CN103241777A - Preparation method of carbon material and carbon-ferroferric oxide composite material - Google Patents
Preparation method of carbon material and carbon-ferroferric oxide composite material Download PDFInfo
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- CN103241777A CN103241777A CN2013101928249A CN201310192824A CN103241777A CN 103241777 A CN103241777 A CN 103241777A CN 2013101928249 A CN2013101928249 A CN 2013101928249A CN 201310192824 A CN201310192824 A CN 201310192824A CN 103241777 A CN103241777 A CN 103241777A
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Abstract
The invention provides a preparation method of a carbon material and a carbon-ferroferric oxide composite material. The method provided by the invention adopts chlorinated polyvinyl chloride and an iron compound as raw materials and comprises the following steps of: heating the obtained chlorinated polyvinyl chloride-iron compound or chlorinated polyvinyl chloride fiber-iron compound until the chlorinated polyvinyl chloride is completely burnt; and cooling to obtain a carbon sphere-iron composite material or carbon fiber-iron composite material. According to the method provided by the invention, in order to obtain the carbon material, the prepared carbon sphere-iron composite material or carbon fiber-iron composite material is mixed with an acid solution, and then the mixture is subjected to precipitation separation after standing to obtain a carbon sphere or carbon fiber. The method provided by the invention adopts chlorinated polyvinyl chloride as a carbon source material for synthesizing the carbon material or carbon-iron compound composite material, and performs dehydrochlorination and crosslinked action of the chlorinated polyvinyl chloride in a combustion reaction process under the fast catalysis of the iron compound to synthesize the carbon-ferroferric oxide composite material or carbon material. The method provided by the invention has a simple process and a higher yield.
Description
Technical field
The present invention relates to technical field of nano material, relate in particular to the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.
Background technology
The diameter that typically refers to of nanometer, carbon micron-spheres and carbon fiber is that tens nanometers are to the carbon material of hundreds of micron.Nanometer, carbon micron-spheres and carbon fiber have good chemical stability, thermostability, good conduction and thermal conductivity and bigger specific surface area, are a kind of carbon materials with wide application prospect.Nanometer, carbon micron-spheres and carbon fiber have been widely used in supported catalyst, absorb polluted matter and preparation ultracapacitor and lithium ion battery etc. at present.
Usually, nanometer, carbon micron-spheres adopt electric arc power generating method, laser evaporation method, electrochemical vapor deposition and catalysis synthesis process preparation.The normally organic hydrocarbon small molecules of carbon source in these methods, as: methane, acetylene, ethene etc. seldom have and adopt organic polymer as the carbon source material of preparation nanometer, carbon micron-spheres.Be the preparation method that the Chinese patent of CN10183547A discloses a kind of carbon micron-spheres as publication number; it is catalyzer that this method adopts heteropolyacid; with furane resin; resol or the bituminous resins of living are carbon source; with high-purity argon gas as the protection gas; be solvent with ethanol or dimethyl sulfoxide (DMSO), the preparation carbon micron-spheres.Expensive and a large amount of its mass preparation carbon micron-spheres that used solvent limitation of this method raw material.Publication number is the method that the Chinese patent of CN10774577A discloses a kind of carbon micron-spheres for another example; this method uses fluidized-bed reactor or spray-dryer to prepare the resol microballoon; then with high-purity argon gas as the protection gas; the carbonized phenolic resin microballoon prepares carbon micron-spheres, and this method equipment used complexity and technology are loaded down with trivial details.
Meanwhile, the mixture of nanometer, carbon micron-spheres and carbon fiber and Z 250 thereof also causes people's attention gradually, this class material combines the performance of nanometer, carbon micron-spheres and carbon fiber excellence and the advantage of Z 250 catalytic activity and magnetic, and the aspect has potential application prospect at photocatalysis degradation organic contaminant, magnetic fractionation by adsorption heavy metal ion and organic pollutant and with polymkeric substance is compound etc.
The method for preparing at present nanometer, carbon micron-spheres/Z 250 is less.Rongbo Zheng etc. has reported and has adopted the method for ultrasonic spray pyrolysis to prepare carbon micron-spheres (the Rongbo Zheng that load has ferriferrous oxide nano-particle, Xianwei Meng, Fangqiong Tang.High-Density Magnetite Nanoparticles Located in Carbon Hollow Microspheres with Good Dispersibility and Durability:Their One-Pot Preparation and Magnetic Properties.European Journal of Inorganic Chemistry, 20:3003～3007.), utilize iron protochloride and citric acid as raw material, adopt the method for ultrasonic spray pyrolysis to prepare the carbon micron-spheres that area load has ferriferrous oxide nano-particle.This method preparation time is longer, and productive rate is lower.Utilize at present for another example polyvinyl chloride or chlorinated polyvinyl chloride are how fast dehydrochlorination makes its crosslinked carbonization as the key issue that presoma prepares nanometer, micron carbon fiber.W.M.Qiao etc. have reported a kind of method (W.M.Qiao for preparing carbon fiber, S.H.Yoon, Y.Korai, I.Mochida, S.Inoue, T.Sakurai, T.Shimohara.Preparation of activated carbon fibers from polyvinyl chloride.Carbon, 7 (24): 1327～1331.), the method for these method two step dechlorinations prepares carbon fiber.But the technology of this scientific and technical literature report is more loaded down with trivial details, the method more complicated, and productive rate is lower.
Summary of the invention
The preparation method who the objective of the invention is to carbon material, carbon-ferriferrous oxide composite material, the productive rate height of the carbon material that method provided by the invention obtains, carbon-ferriferrous oxide composite material.
The invention provides a kind of preparation method of carbon ball-ferriferrous oxide composite material, may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed, obtain chlorinated polyvinyl chloride-iron mixture;
Described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-ferriferrous oxide composite material.
The invention provides a kind of preparation method of carbon fiber-ferriferrous oxide composite material, may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron mixture;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material.
Preferably, the mass ratio of described chlorinated polyvinyl chloride and iron cpd is (85～99.5): (0.5～15).
Preferably, the temperature of described heating is 250 ℃～950 ℃.
Preferably, described iron cpd is one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and the ironic hydroxide.
Preferably, described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, one or more in dimethyl sulfoxide (DMSO) and the acetone.
Preferably, the voltage of described solvent spinning is 5KV～40KV;
The distance of spinning nozzle and collector is 5 centimetres～30 centimetres in the described solvent spinning.
The invention provides a kind of preparation method of carbon ball, may further comprise the steps:
Carbon ball-ferriferrous oxide composite material that the described preparation method of technique scheme is obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains the carbon ball.
The invention provides a kind of preparation method of carbon fiber, may further comprise the steps:
Carbon fiber-ferriferrous oxide composite material that the described preparation method of technique scheme is obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains carbon fiber.
Preferably, the volumetric molar concentration of described acidic solution is 0.5mol/L～2.0mol/L.
The invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Method provided by the invention is raw material with chlorinated polyvinyl chloride and iron cpd, and chlorinated polyvinyl chloride is directly mixed with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes; Or chlorinated polyvinyl chloride and iron cpd dissolved in organic solvent, then the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-iron complexes or the chlorinated polyvinyl chloride fibre-iron complexes that obtains carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after the cooling.The present invention mixes the above-mentioned carbon ball-iron composite material for preparing or carbon fiber-iron composite material in order to obtain carbon material with acidic solution, carry out precipitate and separate after leaving standstill, and obtains carbon ball or carbon fiber.Method provided by the invention is with the carbon source material of chlorinated polyvinyl chloride as synthetic carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action in the combustion reactions process, synthetic carbon-ferriferrous oxide composite material or carbon material.Method technology provided by the invention is simple, and productive rate is higher.Embodiment of the invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can be up to 42.0%, and the yield of preparation carbon ball can be up to 32.8%.
Embodiment
A kind of preparation method of carbon ball-ferriferrous oxide composite material may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed, obtain chlorinated polyvinyl chloride-iron mixture;
Described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-ferriferrous oxide composite material.
Method provided by the invention is carbon source with the chlorinated polyvinyl chloride, under the katalysis of iron cpd, carries out combustion reactions, and dehydrochlorination and carry out crosslinking reaction obtains carbon-ferriferrous oxide composite material.The invention provides method technology and simple to operate, the carbon that obtains-Z 250 yield height.
The present invention mixes chlorinated polyvinyl chloride and iron cpd, obtains chlorinated polyvinyl chloride-iron mixture.The present invention does not have special restriction to the method for described chlorinated polyvinyl chloride and iron cpd mixing, and the technical scheme that adopts solid materials well known to those skilled in the art to mix gets final product.The present invention preferably places ball mill with chlorinated polyvinyl chloride and iron cpd, mixes, and obtains chlorinated polyvinyl chloride-iron mixture.In the present invention, the particle diameter of described chlorinated polyvinyl chloride is preferably 50 nanometers～500 micron, and 70 nanometers～480 micron more preferably most preferably are 100 nanometers～450 micron; Described iron cpd is preferably one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and the ironic hydroxide; The particle diameter of described iron cpd is preferably 5 nanometers～50 micron, and 10 nanometers～45 micron more preferably most preferably are 20 nanometers～40 micron; The mass ratio of described chlorinated polyvinyl chloride and iron cpd is preferably (85～99.5): (0.5～15), more preferably (87～98): (2～13) most preferably are (90～95): (5～10).In the present invention, the speed that described chlorinated polyvinyl chloride and iron cpd mix is preferably 50 rev/mins～100 rev/mins, more preferably 60 rev/mins～90 rev/mins, most preferably is 70 rev/mins～85 rev/mins; The time that described chlorinated polyvinyl chloride and iron cpd mix is preferably 5 minutes～and 20 minutes, more preferably 8 minutes～18 minutes, most preferably be 10 minutes～15 minutes.
After obtaining the mixture of chlorinated polyvinyl chloride-iron, the present invention carries out reacting by heating with described chlorinated polyvinyl chloride-iron mixture, and is complete to the chlorinated polyvinyl chloride burning, obtains carbon ball-ferriferrous oxide composite material.The present invention preferably places ceramic crucible with described chlorinated polyvinyl chloride-iron mixture, heats after adding a cover, and chlorinated polyvinyl chloride takes fire, until the chlorinated polyvinyl chloride burning fully, the no flame in ceramic crucible top produces, and is cooled to room temperature, obtains carbon ball-ferriferrous oxide composite material.In the present invention, the temperature of described heating is preferably 250 ℃～950 ℃, more preferably 280 ℃～920 ℃, most preferably is 300 ℃～900 ℃.
The invention provides a kind of preparation method of carbon fiber-Z 250, may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron mixture;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material.
The present invention mixes chlorinated polyvinyl chloride and iron cpd in organic solvent, then the mixing solutions that obtains is carried out solvent spinning, obtains chlorinated polyvinyl chloride fibre-iron mixture.In the present invention, the particle diameter of described chlorinated polyvinyl chloride is preferably 50 nanometers～500 micron, and 70 nanometers～480 micron more preferably most preferably are 100 nanometers～450 micron; Described iron cpd is preferably one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and the ironic hydroxide; The particle diameter of described iron cpd is preferably 5 nanometers～50 micron, and 10 nanometers～45 micron more preferably most preferably are 20 nanometers～40 micron; The mass ratio of described chlorinated polyvinyl chloride and iron cpd is preferably (85～99.5): (0.5～15), more preferably (87～98): (2～13) most preferably are (90～95): (5～10);
In the present invention, described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, in dimethyl sulfoxide (DMSO) and the acetone one or more, tetrahydrofuran (THF) more preferably, N, dinethylformamide, orthodichlorobenzene, in dimethyl sulfoxide (DMSO) and the acetone one or both, when described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, when orthodichlorobenzene, in dimethyl sulfoxide (DMSO) and the acetone two kinds, two component mass ratioes in the organic solvent are preferably (5～95): (95～5), more preferably (10～90): (90～10) most preferably are (20～80): (80～20); The present invention does not have special restriction to the consumption of described organic solvent, above-mentioned chlorinated polyvinyl chloride and iron cpd can be dissolved fully and get final product, in the present invention, the mass ratio of described organic solvent and chlorinated polyvinyl chloride is preferably (70～97.5): (2.5～30), more preferably (75～95): (5～25) most preferably are (80～90): (10～20).
The present invention does not have special restriction to the method for described solvent spinning, adopts the technical scheme of solvent spinning well known to those skilled in the art to get final product.The present invention preferably places plastic injector with the chlorinated polyvinyl chloride that obtains and the mixing solutions of iron cpd, described syringe is being received on the high-voltage power supply, the positive pole of power supply connects spinning nozzle, the negative pole of power supply connects the copper sheet collector, described collector ground connection of while, after spinning for some time, the fiber that obtains is peeled off from the copper sheet collector, drying obtains thermovyl-iron mixture after removing residual solvent.In the present invention, the voltage of supply of described solvent spinning is preferably 5KV～40KV, and more preferably 10KV～35KV most preferably is 15KV～30KV; Distance between described spinning nozzle and the collector is preferably 5 centimetres～30 centimetres, more preferably 10 centimetres～25 centimetres, most preferably is 15 centimetres～20 centimetres; The present invention does not have special restriction to the time of spinning, and those skilled in the art can select the rational spinning time according to the quality of the matrix material of the amount of mixing solutions and needs.The present invention does not have special restriction to the method for described drying, adopts the technical scheme of drying well known to those skilled in the art to get final product, in the present invention, described drying is preferably vacuum-drying, the temperature of described drying is preferably 70 ℃～90 ℃, more preferably 75 ℃～85 ℃, most preferably is 80 ℃; The time of described drying is preferably 18 hours～and 30 hours, more preferably 21 hours～27 hours, most preferably be 24 hours.
After obtaining chlorinated polyvinyl chloride fibre-iron complexes, the present invention obtains the technical scheme of carbon ball-ferriferrous oxide composite material according to the described chlorinated polyvinyl chloride-iron complexes of technique scheme, prepares carbon fiber-ferriferrous oxide composite material.No longer the process that chlorinated polyvinyl chloride fibre-iron complexes prepares carbon fiber-ferriferrous oxide composite material is given unnecessary details at this.
The invention provides a kind of preparation method of carbon material, remove carbon ball-ferriferrous oxide composite material that technique scheme prepares or the Z 250 in carbon fiber-ferriferrous oxide composite material, can obtain corresponding carbon ball or carbon fiber.
The invention provides a kind of preparation method of carbon ball, may further comprise the steps:
Carbon ball-ferriferrous oxide composite material that the described preparation method of technique scheme is obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains the carbon ball.
The present invention prepares carbon ball-ferriferrous oxide composite material according to the technical scheme of the described preparation carbon of technique scheme ball-ferriferrous oxide composite material.Carbon ball-the Z 250 that obtains is mixed with acidic solution, and Z 250 wherein and acidic solution reaction are dissolved in the solution, with precipitate and separate, obtain the carbon ball after leaving standstill.The solid that the present invention preferably obtains separation to neutral, obtains the carbon ball with washed with de-ionized water.In the present invention, described acidic solution is preferably one or more in hydrochloric acid, nitric acid or the sulfuric acid, more preferably hydrochloric acid; The volumetric molar concentration of described acidic solution is preferably 0.5mol/L～2.0mol/L, more preferably 1.0mol/L～1.5mol/L; The described time of leaving standstill is preferably 24 hours～and 36 hours, more preferably 27 hours～33 hours, most preferably be 30 hours.
The present invention also provides a kind of preparation method of carbon fiber, may further comprise the steps:
Carbon fiber-ferriferrous oxide composite material that the described preparation method of technique scheme is obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains carbon fiber.
The present invention prepares carbon fiber-ferriferrous oxide composite material according to the technical scheme of the described preparation carbon fiber-ferriferrous oxide composite material of technique scheme; Then carbon fiber-the ferriferrous oxide composite material that obtains is mixed with acidic solution, Z 250 wherein and acidic solution reaction are dissolved in the solution, with precipitate and separate, obtain carbon fiber after leaving standstill.The solid that the present invention preferably obtains separation to neutral, obtains carbon fiber with washed with de-ionized water.In the present invention, described acidic solution is preferably one or more in hydrochloric acid, nitric acid or the sulfuric acid, more preferably hydrochloric acid; The volumetric molar concentration of described acidic solution is preferably 0.5mol/L～2.0mol/L, more preferably 1.0mol/L～1.5mol/L; The described time of leaving standstill is preferably 24 hours～and 36 hours, more preferably 27 hours～33 hours, most preferably be 30 hours.
The invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Method provided by the invention is raw material with chlorinated polyvinyl chloride and iron cpd, and chlorinated polyvinyl chloride is directly mixed with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes; Or chlorinated polyvinyl chloride and iron cpd dissolved in organic solvent, then the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-iron complexes or the chlorinated polyvinyl chloride fibre-iron complexes that obtains carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after the cooling.The present invention mixes the above-mentioned carbon ball-iron composite material for preparing or carbon fiber-iron composite material in order to obtain carbon material with acidic solution, carry out precipitate and separate after leaving standstill, and obtains carbon ball or carbon fiber.Method provided by the invention is with the carbon source material of chlorinated polyvinyl chloride as synthetic carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action in the combustion reactions process, synthetic carbon-ferriferrous oxide composite material or carbon material.Method technology provided by the invention is simple, and productive rate is higher.Embodiment of the invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can be up to 42.0%, and the yield of preparation carbon ball can be up to 32.8%.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of carbon material provided by the invention, carbon-ferriferrous oxide composite material is described in detail, but they can not be interpreted as restriction to protection domain of the present invention.
Embodiment 1
By weight, be that the chlorinated polyvinyl chloride of 75 nanometers and 1 part, particle diameter are that the ferric oxide of 10 nanometers adds in the ball mill simultaneously with 99 parts, particle diameter, mixed 10 minutes in that 50 rev/mins speed are following, obtain chlorinated polyvinyl chloride-ferric oxide mixture;
Get above-mentioned chlorinated polyvinyl chloride-ferric oxide mixture 1 gram (comprising 0.99 gram chlorinated polyvinyl chloride and 0.01 gram ferric oxide) and place 15 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 700 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature; Obtain carbon-ferriferrous oxide composite material.
The quality of carbon-ferriferrous oxide composite material that weighing of the present invention obtains is 0.32 gram, and calculating yield is 32.0%; The present invention carries out the scanning electron microscope scanning analysis with the carbon-ferriferrous oxide composite material that obtains, and the result shows that carbon-ferriferrous oxide composite material that the present invention obtains is carbon ball-Z 250 mixture, and median size is 75 nanometers～100 nanometers.
The present invention just volumetric molar concentration is that the aqueous hydrochloric acid of 1.0mol/L joins in carbon ball-Z 250 black mixture that technique scheme obtains, and places 24 hours, and precipitate and separate is 7 with washed with de-ionized water to pH value.Obtain the carbon material of purifying this moment.
The quality that weighing of the present invention obtains carbon material is 0.29 gram, and calculating yield is 29.3%; The present invention carries out the scanning electron microscope scanning analysis with the carbon material that obtains, and the result shows that the carbon material that the present invention obtains is the carbon ball, and median size is 75 nanometers～100 nanometers.
Embodiment 2
By weight, be that 2 microns chlorinated polyvinyl chloride and 2.5 parts, particle diameter are that 20 nanometer ferric oxide add in the ball mill simultaneously with 97.5 parts, particle diameter, mixed 10 minutes in that 50 rev/mins speed are following, obtain mixture;
Get the chlorinated polyvinyl chloride that technique scheme obtains-ferric oxide mixture 1 gram (comprising 0.975 gram chlorinated polyvinyl chloride and 0.025 gram ferric oxide) and place 15 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 700 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
The quality of carbon-ferriferrous oxide composite material that weighing of the present invention obtains is 0.36 gram, and calculating yield is 36.0%; The present invention carries out the scanning electron microscope scanning analysis with the carbon-ferriferrous oxide composite material that obtains, and the result shows that carbon-ferriferrous oxide composite material that the present invention obtains is carbon ball-Z 250 mixture, and median size is 2 microns～2.5 microns.
The present invention just volumetric molar concentration is that the aqueous hydrochloric acid of 1.0mol/L joins carbon ball-Z 250 black mixture that technique scheme obtains, and places 24 hours, and precipitate and separate is 7 with washed with de-ionized water to pH value, obtains the carbon material of purifying this moment.
The quality of the carbon material that weighing of the present invention obtains is 0.32 gram, and calculating yield is 32.8%; The present invention carries out the scanning electron microscope scanning analysis with the carbon material that obtains, and the result shows that the carbon material that the present invention obtains is the carbon ball, and median size is 2 microns～2.5 microns.
Embodiment 3
By weight, be that 20 microns chlorinated polyvinyl chloride and 5 parts, particle diameter are that the ferric oxide of 50 nanometers adds in the ball mill simultaneously with 95 parts, particle diameter, under 50 rev/mins rotating speed, mixed 10 minutes, and obtained chlorinated polyvinyl chloride-ferric oxide mixture;
Get the chlorinated polyvinyl chloride that technique scheme obtains-ferric oxide mixture 1 gram (comprising 0.95 gram chlorinated polyvinyl chloride and 0.05 gram ferric oxide) and place 15 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 700 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
The quality that weighing of the present invention obtains carbon-ferriferrous oxide composite material is 0.41 gram, and calculating yield is 41.0%; The present invention carries out the scanning electron microscope scanning analysis with the carbon-ferriferrous oxide composite material that obtains, and the result shows that the carbon-ferriferrous oxide composite material of the present invention's preparation is carbon ball-Z 250 mixture, and median size is 20 microns～25 microns.
The present invention is that the aqueous hydrochloric acid of 1.0mol/L joins carbon ball-Z 250 black mixture that technique scheme obtains with volumetric molar concentration, places 24 hours, and precipitate and separate is 7 with washed with de-ionized water to pH value, obtains the carbon material of purifying this moment;
The quality of the carbon material that weighing of the present invention obtains is 0.34 gram, and calculating yield is 35.8%; The present invention carries out the scanning electron microscope scanning analysis with the carbon material that obtains, and the result shows that the carbon material that the present invention obtains is the carbon ball, and median size is 20 microns～25 microns.
Embodiment 4
By weight, be that 200 microns chlorinated polyvinyl chloride and 10 parts, particle diameter are that 5 microns ironic hydroxide adds in the ball mill simultaneously with 90 parts, particle diameter, under 50 rev/mins rotating speed, mixed 10 minutes, and obtained chlorinated polyvinyl chloride-ironic hydroxide mixture;
Get the chlorinated polyvinyl chloride that technique scheme obtains-ironic hydroxide mixture 6 grams (comprising 5.4 gram chlorinated polyvinyl chlorides and 0.6 gram ironic hydroxide) and place 30 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 500 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon-ferriferrous oxide composite material.
The quality that weighing of the present invention obtains carbon-ferriferrous oxide composite material is 2.02 grams, and calculating yield is 33.7%; The present invention carries out the scanning electron microscope scanning analysis with the carbon-ferriferrous oxide composite material that obtains, and the result shows that carbon-ferriferrous oxide composite material provided by the invention is carbon ball-Z 250 mixture, and median size is 200 microns～250 microns.
Be that the aqueous hydrochloric acid of 1.0mol/L joins above-mentioned carbon-Z 250 black matrix material with volumetric molar concentration, placed 24 hours that precipitate and separate is 7 with washed with de-ionized water to pH value, obtains the carbon material of purifying.
The quality that weighing of the present invention obtains carbon material is 1.90 grams, and calculating yield is 35.2%; The present invention carries out the scanning electron microscope scanning analysis with the carbon material that obtains, and the result shows that the carbon material of the present invention's preparation is the carbon ball, and median size is 200 microns～250 microns.
Embodiment 5
By weight, be that 100 microns chlorinated polyvinyl chloride and 5 parts, particle diameter are that the ironic hydroxide of 10 nanometers joins tetrahydrofuran (THF)/N that volume ratio is 7:3 with 95 parts, particle diameter, in the dinethylformamide mixed solvent, after the stirring and dissolving, in the mixing solutions injected plastic syringe that obtains, again syringe is connected to the high-voltage power supply of 5KV, positive source connects spinning nozzle, negative pole connects the copper sheet receptor, while receptor ground connection, fixedly the distance between spinning nozzle and the receptor is 5 centimetres, carries out solvent spinning; The fiber that spinning is obtained peels from copper sheet, places the dry 24 little removal residual solvents of 80 ℃ of vacuum drying ovens, obtains chlorinated polyvinyl chloride fibre-ironic hydroxide mixture, and the present invention detects the diameter that obtains fiber and is about 50 nanometers.
Get the chlorinated polyvinyl chloride fibre that technique scheme obtains-ironic hydroxide mixture 2 grams (comprising 1.9 gram chlorinated polyvinyl chlorides and 0.1 gram ironic hydroxide) and place 30 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 500 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon fiber-Z 250 mixture.
The quality that weighing of the present invention obtains carbon fiber-Z 250 mixture is 0.80 gram, calculates yield 40.0%; It is 50 nanometers～75 nanometers that the present invention detects the diameter that obtains carbon fiber-Z 250 mixture.
The present invention is that the aqueous hydrochloric acid of 1.0mo/L joins above-mentioned carbon fiber-Z 250 black mixture with volumetric molar concentration, places 24 hours, and precipitate and separate is 7 with washed with de-ionized water to pH value.Obtain the carbon fiber of purifying this moment.
The quality that weighing of the present invention obtains carbon fiber is 0.65 gram, and calculating yield is 34.2%; It is 50 nanometers～75 nanometers that the present invention detects the diameter that obtains carbon fiber.
Embodiment 6
By weight, be that 200 microns chlorinated polyvinyl chloride and 10 parts, particle diameter are that 20 nano ferriferrous oxides join tetrahydrofuran (THF) and the N that volume ratio is 7:3 with 90 parts, particle diameter, in the mixed solvent of dinethylformamide, after the stirring and dissolving, in the mixing solutions injected plastic syringe that obtains, again syringe is connected to the high-voltage power supply of 40KV, positive source connects spinning nozzle, negative pole connects the copper sheet receptor, while receptor ground connection, fixedly the distance between spinning nozzle and the receptor is 30 centimetres, carries out solvent spinning; The fiber that spinning is obtained peels from copper sheet, places the dry 24 little removal residual solvents of 80 ℃ of vacuum drying ovens, obtains chlorinated polyvinyl chloride fibre-ironic hydroxide mixture, and the present invention detects the diameter that obtains fiber and is about 0.2 micron.
Get the chlorinated polyvinyl chloride fibre that technique scheme obtains-Z 250 mixture 6 grams (comprising 5.4 gram chlorinated polyvinyl chlorides and 0.6 gram Z 250) and place 30 milliliters of crucibles, and add and be placed on the crucible; With combustion gas lamp flame envelope heating crucible bottom, after several seconds, chlorinated polyvinyl chloride takes fire, and the interior temperature of crucible this moment is 700 ℃; To chlorinated polyvinyl chloride not behind the reignition, take off crucible, be put in shady and cool place and be cooled to room temperature, obtain carbon fiber-Z 250 mixture.
The quality that weighing of the present invention obtains carbon fiber-Z 250 mixture is 2.52 grams, and calculating yield is 42.0%; It is 0.2 micron～0.3 micron that the present invention detects the diameter that obtains carbon fiber-Z 250 mixture.
The present invention is that the aqueous hydrochloric acid of 1.0mol/L joins above-mentioned carbon fiber-Z 250 black mixture with volumetric molar concentration, places 24 hours, and precipitate and separate is 7 with washed with de-ionized water to pH value, obtains the carbon fiber of purifying.
The quality of the carbon fiber that weighing of the present invention obtains is 1.80 grams, and calculating yield is 33.3%; It is 0.2 micron～0.3 micron that the present invention detects the diameter that obtains carbon fiber.
As seen from the above embodiment, the invention provides the preparation method of a kind of carbon material, carbon-ferriferrous oxide composite material.Method provided by the invention is raw material with chlorinated polyvinyl chloride and iron cpd, and chlorinated polyvinyl chloride is directly mixed with iron cpd, obtains chlorinated polyvinyl chloride-iron complexes; Or chlorinated polyvinyl chloride and iron cpd dissolved in organic solvent, then the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron complexes; Then chlorinated polyvinyl chloride-iron complexes or the chlorinated polyvinyl chloride fibre-iron complexes that obtains carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-iron composite material or carbon fiber-iron composite material after the cooling.The present invention mixes the above-mentioned carbon ball-iron composite material for preparing or carbon fiber-iron composite material in order to obtain carbon material with acidic solution, carry out precipitate and separate after leaving standstill, and obtains carbon ball or carbon fiber.Method provided by the invention is with the carbon source material of chlorinated polyvinyl chloride as synthetic carbon material or carbon-iron cpd matrix material, under the quick catalysis of iron cpd, chlorinated polyvinyl chloride carries out dehydrochlorination and crosslinked action in the combustion reactions process, synthetic carbon-ferriferrous oxide composite material or carbon material.Method technology provided by the invention is simple, and productive rate is higher.Embodiment of the invention result shows, method provided by the invention prepares the yield of carbon fiber-ferriferrous oxide composite material can be up to 42.0%, and the yield of preparation carbon ball can be up to 32.8%.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a carbon ball-ferriferrous oxide composite material may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed, obtain chlorinated polyvinyl chloride-iron mixture;
Described chlorinated polyvinyl chloride-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon ball-ferriferrous oxide composite material.
2. the preparation method of a carbon fiber-ferriferrous oxide composite material may further comprise the steps:
Chlorinated polyvinyl chloride and iron cpd are mixed in organic solvent, the mixing solutions that obtains is carried out solvent spinning, obtain chlorinated polyvinyl chloride fibre-iron mixture;
Described chlorinated polyvinyl chloride fibre-iron mixture is carried out reacting by heating, complete to the chlorinated polyvinyl chloride burning, obtain carbon fiber-ferriferrous oxide composite material.
3. according to any described preparation method of claim 1～2, it is characterized in that the mass ratio of described chlorinated polyvinyl chloride and iron cpd is (85～99.5): (0.5～15).
4. according to any described preparation method of claim 1～2, it is characterized in that the temperature of described heating is 250 ℃～950 ℃.
5. according to any described preparation method of claim 1～2, it is characterized in that described iron cpd is one or more in iron protoxide, ferric oxide, Z 250, ferrous hydroxide and the ironic hydroxide.
6. preparation method according to claim 2 is characterized in that, described organic solvent is tetrahydrofuran (THF), N, dinethylformamide, orthodichlorobenzene, one or more in dimethyl sulfoxide (DMSO) and the acetone.
7. preparation method according to claim 2 is characterized in that, the voltage of described solvent spinning is 5KV～40KV;
The distance of spinning nozzle and collector is 5 centimetres～30 centimetres in the described solvent spinning.
8. the preparation method of a carbon ball may further comprise the steps:
Carbon ball-ferriferrous oxide composite material that claim 1 and 3～5 any described preparation methods are obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains the carbon ball.
9. the preparation method of a carbon fiber may further comprise the steps:
Carbon fiber-ferriferrous oxide composite material that any described preparation method of claim 2～7 is obtained mixes with acidic solution, leaves standstill postprecipitation and separates, and obtains carbon fiber.
10. any described preparation method is characterized in that according to Claim 8～9, and the volumetric molar concentration of described acidic solution is 0.5mol/L～2.0mol/L.
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| CN103949217A (en) * | 2014-05-22 | 2014-07-30 | 中国科学院长春应用化学研究所 | Method for preparing ferroferric oxide and carbon foam complex and method for preparing carbon foam |
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| CN108377637A (en) * | 2018-02-13 | 2018-08-07 | 南通大学 | A kind of activated carbon fiber-ferriferrous oxide composite material and preparation method thereof |
| CN108377637B (en) * | 2018-02-13 | 2019-10-11 | 南通大学 | A kind of activated carbon fiber-ferriferrous oxide composite material and preparation method thereof |
| CN108658057A (en) * | 2018-07-03 | 2018-10-16 | 中国矿业大学(北京) | A kind of atmospheric preparation method of magnetism Carbon foam |
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