CN101376114B - Method for preparing metal or metallic oxide/carbon composite material - Google Patents
Method for preparing metal or metallic oxide/carbon composite material Download PDFInfo
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- CN101376114B CN101376114B CN2008102280425A CN200810228042A CN101376114B CN 101376114 B CN101376114 B CN 101376114B CN 2008102280425 A CN2008102280425 A CN 2008102280425A CN 200810228042 A CN200810228042 A CN 200810228042A CN 101376114 B CN101376114 B CN 101376114B
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Abstract
The invention belongs to the scientific and technical field of carbon materials, and provides a method for preparing metal or metal oxide/carbon composite materials by asphaltine. The method takes theby-product asphaltine in the coal liquefaction process as a carbon source, takes a pyrolytic polymer as a pore-forming agent, and takes easily-pyrolytic metal salt as a metal precursor; and then themetal or the metal oxide/carbon composite materials are prepared by one step after the physical blending and carbonizing reductive treatment. The metal or the metal oxide/carbon composite materials prepared by the method have the controllable appearance that the metal or the metal oxide is uniformly dispersed in a carbon carrier with the grain diameter of 3-50nm. The preparation process has simpleroutes, mild conditions, conventional equipment, low cost, and controllable output of products, and is suitable for mass production. The prepared metal or the prepared metal oxide/carbon composite materials can be used as a highly-active catalyst, an adsorbent, a magnetic separation material, an electrode material and the like.
Description
Technical field
The invention belongs to inorganic non-metallic materials science technology branch-carbon material science and technology field, relating to a kind of is carbon source with coal direct liquefaction accessory substance asphalitine, prepares the method for metal/carbon composite or metal oxide/carbon composite.
Background technology
Along with the increase of global oil extraction and the minimizing of reserves, the breach of oil supply is increasing, directly causes the rise at full speed of oil price.China greatly develops the coal-based clean energy with the coal for the raw material substitution oil and is considered to current solution oil shortage as the oil-poor big country of rich coal, realizes that the coal high-tech transforms and the most feasible important technology approach of coal industry sustainable development.Coal liquefaction be a kind of coal with solid under hydrogen and catalyst action, be converted into the advanced clean coal technology of liquid fuel, industrial chemicals and product by hydrocracking.Coal is through hydrogenation, the aromatic hydrocarbons industrial chemicals that can change into liquid fuels such as qualified gasoline, diesel oil, liquefied petroleum gas and be difficult to make by the natural stone wet goods, the pressure of oil has been alleviated in the employing of this technology, utilize the coal resources of China's cheapness fully, improved the utilization rate of coal resources greatly." the DCL/Direct coal liquefaction key technology " that group of Shenhua bears is that raw material directly prepares oil product with the coal, and this has special significance to the energy security of China and the sustainable development of economic society.At present group of Shenhua has first cover in the world prepares oil product for the raw material direct liquefaction with the coal industrial demonstration plant, and production capacity reaches megaton.But in the coal direct liquefaction production process, no matter adopt which kind of coal direct liquefaction technology, no matter take which kind of solid-liquid separating method, except obtaining fluid product, the capital inevitably produces the liquefied residue that accounts for liquefaction raw coal total amount about 30%, and so many level of residue has immeasurable influence to the resource utilization and the economy of liquefaction process.Therefore, how efficient, reasonable use coal liquefaction residue just becomes an important topic improving Technology of direct coal liquefaction.
The coal direct liquefaction residue is the material of a kind of high charcoal, high ash and high-sulfur, mainly is made up of unconverted coal, inorganic mineral and catalyst for coal liquefaction.In general, the method difference of coal liquefaction, the coal liquefaction residue that is produced is formed also different.According to the character characteristics of liquefied residue and the requirement of liquefaction process, at present the coal direct liquefaction residue to utilize approach to mainly contain following several: 1. gasification hydrogen-producing, as: with liquefied residue gasification preparation synthesis gas, the synthesis gas that obtains is produced H after purify and conversion etc. handled with the texaco gasification technology
2, this be coal liquefaction residue generally utilize mode; 2. coking system oil, higher boiling oils that content in the residue is higher and bitumen further are converted into retortable oil, gas and coke by the method for coking, to reclaim the oil in the residue, improve the yield of fluid product; 3. boiler oil, liquefied residue has higher caloric value, therefore can be used as the fuel of boiler and kiln.In addition, coal liquefaction residue has also been obtained researcher's concern as the carbon matrix precursor of the carbon material of production high added value, this has further expanded the application of coal liquefaction residue.Adopting the coal direct liquefaction residue as Qiu Jieshan seminar is carbon matrix precursor, using plasma method and arc discharge method are prepared carbon nano-fiber and CNT respectively, have proposed a kind of method (Fuel.2008.87 (15-16): 3474-3476 that efficiently utilizes the coal direct liquefaction residue; Coal conversion, 2007,30 (3): 41-44), realized producing the application of high value added product with coal liquefaction residue.
Though residual deliquescence accelerant pyrite can play the effect of catalyst in the coal liquefaction residue in the preparation novel charcoal material, also contain the mineral matter that comes from a large number in the coal and the ash content of deliquescence accelerant in the liquefied residue, and Fe in the ash component
2O
3And SO
3The general raw coal of content want high a lot, the existence of ash content will influence the structure and the composition of preparation raw material of wood-charcoal material greatly.In order to determine the optimum utilization approach of coal direct liquefaction residue, the researcher has carried out detailed investigating to the composition of coal direct liquefaction residue.Result of study shows, contains the higher boiling heavy organic matter about 50% in the coal direct liquefaction residue, as mink cell focus and asphalitine etc.Asphalitine is a kind of organic polymer mixture, the fragrant slice that condenses that basic structural unit is made up of a plurality of aromatic rings is a core, be connected with alkyl side chain or cycloalkane that several length differ on every side, and contain the sheet molecule that hetero atoms such as a small amount of sulphur, nitrogen, oxygen are formed.Technical process and condition difference in the DCL/Direct coal liquefaction process, residue medium pitch matter components contents is also different, because it has the armaticity height, the phosphorus content height, polymerization or crosslinked characteristics take place easily, therefore the asphalitine in the coal direct liquefaction residue are separated by organic matter that effectively utilize undoubtedly can be to the macroeconomic generation crucial effects of raising resource utilization and coal liquefaction in addition.People such as Liu Zhenyu study as road asphalt modifier the coal direct liquefaction residue, bitumen is close recklessly for its modified effect and Trinida, asphalitine one asphaltene in the coal direct liquefaction residue, the adding of pre-asphaltene can improve the softening point of pitch, and has strengthened the cooperative effect between each component; People such as Zhou Ying utilize the asphaltene that extracts in the coal direct liquefaction residue and pre-asphaltene for carbon source has prepared orderly mesopore charcoal, this material can be used for the electrode material of electrochemical capacitor.Up to now, not seeing with asphaltene and pre-asphaltene as yet is the relevant report of feedstock production composite.
Metal/carbon composite or metal oxide/carbon composite have unique physicochemical characteristics, caused the very big interest of numerous scientific research personnel and enterprise group in recent years, the novel special material that is considered to a kind of extensive application prospect can be used as uses such as catalyst, novel absorption material, electron and electrician material and electric wave shielding material.This composite is with respect to general raw material of wood-charcoal material, and the most outstanding advantage is the remarkable improvement of its catalytic performance, absorption property, electrical property and magnetic property.The raw material of wood-charcoal material self has unique physical and chemical performance, with its as matrix come synthetic composite material can be applied to other materials be difficult to use or use less than the field.Along with the day by day raising of people to metal/carbon composite or metal oxide/carbon composite requirement, the development of metallic particle diameter is less and be dispersed in composite on the carrier, become the demand that promotes industrial development, selecting cheap raw material and suitable preparation method is the important component part that obtains this type of material.Traditional metal/carbon composite or metal oxide/carbon composite synthetic method mainly contains the liquid impregnation method, absorption method, ion-exchange etc., but these method steps are loaded down with trivial details, complex process.Fa Zhan the method for preparing metal/carbon composite or metal oxide/carbon composite thereupon, as sol-gel process, the hot charing reducing process of hydro-thermal solvent, organic precursor pyrolysis charring methods etc. are introduced metal component simultaneously in the process of synthetic raw material of wood-charcoal material, simplified technological process greatly, but these methods can not effectively be controlled the pore-size distribution of charcoal carrier or the particle diameter of metallic, and severe reaction conditions.
The utilization of at present relevant coal direct liquefaction accessory substance asphaltene, pre-asphaltene and the aspect of using it for preparation metal/carbon composite or metal oxide/carbon composite rarely have report, close with present techniques or similar research report has CN1948148A and CN1386722A etc., its research contents to relate to utilize asphaltene and pre-asphaltene to prepare orderly mesopore raw material of wood-charcoal material and utilizes hydrocarbon compound and the transistion metal compound carbonization reaction prepares nano metal particles/carbon composite etc.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for feedstock production metal/carbon composite or metal oxide/carbon composite with the asphalitine, select coal direct liquefaction accessory substance asphalitine as carbon source, utilize pyrolyzed-polymer to be pore-foaming agent, easily the pyrolysis slaine is a metal precursor, directly prepare the composite that metals or metal oxide particle are evenly distributed on carbon matrix in a large number by asphalitine, for a new way is opened up in the utilization of coal liquefaction accessory substance.
Technical scheme of the present invention is: be the method for feedstock production metal/carbon composite or metal oxide/carbon composite with the asphalitine, be with a kind of at normal temperatures for solid-state material asphalt matter be carbon source, pyrolyzed-polymer is a pore-foaming agent, easily the pyrolysis slaine is a metal precursor, one step preparation metal/carbon composite or metal oxide/carbon composite, the preparation method realizes by following steps:
(1) asphalitine is placed oxygen or air pre-oxidation treatment: the heating rate with 0.5-5 ℃/min rises to 150 ℃-350 ℃ from room temperature, and under this temperature constant temperature 2-8h;
(2) with above-mentioned carbon source, pore-foaming agent, metal precursor with mass ratio 1: 0.5-5: the 0.1-0.5 blend is ground, then mixture is placed in the retort, under the protection of inert gas, heating rate with 1-10 ℃/min rises to 500 ℃-800 ℃ from room temperature, and under this temperature constant temperature 3-6h, treat that the retort temperature naturally cools to room temperature, can obtain metal/carbon composite; If feeding percentage by volume in the carbonization process is the oxygen of 1%-5%, can obtain metal oxide/carbon composite.
It is asphalitine that the above-mentioned raw materials asphalitine is selected from asphaltene, pre-asphaltene, carbobitumen matter or oil; Pore-foaming agent is selected from polyethylene glycol, polyvinyl butyral resin or polyvinyl alcohol; The chloride of metal precursor chosen from Fe, cobalt, nickel, nitrate, acetate, sulfate, acetylacetone,2,4-pentanedione based compound or carbonyls.
Characteristics of the present invention are to be raw material with the accessory substance asphaltene of coal direct liquefaction process or pre-asphaltene, with normal temperature is down that solid-state organic matter asphalitine and pyrolyzed-polymer, easy pyrolysis slaine passes through physical mixed, the charing reduction obtains metal/carbon composite or metal oxide/carbon composite, this method preparation were established is simple, mild condition, the equipment routine realizes easily, controllable output of products, suitable batch production.Product has the pore-size distribution of homogeneous, and metal or metal oxide particle are evenly dispersed in the carbon matrix with smaller particle size.
The invention has the beneficial effects as follows 1, the invention provides a kind of method by the synthetic high added value novel metal/carbon composite of coal direct liquefaction accessory substance or metal oxide/carbon composite.The byproduct that adopts the coal direct liquefaction process has been opened up the new way of coal liquefaction residue processing and utilization as raw material, has reduced the cost of coal hydrogenation liquefaction, has enriched the content of coal liquefaction science.2, the present invention is that a kind of descending with normal temperature is that solid-state asphalitine is a raw material, the new method for preparing high-performance novel metal/carbon composite or metal oxide/carbon composite through preliminary treatment, enrich and developed the research contents of metal/carbon composite or metal oxide/carbon composite preparation, expanded the raw material sources of preparation composite.3, the present invention is less demanding to equipment, and parameter is controlled easily, and practical operation is simple, is easy to amplify.4, the composite of gained of the present invention has the pore-size distribution of homogeneous, metal or metal oxide particle are evenly dispersed in the carbon matrix with smaller particle size, and this class composite has a wide range of applications in fields such as catalysis, absorption, electrochemistry, Magnetic Isolation.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the cobalt/carbon composite of embodiment 1 gained, the microstructure of having showed cobalt/carbon composite.
Fig. 2 is the XRD spectra of the cobalt/carbon composite of embodiment 1 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that cobalt in the cobalt/carbon composite of embodiment 1 gained exists with the form of simple substance cobalt.
Fig. 3 is the nitrogen adsorption isotherm and the pore size distribution curve of the cobalt/carbon composite of embodiment 1 gained, is used for characterizing the duct adsorpting characteristic and the pore-size distribution situation of product.Wherein ●-adsorption curve, zero-desorption curve, ordinate are represented adsorbance (cm
3/ g), abscissa is represented relative pressure; Illustration is a pore size distribution curve, ordinate indication window volume (cm
3/ g), abscissa is represented duct diameter dimension (nm).
Fig. 4 is the transmission electron microscope photo of the cobalt/carbon composite of embodiment 2 gained, the microstructure of having showed cobalt/carbon composite.
Fig. 5 is the XRD spectra of the cobalt/carbon composite of embodiment 2 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that cobalt in the cobalt/carbon composite of embodiment 2 gained exists with the form of simple substance cobalt.
Fig. 6 is the nitrogen adsorption isotherm and the pore size distribution curve of the cobalt/carbon composite of embodiment 2 gained, is used for characterizing the duct adsorpting characteristic and the pore-size distribution situation of product.Wherein ●-adsorption curve, zero-desorption curve, ordinate are represented adsorbance (cm
3/ g), abscissa is represented relative pressure; Illustration is a pore size distribution curve, ordinate indication window volume (cm
3/ g), abscissa is represented duct diameter dimension (nm).
Fig. 7 is the XRD spectra of the cobalt oxide/carbon composite of embodiment 3 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that cobalt in the cobalt oxide/carbon composite of embodiment 3 gained exists with the form of cobaltosic oxide.
Fig. 8 is the transmission electron microscope photo of the cobalt oxide/carbon composite of embodiment 3 gained, the microstructure of having showed cobalt oxide/carbon composite.
Fig. 9 is the EDX figure of the cobalt oxide/carbon composite of embodiment 3 gained, has showed the main component of cobalt oxide/carbon composite.
Figure 10 is the XRD spectra of the cobalt/carbon composite of embodiment 4 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that cobalt in the cobalt/carbon composite of embodiment 4 gained exists with the form of simple substance cobalt.
Figure 11 is the transmission electron microscope photo of the cobalt/carbon composite of embodiment 4 gained, the microstructure of having showed cobalt/carbon composite.
Figure 12 is the XRD spectra of the cobalt/carbon composite of embodiment 5 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that cobalt in the cobalt/carbon composite of embodiment 5 gained exists with the form of simple substance cobalt.
Figure 13 is the transmission electron microscope photo of the cobalt/carbon composite of embodiment 5 gained, the microstructure of having showed cobalt/carbon composite.
Figure 14 is the XRD spectra of the nickel/carbon composite of embodiment 6 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that nickel in the nickel/carbon composite of embodiment 6 gained exists with the form of elemental nickel.
Figure 15 is the transmission electron microscope photo of the nickel/carbon composite of embodiment 6 gained, the microstructure of having showed nickel/carbon composite.
Figure 16 is the XRD spectra of the nickel/carbon composite of embodiment 7 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that nickel in the nickel/carbon composite of embodiment 7 gained exists with the form of elemental nickel.
Figure 17 is the XRD spectra of the composite of embodiment 8 gained, and ordinate is an intensity, and abscissa is 2 θ, has shown that nickel in the composite of embodiment 8 gained exists with the form of elemental nickel and nickel oxide.
The specific embodiment
The present invention is further described below by embodiment.
Embodiment 1
With the asphaltene in the coal direct liquefaction residue is carbon source, and polyethylene glycol is a pore-foaming agent, and cobalt nitrate is that metal precursor prepares cobalt/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 50g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, the toluene DDGS is removed toluene solvant by Rotary Evaporators at 80 ℃ of following reduction vaporizations, and the gained solid is asphaltene.2, asphaltene heating rate with 1 ℃/min in air is risen to 300 ℃ from room temperature, and insulation 4h carries out pre-oxidation treatment under this temperature.3, the asphaltene of pre-oxidation, the polyethylene glycol (molecular weight 6000) that ground 80 mesh sieves, cobalt nitrate are mixed, grind with mass ratio at 1: 1: 0.2.4, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 600 ℃ from room temperature with the heating rate of 1 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain cobalt/carbon composite.With equipment such as transmission electron microscope, X-ray diffraction, physical adsorption appearances product is carried out phenetic analysis, the results are shown in accompanying drawing 1,2,3.
With the pre-asphaltene in the coal direct liquefaction residue is carbon source, and polyethylene glycol is a pore-foaming agent, and cobalt nitrate is that metal precursor prepares cobalt/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 50g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, after the extracting gained insoluble matter drying, grind into powder is crossed 80 mesh sieves, behind 92 ℃ of following extracting 50h, the oxolane DDGS of gained is removed the solid matter that obtains behind the tetrahydrofuran solvent with 50 ℃ of reduction vaporizations of Rotary Evaporators and is pre-asphaltene through oxolane.2, pre-asphaltene, the polyethylene glycol (molecular weight 6000) that ground 80 mesh sieves, cobalt nitrate are mixed, grind with mass ratio at 1: 1: 0.2.3, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 600 ℃ from room temperature with the heating rate of 1 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain cobalt/carbon composite.With equipment such as transmission electron microscope, X-ray diffraction, physical adsorption appearances product is carried out phenetic analysis, the results are shown in accompanying drawing 4,5,6.
Embodiment 3
With the asphaltene in the coal direct liquefaction residue is carbon source, and polyethylene glycol is a pore-foaming agent, and cobalt nitrate is that metal precursor prepares cobalt oxide/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 40g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, the toluene DDGS is removed toluene solvant by Rotary Evaporators at 80 ℃ of following reduction vaporizations, and the gained solid is asphaltene.2, asphaltene heating rate with 1 ℃/min in air is risen to 300 ℃ from room temperature, and insulation 4h carries out pre-oxidation treatment under this temperature.3, the asphaltene of pre-oxidation, the polyethylene glycol (molecular weight 6000) that ground 80 mesh sieves, cobalt nitrate are mixed, grind with mass ratio at 1: 1: 0.2.4, the mixture that obtains is placed in the retort, under protection of nitrogen gas, feeds percent by volume and be 1% oxygen, rise to 600 ℃ from room temperature with the heating rate of 1 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain cobalt oxide/carbon composite.With X-ray diffraction, transmission electron microscope product is carried out phenetic analysis, the results are shown in accompanying drawing 7,8,9.
Embodiment 4
With the asphaltene in the coal direct liquefaction residue is carbon source, and polyvinyl butyral resin is a pore-foaming agent, and carbonyl cobalt is that metal precursor prepares cobalt/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 40g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, the toluene DDGS is removed toluene solvant by Rotary Evaporators at 80 ℃ of following reduction vaporizations, and the gained solid is asphaltene.2, asphaltene heating rate with 1 ℃/min in air is risen to 300 ℃ from room temperature, and insulation 4h carries out pre-oxidation treatment under this temperature.3, asphaltene, polyvinyl butyral resin, the cobalt acetate with pre-oxidation mixes, grinds with mass ratio at 1: 1: 0.2.4, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 600 ℃ from room temperature with the heating rate of 1 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain cobalt/carbon composite.With X-ray diffraction, transmission electron microscope product is carried out phenetic analysis, the results are shown in accompanying drawing 10,11.
Embodiment 5
With the asphaltene in the coal direct liquefaction residue is carbon source, and polyethylene glycol is a pore-foaming agent, and carbonyl cobalt is that metal precursor prepares cobalt/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 30g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, the toluene DDGS is removed toluene solvant by Rotary Evaporators at 80 ℃ of following reduction vaporizations, and the gained solid is asphaltene.2, asphaltene heating rate with 1 ℃/min in air is risen to 300 ℃ from room temperature, and insulation 4h carries out pre-oxidation treatment under this temperature.3, the asphaltene of pre-oxidation, the polyethylene glycol (molecular weight 6000) that ground 80 mesh sieves, carbonyl cobalt are mixed, grind with mass ratio at 1: 1: 0.2.4, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 600 ℃ from room temperature with the heating rate of 1 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain cobalt/carbon composite.With X-ray diffraction, transmission electron microscope product is carried out phenetic analysis, the results are shown in accompanying drawing 12,13.
With the asphaltene in the coal direct liquefaction residue is carbon source, and polyvinyl butyral resin is a pore-foaming agent, and nickel acetylacetonate is that metal precursor prepares nickel/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 30g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, the toluene DDGS is removed toluene solvant by Rotary Evaporators at 80 ℃ of following reduction vaporizations, and the gained solid is asphaltene.2, asphaltene heating rate with 2 ℃/min in air is risen to 350 ℃ from room temperature, and insulation 2h carries out pre-oxidation treatment under this temperature.3, asphaltene, polyvinyl butyral resin, the nickel acetylacetonate with pre-oxidation mixes, grinds with mass ratio at 1: 2: 0.3.4, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 800 ℃ from room temperature with the heating rate of 3 ℃/min, and under this temperature constant temperature 3h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain nickel/carbon composite.With X-ray diffraction, transmission electron microscope product is carried out phenetic analysis, the results are shown in accompanying drawing 14,15.
Embodiment 7
With the pre-asphaltene in the coal direct liquefaction residue is carbon source, and polyvinyl butyral resin is a pore-foaming agent, and nickel chloride is that metal precursor prepares nickel/carbon composite.Its concrete steps are as follows: 1, take by weighing the coal direct liquefaction residue of 50g without any processing, pulverize and cross 80 mesh sieves, residue powder n-hexane cable-styled extracting 50h under 92 ℃, ground 80 mesh sieves after the gained insoluble matter drying, with toluene at 140 ℃ of following extracting 50h, last mistake 80 mesh sieves of pulverizing after the extracting gained insoluble matter drying, behind 92 ℃ of following extracting 50h, the oxolane DDGS of gained is removed the solid matter that obtains behind the tetrahydrofuran solvent with 50 ℃ of reduction vaporizations of Rotary Evaporators and is pre-asphaltene through oxolane.2, pre-asphaltene, polyvinyl butyral resin, nickel chloride are mixed, grind with mass ratio at 1: 1.4: 0.4.3, the mixture that obtains is placed in the retort, under protection of nitrogen gas, rises to 500 ℃ from room temperature with the heating rate of 10 ℃/min, and under this temperature constant temperature 4h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain nickel/carbon composite.With X-ray diffraction product is carried out phenetic analysis, the results are shown in accompanying drawing 16.
With asphalt is carbon source, and polyvinyl butyral resin is a pore-foaming agent, and nickelous sulfate is that metal precursor prepares nickel/carbon composite.Its concrete steps are as follows: 1, asphalt heating rate with 0.5 ℃/min in air is risen to 200 ℃ from room temperature, and insulation 3h carries out pre-oxidation treatment under this temperature.2, asphalt, polyvinyl butyral resin, the nickelous sulfate with pre-oxidation mixes, grinds with mass ratio at 1: 0.6: 0.2.3, the mixture that obtains is placed in the retort, under the protection of argon gas, rises to 700 ℃ from room temperature with the heating rate of 5 ℃/min, and under this temperature constant temperature 2h.Treat that afterwards the retort temperature naturally cools to room temperature, just can obtain nickel/nickel oxide/carbon composite.With X-ray diffraction product is carried out phenetic analysis, the results are shown in accompanying drawing 17.
Claims (2)
1. the preparation method of a metal/carbon composite or metal oxide/carbon composite, it is characterized in that, this method be with at normal temperatures for solid-state material asphalt matter be carbon source, polyethylene glycol, polyvinyl butyral resin or polyvinyl alcohol are pore-foaming agent, the chloride of iron, cobalt, nickel, nitrate, acetate, sulfate, acetylacetone,2,4-pentanedione based compound or carbonyls are metal precursor, one step was prepared metal/carbon composite or metal oxide/carbon composite, and concrete steps are as follows:
(1) material asphalt matter is placed oxygen or air pre-oxidation treatment: the heating rate with 0.5-5 ℃/min rises to 150 ℃-350 ℃ from room temperature, and under this temperature constant temperature 2-8h;
(2) with above-mentioned (1) products therefrom charcoal, pore-foaming agent, metal precursor with mass ratio 1: 0.5-5: the 0.1-0.5 blend is ground, then mixture is placed in the retort, under the protection of nitrogen or argon gas, heating rate with 1-10 ℃/min rises to 500 ℃-800 ℃ from room temperature, and under this temperature constant temperature 3-6h, treat that the retort temperature naturally cools to room temperature, can obtain metal/carbon composite; If feeding percentage by volume in the carbonization process is the oxygen of 1%-5%, can obtain metal oxide/carbon composite.
2. the preparation method of metal/carbon composite according to claim 1 or metal oxide/carbon composite is characterized in that, described material asphalt matter is selected from asphaltene, pre-asphaltene, coal tar pitch matter or asphalt matter.
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| CN108417845A (en) * | 2018-03-07 | 2018-08-17 | 上海应用技术大学 | A kind of porous carbon composite and preparation method thereof containing cobalt and nickel |
| CN110767912B (en) * | 2019-11-04 | 2022-02-01 | 石河子大学 | Preparation method of pitch-derived carbon-based non-noble metal oxygen reduction catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386722A (en) * | 2002-04-05 | 2002-12-25 | 北京化工大学 | Process for preparing nano metal particles/carbon composite material |
| CN1401563A (en) * | 2001-08-29 | 2003-03-12 | 中国科学院山西煤炭化学研究所 | Method for mfg. metal-carbon composite nanomaterial |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401563A (en) * | 2001-08-29 | 2003-03-12 | 中国科学院山西煤炭化学研究所 | Method for mfg. metal-carbon composite nanomaterial |
| CN1386722A (en) * | 2002-04-05 | 2002-12-25 | 北京化工大学 | Process for preparing nano metal particles/carbon composite material |
Non-Patent Citations (7)
| Title |
|---|
| JP特开2004-142956A 2004.05.20 |
| JP特开2004-143189A 2004.05.20 |
| JP特开平6-322376A 1994.11.22 |
| 邱介山等.由中间相沥青制备泡沫炭：Fe(NO3)3的影响.新型炭材料20 3.2005,20(3),193-197. |
| 邱介山等.由中间相沥青制备泡沫炭:Fe(NO3)3的影响.新型炭材料20 3.2005,20(3),193-197. * |
| 陈学刚等.纳米金属粒子/炭复合材料及其研究进展.碳素技术 5.2000,(5),16-21. |
| 陈学刚等.纳米金属粒子/炭复合材料及其研究进展.碳素技术 5.2000,(5),16-21. * |
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