %.
(4) rearrangement solution of HTS
Method according to the embodiment 9 of China's application 99126289.1 obtains the rearrangement solution of HTS, specific to prepare Process is：
According to TS-1 molecular sieves (gram)：Tetraethyl ammonium hydroxide (mole)：Water (mole)=100：0.25：60 ratio is mixed Close uniformly, mixture is placed in stainless steel sealing reactor, constant temperature is placed 3 days under 175 DEG C and self-generated pressure.Cool down release Afterwards, filtered, gained filtrate is the rearrangement solution of HTS.
After testing, on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 1.1 weight %, with TiO2Meter The contents of titanium elements be 0.02 weight %, the content of TPAOH is 3.6 weight %.Rearrangement solution is concentrated into (concentration Liquid numbering is TS-D) extremely on the basis of the total amount of rearrangement solution, with SiO2The content of the element silicon of meter is 4.4 weight %, with TiO2Meter The contents of titanium elements be 0.08 weight %, the content of TPAOH is 14.4 weight %.
(5) crystallization mother liquor of Si-Al molecular sieve
With reference to the method for US4410501 embodiments 1 sial is prepared using silicon source aluminium isopropoxide replacement titanium source tetraethyl titanate Molecular sieve, and collect crystallization mother liquor.Specific operation process is：
Without CO2Atmosphere under, 455g tetraethyl orthosilicates are positioned in heatproof glass container, with stirring add 15g Aluminium isopropoxide, be subsequently added into by 800g mass concentrations be 25% the TPAOH aqueous solution, mix 4h after, in 80-90 DEG C heating stirring drives ethanol out of after 5 hours completely.Then 1.5L is added water to, obtained mixture is transferred to outfit stirring In the autoclave of device, hydrothermal crystallizing 10 days under 175 DEG C, self-generated pressure, obtained reactant mixture is filtered, collected Crystallization mother liquor.
After testing, on the basis of the total amount of crystallization mother liquor (being AS-F by crystallization mother liquor numbering), with SiO2The element silicon of meter Content be 2.3 weight %, with Al2O3The content of the aluminium element of meter is 0.14 weight %, and the content of TPAOH is 12.5 weight %.By crystallization mother liquor concentration (concentrate numbering is AS-E) extremely on the basis of the total amount of concentrate, with concentrate Total amount on the basis of, with SiO2The content of the element silicon of meter is 8.28 weight %, with Al2O3The content of the aluminium element of meter is 0.50 Weight %, the content of TPAOH is 45 weight %.
Embodiment 1-36
The condition provided according to table 3, nano-carbon material is molded respectively using following methods.
Nano-carbon material is well mixed with binding agent source under environment temperature (25 DEG C) respectively, mixture feeding will be obtained After being dried and be optionally calcined in strip mould, obtain nano-carbon material formed body and (randomly select part formed body to enter Row polishing, obtain the batten that length is 3-5mm and be used to determine crushing strength and porosity, as a result listed in table 3), will be surplus Sieved after remaining formed body is broken, obtain graininess formed body, its mean particle size (abbreviation particle diameter) is listed in table 3.
Table 3
1：The dosage of nano-carbon material is 10g2：TPAOH3：Tetraethyl ammonium hydroxide4：Dosage is to aoxidize Thing meter
5：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Embodiment 37-65
Using following methods, nano-carbon material is molded by the condition provided according to table 4 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 4), by remaining formed body it is broken after sieved, obtain Granular formed body, its mean particle size are listed in table 4.
Embodiment 66
Difference with embodiment 37 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 67
Difference with embodiment 37 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 37 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 37 Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Embodiment 68
Difference with embodiment 38 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 69
Difference with embodiment 38 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 38 of back flow reaction at a temperature of the hydro-thermal process temperature identical of embodiment 38 Heat treatment time is identical, and the mixture that back flow reaction is obtained is sent into mould.
Table 4
1：The dosage of nano-carbon material is 10g2：TPAOH3：TMAH4：Tetraethyl hydrogen-oxygen Change ammonium5：Dosage is in terms of oxide
6：The species and dosage of the inorganic agent additionally added outside contained inorganic agent in binding agent source
Testing example 1-69
The catalytic performance of the catalyst prepared using following methods successively testing example 1-69.
The graininess formed body respectively prepared by 0.25g embodiments 1-69 is micro- in universal fixed bed as Catalyst packing In type quartz tube reactor, the end seal of miniature quartz pipe reactor two has quartz sand, will under the conditions of 0MPa (gauge pressure) and 450 DEG C (concentration of normal butane is 2.16 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 4500h-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 5.
Test comparison example 1-5
Using the catalytic for testing multi-walled carbon nanotube A, B, C, D and E successively with testing example 1-69 identicals method Energy.
Table 5
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 (36)

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 C element, O elements and at least one metallic element, the metal Element is selected from 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 total amount of element is 1-10 weight %, more preferably preferably 2-8 weight %, 3-7 weight %, and more preferably 5-6 is heavy Measure %；The total amount of the metallic element is 0.1-10 weight %, more preferably preferably 0.2-8 weight %, 0.5-5 weight %, More preferably 1-4 weight %；The total amount of C element is 80-98.9 weight %, preferably 84-97.8 weight %, is more preferably 88-96.5 weight %, more preferably 90-94 weight %.
3. formed body according to claim 1 or 2, wherein, the total content of the oxygen element determined by x-ray photoelectron power spectrum For IO t, the content of the O elements determined by the peak in the range of 529.5-530.8eV in x-ray photoelectron power spectrum is IO m, IO m/IO t In the range of 0.01-0.3, preferably in the range of 0.02-0.25, more preferably in the range of 0.05-0.23, further preferably In the range of 0.09-0.18.
4. according to the formed body described in any one in claim 1-3, wherein, by 531.0- in x-ray photoelectron power spectrum The amount for the O elements that peak in the range of 532.5eV determines is IO c, in the range of 532.6-533.5eV in x-ray photoelectron power spectrum The amount for the O elements that peak determines is IO e, IO c/IO eIn the range of 1-3, preferably in the range of 1.2-2.5, more preferably in 1.4-2 In the range of, further preferably in the range of 1.5-1.8.
5. according to the formed body described in any one in claim 1-4, wherein, in the nano-carbon material, by X ray photoelectricity The amount for the C element that peak in sub- 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 eIn the range of 1-2.5, the model preferably in 1.2-2.2 In enclosing, more preferably in the range of 1.5-2, further preferably in the range of 1.8-2.
6. according to the formed body described in any one in claim 1-5, wherein, with the nano-carbon material by X ray light It is true by the peak in the range of 284.7-284.9eV in x-ray photoelectron power spectrum on the basis of the total amount for the C element that electron spectrum determines The content of fixed C element is 60-98 weight %, preferably 65-90 weight %, more preferably 75-85 weight %, by X ray light The content for the C element that peak in electron spectrum in the range of 286.0-288.8eV determines is 2-40 weight %, and preferably 10-35 is heavy Measure %, more preferably 15-25 weight %.
7. according to the formed body described in any one in claim 1-6, wherein, the metallic element be sodium, potassium, magnesium, calcium and It is more than one or both of barium；Preferably more than one or both of magnesium, barium and calcium.
8. according to the formed body described in any one in claim 1-7, wherein, the nano-carbon material is CNT, excellent Elect multi-walled carbon nanotube as；
Preferably, the specific surface area of the multi-walled carbon nanotube is in 50-500m2In the range of/g, preferably in 80-300m2/ g model In enclosing, more preferably in 100-250m2In the range of/g, further 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 0.02-0.3 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.
9. 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 is made using the method comprised the following steps：One kind is dispersed with raw material nano carbon material and at least A kind of aqueous dispersions of alkaline metal cpds are reacted in closed container, the metal member in the alkaline metal cpds Element is selected from group ia metal element and group iia metallic element, and in course of reaction, the temperature of the aqueous dispersions is maintained at 80- In the range of 310 DEG C.
10. formed body according to claim 9, wherein, raw material nano carbon material：The weight ratio of alkaline metal cpds exists 1：In the range of 0.01-5, preferably 1：In the range of 0.02-2, more preferably 1：In the range of 0.02-1, further preferably exist 1：In the range of 0.02-0.5, still more preferably 1：In the range of 0.1-0.3.
11. the formed body according to claim 9 or 10, wherein, raw material nano carbon material：H2O weight ratio is 1：2-100 In the range of, preferably 1：In the range of 3-80, more preferably 1：In the range of 5-60, further preferably 1：8-40 scope It is interior.
12. according to the formed body described in any one in claim 9-11, wherein, the alkaline metal cpds, which are selected from, contains institute The hydroxide of metallic element and the basic salt containing the metallic element are stated, is preferably selected from the hydroxide containing the metallic element Thing, the carbonate containing the metallic element and the bicarbonate containing the metallic element, more preferably calcium hydroxide, barium carbonate, It is more than one or both of calcium carbonate, calcium bicarbonate, barium hydroxide and magnesium hydroxide, more preferably calcium hydroxide, hydrogen It is more than one or both of magnesia and barium hydroxide.
13. according to the formed body described in any one in claim 9-12, wherein, in course of reaction, the aqueous dispersions Temperature is maintained in the range of 100-300 DEG C, is preferably remained in the range of 120-250 DEG C；
Preferably, the duration of the reaction in the range of 0.5-144 hours, preferably in the range of 2-72 hours, more It is preferred that in the range of 4-24 hours.
14. according to the formed body described in any one in claim 9-13, wherein, in the raw material nano carbon material, N element Content be not higher than 0.2 weight %, preferably not higher than 0.02 weight %；The content of O elements be not higher than 1.5 weight %, Preferably not higher than 0.3 weight %；The total amount of metallic element is below 2.5 weight %, preferably below 0.5 weight %.
15. according to the formed body described in any one in claim 9-14, wherein, the raw material nano carbon material is carbon nanometer Pipe；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 100-260m2/ g, more preferably 120-190m2/g；
Preferably, total weight loss rate of the multi-walled carbon nanotube in 400-800 DEG C of temperature range is w800, at 400-500 DEG C Temperature range in total weight loss rate be w500, w500/w800In the range of 0.01-0.5, preferably in the range of 0.02-0.4, The weight-loss ratio determines in air atmosphere.
16. according to the formed body described in any one in claim 9-15, wherein, methods described also includes what is obtained from reaction Solid matter is isolated in mixture, 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.
17. according to the formed body described in any one in claim 1-16, 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.
18. according to the formed body described in any one in claim 1-17, 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 %.
19. 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 C element, O elements and at least one metallic element, the metallic element be selected from group ia metal element and Group iia metallic element.
20. according to the method for claim 19, wherein, the mixture also contains at least one alkali；
Preferably, alkali, urea, hydrazine, amine and the season that the alkali is ammonia, cation is the alkali of alkali metal, cation is alkaline-earth metal More than one or both of ammonium alkali, quaternary ammonium base is preferably selected from, is more preferably selected from synthesis of titanium silicon molecular sieve template, further It is preferably selected from the compound shown in Formula II：
In Formula II, R5、R6、R7And R8Respectively C1-C20Alkyl, preferably respectively C1-C6Alkyl；
The alkali and the mol ratio in the binding agent source are preferably 0.05-15：1, preferably 0.1-12：1, more preferably 0.12- 6：1, the binding agent source is in terms of oxide.
21. the method according to claim 19 or 20, wherein, before the mixture is molded, this method also includes will The mixture carries out hydro-thermal process.
22. according to the method for claim 21, wherein, the hydro-thermal process is carried out at a temperature of 100-200 DEG C, described The duration of hydro-thermal process is 0.5-24 hours.
23. according to the method described in any one in claim 19-22, wherein, at least part binding agent source, at least partly may be used The alkali and at least part water of choosing come from molecular sieve preparation solution, and the molecular sieve preparation solution is the crystallization mother liquor of siliceous molecular sieve With the mixed liquor reset more than one or both of modified mother liquor of siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor of silica zeolite and/or resets modification liquid, HTS One or both of crystallization mother liquor and/or rearrangement modification liquid of crystallization mother liquor and/or rearrangement modification liquid and Si-Al molecular sieve Mixed liquor above.
24. 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 C element, O elements and at least one metal by x-ray photoelectron power spectrum Element, the metallic element are selected from group ia metal element and group iia metallic element.
25. forming method according to claim 24, wherein, the aqueous dispersions also contain at least one inorganic agent, institute It is organic base and/or alkaline metal cpds to state inorganic agent, and the metallic element in the alkaline metal cpds is selected from group ia Metallic element and group iia metallic element；
Preferably, the organic base is selected from quaternary ammonium base and amine, is more preferably selected from synthesis of titanium silicon molecular sieve template, further excellent Choosing is selected from further preferably selected from the compound shown in Formula II：
In Formula II, R5、R6、R7And R8Respectively C1-C20Alkyl, preferably respectively C1-C6Alkyl；
Preferably, the inorganic agent is organic base and/or alkaline metal cpds, on the basis of the total amount of the inorganic agent, institute The content for stating organic base is preferably 20-100 weight %, more preferably 20-95 weight %, more preferably 40-92 weight %；
It is highly preferred that the inorganic agent is organic base and/or alkaline metal cpds, and at least part organic base is quaternary ammonium base, On the basis of the total amount of the inorganic agent, the content of the organic base is preferably 20-100 weight %, and more preferably 20-95 is heavy % is measured, more preferably 40-92 weight %, the content of the quaternary ammonium base is preferably 40-100 weight %.
26. according to the method for claim 25, wherein, the inorganic agent and the mol ratio in the binding agent source are 0.05- 15：1, preferably 0.1-8：1, more preferably 0.5-5：1, the binding agent source is in terms of oxide.
27. according to the method described in any one in claim 24-26, 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 modified mother liquor of mother liquor and siliceous molecular sieve；
Preferably, the molecular sieve preparation solution is the crystallization mother liquor of silica zeolite and/or resets modification liquid, HTS One or both of crystallization mother liquor and/or rearrangement modification liquid of crystallization mother liquor and/or rearrangement modification liquid and Si-Al molecular sieve Mixed liquor above.
28. according to the method described in any one in claim 24-27, wherein, temperature of the hydro-thermal process at 100-200 DEG C Degree is lower to be carried out, and the duration of the hydro-thermal process is 0.5-24 hours.
29. according to the method described in any one in claim 19-28, 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 %.
30. according to the method described in any one in claim 19-29, wherein, the dosage in the binding agent source causes finally In the formed body of preparation, the content of nano-carbon material is 5-95 weight %, and preferably 6-94 weight %, more preferably 75-95 are heavy % is measured, more preferably 85-95 weight %, the content of the heat-resistant inorganic oxide is 5-95 weight %, preferably 6-94 Weight %, more preferably 5-25 weight %, more preferably 5-15 weight %.
31. according to the method described in any one in claim 19-30, wherein, the surface treated nano-carbon material For the nano-carbon material described in any one in claim 2-8 and 9-16.
32. according to the method described in any one in claim 19-31, 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 350-650 DEG C, the roasting is held The continuous time is 1-12 hours, preferably 2-4 hours.
33. nano-carbon material formed body prepared by a kind of method in 19-32 as claim described in any one.
34. catalyst of the nano-carbon material formed body as hydrocarbon dehydrogenation reaction in claim 1-18 and 33 described in any one Application, the hydrocarbon is preferably alkane, more preferably C2-C12Alkane, more preferably normal butane.
35. 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 1-18 and 33.
36. according to the method for claim 35, wherein, the hydrocarbon is alkane, preferably C2-C12Alkane, more preferably Normal butane.
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