CN101445234B - A preparation method of graphitized carbon nano material - Google Patents
A preparation method of graphitized carbon nano material Download PDFInfo
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- CN101445234B CN101445234B CN200910071219XA CN200910071219A CN101445234B CN 101445234 B CN101445234 B CN 101445234B CN 200910071219X A CN200910071219X A CN 200910071219XA CN 200910071219 A CN200910071219 A CN 200910071219A CN 101445234 B CN101445234 B CN 101445234B
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Abstract
The present invention discloses a preparation method of graphitized carbon nano material which relates to a preparation method of carbon nano material. Problems like high cost and environment pollution in existing graphitized carbon nano material process are solved through the invention. The method is as following: 1. pretreatment of carbon source; 2. energizing agent in solvent and carbon source after pretreatment; 3. pre-carbonization; 4. heat treating; 5. acid treatment; 6. physical activation or chemical activation. The invention has features like simple process, little pollution to environment, low cost, simple equipment and easy commercialization.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanomaterial.
Background technology
In recent years, owing to the using value at aspects such as separation, energy storage, electrocatalysis, medicament transport, the research of nano-carbon material has caused the very big concern of academia and business circles.Because graphite has high thermostability, chemical stability, electroconductibility, high electronic conductivity, field emission performance and metal and characteristic of semiconductor, thereby the carbon nanomaterial with graphite-structure has bigger improvement on performance, can be applied to prepare the anode material of industrial electrode, lithium ion battery and as the carrier of electrochemical catalyst.In addition, the microscopic appearance of carbon material also has very big influence to its application, such as the graphite capsule can be used as support of the catalyst, also can be used for dye adsorption and medicament storage, and lamella graphite can be used as awkward silence at a meeting transistor radiator.Therefore, the new method of the exploitation graphitization nano carbon material for preparing multiple pattern is subjected to investigator's extensive concern.
At present, the method for synthetic graphite carbon nanomaterial mainly contains methods such as arc discharge method, chemical Vapor deposition process, laser ablation method, electron beam irradiation method and the carbonaceous metallized compound of thermolysis.According to the difference of employed method and use carbon matrix precursor, the graphitized carbon material of multiple pattern such as Nano capsule, nanotrees, nanometer volume, nanofiber, nano belt, nanometer sheet, nanometer angle, nm wall etc. successfully are synthesized.Yet these methods have following shortcoming: temperature of reaction is higher, complex process, productive rate is low and have by product to generate, and the product needed of preparation is further purified and could be used, thereby has increased cost greatly; In addition, employed carbon source mostly is the nonrenewable resources that benzene, toluene, acetylene, methane etc. extract from coal, ore, and on preparation technology, environmental pollution is comparatively serious, thereby is unfavorable for commercial applications.Solid-phase pyrolysis is considered to a kind of comparatively effectively preparation method, and product pattern, size homogeneous by the kind of simple adjustment carbon source and catalyzer, can make the graphitization nano carbon material of different-shape.Many at present employing resol etc. are as carbon source, and this class material is the extract of oil, and under the situation of current scarcity of resources, cost also can be higher, limited it and commercially produced.
Summary of the invention
The objective of the invention is to have cost height, problem of environment pollution caused in order to solve existing preparation graphitized carbon nano material; And provide a kind of preparation method of graphitized carbon nano material.
The preparation method of graphitized carbon nano material is finished by following step among the present invention: one, carbon source is carried out pre-treatment 1～10h; Two, add catalyzer and through pretreated carbon source in solvent, stir 8h under 50 ℃, 100～300r/min stirring velocity, wherein the mass ratio of carbon source and catalyzer is 0.025～1: 1; Three, be pre-carburising step two mixtures 2～8h under 80～450 ℃ of conditions in temperature, pre-carburizing atmosphere is the mixed gas of one or more gases in air, oxygen, nitrogen, argon gas, the helium; Four, the heat-up rate with 1～15 ℃/min rises to 400～1200 ℃ by room temperature, at heat-treating atmosphere, heat-treating atmosphere flow is that 30～2000mL/min, thermal treatment temp are under 400～1200 ℃ of conditions, the step 3 product is heat-treated 10min～10h, and wherein heat-treating atmosphere is the mixed gas of one or more gases in nitrogen, argon gas, helium, carbon monoxide, carbonic acid gas, hydrogen sulfide, hydrogen and the water vapour; Five, being added to mass concentration after the product of step 4 is ground is in 15%～20% the nitric acid or hydrochloric acid, 6～14h refluxes under 110～140 ℃ of conditions, be washed with distilled water to neutrality, drying under 110～120 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions then; Six, the product to step 5 carries out physically activated or chemical activation, obtains graphitized carbon nano material after the drying.
The carbon source of step 1 is farm-forestry crop extract or agriculture and forestry organic waste material; The farm-forestry crop extract is glucose, sucrose, fructose or starch; Agriculture and forestry organic waste material is cornstalk, sorghum stalk, beet pulp, bagasse or wood chip.
The pretreated method of carbon source described in the step 1 is microwave method, hydrothermal method, ultrasonic method, spray method, acidic treatment or alkaline purification method.
Catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close a kind of or wherein several mixing in potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, the nickelous acetate.
Solvent described in the step 2 is a kind of or wherein several mixing in water, methyl alcohol, ethanol, the Virahol.
Physically activated method described in the step 6 is as follows: under water vapour, carbonic acid gas, hydrogen or carbon monoxide atmosphere, and physically activated temperature is that 200～500 ℃, physical gas flow are under 100～4000mL/min condition, with the physically activated 0.5～24h of the product of step 5.
Chemical activation method described in the step 6 is as follows: in activation temperature is under 80～180 ℃ of conditions, the product of step 5 activates 3～12h in inorganic solution, wherein the mass concentration of inorganic solution is 10%～45%, and inorganic solution is a kind of or wherein two kinds the mixing in potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid, the potassium permanganate.
Drying described in the step 6 is to dry under 110～120 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions.
The present invention adopts farm-forestry crop extract and agriculture and forestry organic waste material to make carbon source, and its wide material sources and inexpensive have solved environmental issue on the one hand, greatly reduce the cost of synthetic graphite carbon nanomaterial on the other hand.The present invention is based on the coordination process of electrostatic interaction, complexing action and other weak interaction, contain dissolution in low temperature-coordination-high temperature graphitization process, its energy consumption is low.Preparation technology of the present invention is simple, and experimental installation is simple, and cost is low, is easy to realize commercialization.The inventive method can prepare the graphitized carbon nano material and the graphitized carbon/magnetic particle matrix material of various patterns such as the cryptomere, sheet of nano-scale, fibrous, spirrillum, web-like, tubulose, horn shape, band shape, be applied to the organic dye fractionation by adsorption, electrochemistry aspect, super-capacitor aspect.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the graphitized carbon nano material of embodiment 53 preparations.Fig. 2 is the Raman spectrogram of the graphitized carbon nano material of embodiment 53 preparations.Fig. 3 is the transmission electron microscope photo of the graphitized carbon nano material of embodiment 53 preparations.Fig. 4 is that the high score rate of the graphitized carbon nano material of embodiment 53 preparations is distinguished the transmitted electron micro.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment graphitized carbon nano material is finished by following step: one, carbon source is carried out pre-treatment 1～10h; Two, add catalyzer and through pretreated carbon source in solvent, stir 8h under 50 ℃, 100～300r/min stirring velocity, wherein the mass ratio of carbon source and catalyzer is 0.025～1: 1; Three, be pre-carburising step two mixtures 2～8h under 80～450 ℃ of conditions in temperature, pre-carburizing atmosphere is the mixed gas of one or more gases in air, oxygen, nitrogen, argon gas, the helium; Four, the heat-up rate with 1～15 ℃/min rises to 400～1200 ℃ by room temperature, at heat-treating atmosphere, heat-treating atmosphere flow is that 30～2000mL/min, thermal treatment temp are under 400～1200 ℃ of conditions, the step 3 product is heat-treated 10min～10h, and wherein heat-treating atmosphere is the mixed gas of one or more gases in nitrogen, argon gas, helium, carbon monoxide, carbonic acid gas, hydrogen sulfide, hydrogen and the water vapour; Five, being added to mass concentration after the product of step 4 is ground is in 15%～20% the nitric acid or hydrochloric acid, 6～14h refluxes under 110～140 ℃ of conditions, be washed with distilled water to neutrality, drying under 110～120 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions then; Six, the product to step 5 carries out physically activated or chemical activation, obtains graphitized carbon nano material after the drying.
When the pre-carburizing atmosphere of present embodiment step 3 is mixture, press between various pre-carburizing atmospheres arbitrarily than mixing.When the heat-treating atmosphere in the step 4 is mixture, press between various heat-treating atmospheres arbitrarily than mixing.Reach granularity at 20～40nm through grinding in the step 5.
Embodiment two: what present embodiment and embodiment one were different is: the carbon source of step 1 is farm-forestry crop extract or agriculture and forestry organic waste material.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment two were different is: the farm-forestry crop extract is glucose, sucrose, fructose or starch.Other step and parameter are identical with embodiment two.
Embodiment four: what present embodiment and embodiment two were different is: agriculture and forestry organic waste material is cornstalk, sorghum stalk, beet pulp, bagasse or wood chip.Other step and parameter are identical with embodiment two.
Embodiment five: what present embodiment and embodiment four were different is: agriculture and forestry organic waste material is cornstalk or jowar stalk, in the step 1 agriculture and forestry organic waste material is pulverized back pre-treatment 1～10h, before the operation of carrying out step 2, carry out being washed with water to after the centrifugation pH=6～8 of washing lotion.Other step and parameter are identical with embodiment four.
Embodiment six: what present embodiment and embodiment one, two, three or four were different is: the pretreated method of the carbon source described in the step 1 is microwave method, hydrothermal method, ultrasonic method, spray method, acidic treatment or alkaline purification method.Other step and parameter are identical with embodiment one, two, three or four.
Embodiment seven: present embodiment and embodiment six are different: adopting microwave method pre-treatment carbon source is to be undertaken by following reaction: be under the condition of 3.0～8.0kW at microwave intensity, to carbon source microwave treatment 10～60min, promptly finish the pre-treatment of carbon source.Other step and parameter are identical with embodiment six.
Embodiment eight: present embodiment and embodiment six are different: adopting hydrothermal method pre-treatment carbon source is to be undertaken by following reaction: in temperature is under 120～180 ℃ of conditions, to carbon source hydrothermal treatment consists 4～8h, promptly finishes the pre-treatment of carbon source.Other step and parameter are identical with embodiment six.
Embodiment nine: present embodiment and embodiment six are different: adopt ultrasonic method pre-treatment carbon source to be undertaken by following reaction: adopting ultrasonic method pre-treatment carbon source is to be undertaken by following reaction: in frequency is under 2～6KHz condition, to carbon source supersound process 0.5～2h, promptly finish the pre-treatment of carbon source.Other step and parameter are identical with embodiment six.
Embodiment ten: present embodiment and embodiment six are different: adopting spray method pre-treatment carbon source is to be undertaken by following reaction: with carbon source and activator mix, at 220V, the pre-treatment of spraying under 60～100Hz frequency, wherein activator is that mass concentration is 10～20% hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide or potassium hydroxide.Other step and parameter are identical with embodiment six.
Embodiment 11: present embodiment and embodiment six are different: adopting acidic treatment pre-treatment carbon source is to be undertaken by following reaction: it is that supersound process 3～6h gets final product in 10～15% the hydrochloric acid soln that carbon source is joined mass concentration.Other step and parameter are identical with embodiment six.
Embodiment 12: present embodiment and embodiment six are different: adopting alkaline purification method pre-treatment carbon source is to be undertaken by following reaction: it is to stir 0.5～4h in 10%～20% the KOH solution that carbon source is added mass concentration, hydrothermal treatment consists 2～5h again, be washed with distilled water to pH=6～8 of washing lotion, getting final product after the oven dry under 80～100 ℃ of conditions again.Other step and parameter are identical with embodiment six.
Embodiment 13: what present embodiment was different with embodiment one or six is: the catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close a kind of or wherein several mixing in potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, the nickelous acetate.Other step and parameter are identical with embodiment one or six.
When catalyzer is mixture in the present embodiment, press between various catalyzer arbitrarily than mixing.
Embodiment 14: what present embodiment was different with embodiment one or 13 is: the solvent described in the step 2 is a kind of or wherein several mixing in water, methyl alcohol, ethanol, the Virahol.Other step and parameter are identical with embodiment one or 13.
When solvent is mixture in the present embodiment, press between all kinds of SOLVENTS arbitrarily than mixing.
Embodiment 15: what present embodiment and embodiment one were different is: pre-carbonization temperature is 100～400 ℃ in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 16: what present embodiment and embodiment one were different is: pre-carbonization temperature is 150～350 ℃ in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 17: what present embodiment and embodiment one were different is: pre-carbonization temperature is 200～300 ℃ in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 18: what present embodiment and embodiment one were different is: pre-carbonization temperature is 250 ℃ in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 19: what present embodiment and embodiment one were different is: pre-carbonization time is 3～7h in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 20: what present embodiment and embodiment one were different is: pre-carbonization time is 4～6h in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 21: what present embodiment and embodiment one were different is: pre-carbonization time is 5h in the step 3.Other step and parameter are identical with embodiment one.
Embodiment 22: what present embodiment and embodiment one were different is: the heat-treating atmosphere flow is 100～1000mL/min in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 23: what present embodiment and embodiment one were different is: the heat-treating atmosphere flow is 200～800mL/min in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 24: what present embodiment and embodiment one were different is: the heat-treating atmosphere flow is 500mL/min in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 25: what present embodiment and embodiment one were different is: thermal treatment temp is 500～1000 ℃ in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 26: what present embodiment and embodiment one were different is: thermal treatment temp is 600～800 ℃ in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 27: what present embodiment and embodiment one were different is: thermal treatment temp is 700 ℃ in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 28: what present embodiment and embodiment one were different is: thermal treatment 30min～8h in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 29: what present embodiment and embodiment one were different is: thermal treatment 1～5h in the step 4.Other step and parameter are identical with embodiment one.
Embodiment 30: what present embodiment and embodiment one were different is: thermal treatment 2h in the step 4.Other step and parameter are identical with embodiment one.
The embodiment hentriaconta-: what present embodiment and embodiment one were different is: dry under 100～120 ℃ of conditions in the step 5.Other step and parameter are identical with embodiment one.
Embodiment 32: what present embodiment and embodiment one were different is: dry under 110 ℃ of conditions in the step 5.Other step and parameter are identical with embodiment one.
Embodiment 33: what present embodiment and embodiment one were different is: in the step 5 under 65～75 ℃ of conditions vacuum-drying 6.5～7.5h.Other step and parameter are identical with embodiment one.
Embodiment 34: what present embodiment and embodiment one were different is: in the step 5 under 70 ℃ of conditions vacuum-drying 7h.Other step and parameter are identical with embodiment one.
Embodiment 35: what present embodiment and embodiment one, two, 13 or 14 were different is: the physically activated method described in the step 6 is as follows: under water vapour, carbonic acid gas, hydrogen or carbon monoxide atmosphere, and physically activated temperature is that 200～500 ℃, physical gas flow are under 100～4000mL/min condition, with the physically activated 0.5～24h of the product of step 5.Other step and parameter are identical with embodiment one, two, 13 or 14.
Rising to 200～500 ℃ temperature rise rate by room temperature in the present embodiment is 5～10 ℃/min.
Embodiment 36: what present embodiment and embodiment 35 were different is: physically activated temperature is 250～450 ℃.Other step and parameter are identical with embodiment 35.
Embodiment 37: what present embodiment and embodiment 35 were different is: physically activated temperature is 300 ℃.Other step and parameter are identical with embodiment 35.
Embodiment 38: what present embodiment and embodiment 35 were different is: the physical gas flow is 200～3000mL/min.Other step and parameter are identical with embodiment 35.
Embodiment 39: what present embodiment and embodiment 35 were different is: the physical gas flow is 500～2000mL/min.Other step and parameter are identical with embodiment 35.
Embodiment 40: what present embodiment and embodiment 35 were different is: the physical gas flow is 1000mL/min.Other step and parameter are identical with embodiment 35.
Embodiment 41: what present embodiment and embodiment 35 were different is: the physically activated 1～20h of being.Other step and parameter are identical with embodiment 35.
Embodiment 42: what present embodiment and embodiment 35 were different is: the physically activated 5～15h of being.Other step and parameter are identical with embodiment 35.
Embodiment 43: what present embodiment and embodiment 35 were different is: physically activatedly be 10h.Other step and parameter are identical with embodiment 35.
Embodiment 44: what present embodiment and embodiment one, two, 13 or 14 were different is: the chemical activation method described in the step 6 is as follows: in activation temperature is under 80～180 ℃ of conditions, the product of step 5 activates 3～12h in inorganic solution, wherein the mass concentration of inorganic solution is 10%～45%, and inorganic solution is a kind of or wherein two kinds the mixing in potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid, the potassium permanganate.Other step and parameter are identical with embodiment one, two, 13 or 14.
When inorganic solution is mixture in the present embodiment, press between various inorganic solutions arbitrarily than mixing.Method in the present embodiment prepares graphitized carbon nano material and has bigger serface.
Embodiment 45: what present embodiment and embodiment 44 were different is: activation temperature is 100～150 ℃.Other step and parameter are identical with embodiment 44.
Embodiment 46: what present embodiment and embodiment 44 were different is: activation temperature is 120 ℃.Other step and parameter are identical with embodiment 44.
Embodiment 47: what present embodiment and embodiment 44 were different is: soak time is 5～10h.Other step and parameter are identical with embodiment 44.
Embodiment 48: what present embodiment and embodiment 44 were different is: soak time is 8h.Other step and parameter are identical with embodiment 44.
Embodiment 49: what present embodiment and embodiment 44 were different is: the mass concentration of inorganic solution is 20%～35%.Other step and parameter are identical with embodiment 44.
Embodiment 50: what present embodiment and embodiment 44 were different is: the mass concentration of inorganic solution is 30%.Other step and parameter are identical with embodiment 44.
Embodiment 51: what present embodiment and embodiment one, two, 13 or 14 were different is: drying is to dry under 110～120 ℃ of conditions in the step 6.Other step and parameter are identical with embodiment one, two, 13 or 14.
Embodiment 52: what present embodiment and embodiment one, two, 13 or 14 were different is: drying is vacuum-drying 6～8h under 60～80 ℃ of conditions in the step 6.Other step and parameter are identical with embodiment one, two, 13 or 14.
Embodiment 53: the preparation method of present embodiment graphitized carbon nano material is finished by following step: one, 10g jowar stalk particle (40～60 order) is added the 150mL mass concentration and be in 10% the KOH solution and stir 0.5～4h, hydrothermal treatment consists 2～5h again, be washed with distilled water to pH=6～8 of washing lotion, under 80～100 ℃ of conditions, dry again; Two, will join 100mL concentration through pretreated carbon source is in the 1mol/L ferric chloride in aqueous solution, stirs 8h under 50 ℃, 120～180r/min stirring velocity, is washed with water to pH=6～8 of washing lotion after the centrifugation; Three, be under 100 ℃ of conditions in nitrogen atmosphere, pre-carbonization temperature, the step 2 product is carried out pre-carbonization 2h; Four, the heat-up rate with 10 ℃/min rises to 1000 ℃ by room temperature, is that 60mL/min, thermal treatment temp are under 1000 ℃ of conditions at heat-treating atmosphere, heat-treating atmosphere flow, and the step 3 product is heat-treated 2h; Five, being added to the 150mL mass concentration after the product of step 4 is ground is in 20% the hydrochloric acid, and the 14h that refluxes under 110 conditions is washed with distilled water to pH=6～8 of washing lotion, dries under 110 ℃ of conditions then; Six, under carbon dioxide atmosphere, and physically activated temperature is that 300 ℃, physical gas flow are under the 100mL/min condition, with the physically activated 4h of the product of step 5, obtaining graphitized carbon nano material after the oven dry under 100 ℃ of conditions.
Rising to 300 ℃ temperature rise rate by room temperature in the present embodiment is 5 ℃/min.
The X-ray diffraction spectrogram of this graphitized carbon nano material as can be seen from the figure, has tangible crystal face diffraction peak as shown in Figure 1 on (002), (100) and (004) three crystal face, illustrate that this material has carbonization structure.The Raman spectrogram of this graphitized carbon nano material can find out significantly from figure that as shown in Figure 2 two characteristic peak G of graphite are with and the D band, and the ratio IG/ID=3.1 of the intensity at two peaks proves that further the degree of graphitization of product is higher.The transmission electron microscope photo of this graphitized carbon nano material as shown in Figure 3, as can be seen from the figure the microscopic appearance of product is the hollow cryptomere of size homogeneous, is of a size of about 40nm.The high resolution transmission electron microscopy photo of this graphitized carbon nano material can obviously be found out the warp architecture of cryptomere as shown in Figure 4 from figure, recording spacing is 0.34nm, is (002) spacing of graphite.
Embodiment 54: what present embodiment and embodiment 53 were different is: catalyzer is iron protochloride, ferrous sulfate or ferric sulfate in the step 2.Other step and parameter are identical with embodiment 53.
Embodiment 55: what present embodiment and embodiment 53 were different is: the carbon source in the step 1 is a cornstalk, and the catalyzer in the step 2 is the 0.015mol nickelous chloride, and thermal treatment temp is 800 ℃ in the step 4.Other step and parameter are identical with embodiment 53.
By the transmission electron microscope test, the result shows that product is the nanometer spirrillum graphite carbon of size homogeneous.
Embodiment 56: present embodiment is implemented 55 and different is with concrete: catalyzer is single nickel salt, nickelous acetate, cobaltous acetate in the step 2.Other step and parameter are identical with embodiment 55.
Embodiment 57: what present embodiment and embodiment 56 were different is: carbon source is a beet pulp in the step 1, and catalyzer is the 0.02mol cobalt chloride in the step 2, and the thermal treatment temp in the step 4 is 1100 ℃.Other step and parameter are identical with embodiment 55.
By the transmission electron microscope test, the result shows that product is the nano-sheet graphite carbon of size homogeneous.
Embodiment 58: what present embodiment and embodiment 53 were different is: carbon source is a bagasse in the step 1, and the catalyzer in the step 2 is the 0.015mol rose vitriol, and the thermal treatment temp in the step 4 is 900 ℃.Other step and parameter are identical with embodiment 55.
By the transmission electron microscope test, the result shows that product is the nanometer fibrous graphite carbon of size homogeneous.
Embodiment 59: what present embodiment and embodiment 53 were different is: carbon source is a wood chip in the step 1, and catalyzer is 0.02mol three oxalic acid and 0.02mol potassium ferrite, and heat treatment time is 4h.Other step and parameter are identical with embodiment 55.
By the transmission electron microscope test, the result shows that product is the nanotube-shaped graphite carbon of size homogeneous.
Embodiment 60: the preparation method of present embodiment graphitized carbon nano material is finished by following step: one, taking by weighing 10g starch, join the 200mL mass concentration and be 10% hydrochloric acid soln, is supersound process 3～6h under the 4KHz condition in frequency; Two, will add the 0.015mol Xiao Suangu in the 300mL water and, under 50 ℃, 150～160r/min stirring velocity, stir 8h through pretreated carbon source; Three, be under 200 ℃ of conditions in air atmosphere, pre-carbonization temperature, the step 2 product is carried out pre-carbonization 4h; Four, the heat-up rate with 10 ℃/min rises to 900 ℃ by room temperature, is that 60mL/min, thermal treatment temp are under 900 ℃ of conditions at nitrogen atmosphere, heat-treating atmosphere flow, and the step 3 product is heat-treated 3h; Five, being added to the 150mL mass concentration after the product of step 4 is ground is in 15% the nitric acid, and the 14h that refluxes under 110 ℃ of conditions is washed with distilled water to pH=6～8 of washing lotion, then oven dry under 110 ℃ of conditions or under 80 ℃ of conditions vacuum-drying 6h; Six, under steam atmosphere, and physically activated temperature is that 300 ℃, physical gas flow are under the 100mL/min condition, with the physically activated 4h of the product of step 5, obtaining graphitized carbon nano material behind the vacuum-drying 7h under 60 ℃ of conditions.
Again product is activated 4h under 300 ℃ of atmosphere, obtain the finished product.By the transmission electron microscope test, the result shows that product is the nano strip graphite carbon of size homogeneous.
Embodiment 61: what present embodiment and embodiment 60 were different is: catalyzer is nickelous nitrate, iron nitrate or Iron nitrate in the step 2.Other step and parameter are identical with embodiment 60.
Embodiment 62: what present embodiment and embodiment 60 were different is: carbon source is a glucose in the step 1, and catalyzer is the 0.025mol nickelous nitrate in the step 2, and the physically activated time is 6h in the step 6.Other step and parameter are identical with embodiment 60.
By the transmission electron microscope test, the result shows that product is the nanometer horn shape graphite carbon of size homogeneous.
Embodiment 63: what present embodiment and embodiment 60 were different is: carbon source is a fructose in the step 1, catalyzer is a 0.015mol ferric sulfate in the step 2, heat treatment time is 4h in the step 4, and the sulphuric acid soln of employing 25% carries out acid treatment in the step 5.Other step and parameter are identical with embodiment 60.
By the transmission electron microscope test, the result shows that product is the nano strip graphite carbon of size homogeneous.
Embodiment 64: what present embodiment and embodiment 60 were different is: carbon source is a sucrose in the step 1, and catalyzer is the 0.03mol Tripotassium iron hexacyanide in the step 2, and heat treatment time is 4h in the step 4.Other step and parameter are identical with embodiment 60.
By the transmission electron microscope test, the result shows that product is the nanometer cryptomere graphite carbon of size homogeneous.
Claims (5)
1. the preparation method of graphitized carbon nano material is characterized in that the preparation method of graphitized carbon nano material is finished by following step: one, carbon source is carried out pre-treatment 1～10h; Two, add catalyzer and through pretreated carbon source in solvent, stir 8h under 50 ℃, 100～300r/min stirring velocity condition, wherein the mass ratio of carbon source and catalyzer is 0.025～1: 1; Three, be mixture 2～8h that pre-carburising step two obtains under 80～450 ℃ of conditions in temperature, pre-carburizing atmosphere is the mixed gas of one or more gases in air, oxygen, nitrogen, argon gas, the helium; Four, the heat-up rate with 1～15 ℃/min rises to 400～1200 ℃ by room temperature, at heat-treating atmosphere, heat-treating atmosphere flow is that 30～2000mL/min, thermal treatment temp are under 400～1200 ℃ of conditions, product to step 3 is heat-treated 10min～10h, and wherein heat-treating atmosphere is the mixed gas of one or more gases in nitrogen, argon gas, helium, carbon monoxide, carbonic acid gas, hydrogen sulfide, hydrogen and the water vapour; Five, being added to mass concentration after the product of step 4 is ground is in 15%～20% the nitric acid or hydrochloric acid, 6～14h refluxes under 110～140 ℃ of conditions, be washed with distilled water to neutrality, drying under 110～120 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions then; Six, the product to step 5 carries out physically activated or chemical activation, obtains graphitized carbon nano material after the drying; Wherein, the carbon source of step 1 is farm-forestry crop extract or agriculture and forestry organic waste material; The farm-forestry crop extract is glucose, sucrose, fructose or starch; Agriculture and forestry organic waste material is cornstalk, sorghum stalk, beet pulp, bagasse or wood chip; Pretreated method described in the step 1 is microwave method, hydrothermal method, ultrasonic method, spray method, acidic treatment or alkaline purification method; Adopt microwave method pre-treatment carbon source to be undertaken: to be under the condition of 3.0～8.0kW at microwave intensity, to carbon source microwave treatment 10～60min by following reaction; Adopt hydrothermal method pre-treatment carbon source to be undertaken by following reaction: in temperature is under 120～180 ℃ of conditions, to carbon source hydrothermal treatment consists 4～8h; Adopt ultrasonic method pre-treatment carbon source to be undertaken by following reaction: in frequency is under 2～6KHz condition, to carbon source supersound process 0.5～2h; Adopt spray method pre-treatment carbon source to be undertaken: with carbon source and activator mix by following reaction, at 220V, the pre-treatment of spraying under 60～100Hz frequency, wherein activator is that mass concentration is 10%～20% hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide or potassium hydroxide; Adopt acidic treatment pre-treatment carbon source to be undertaken by following reaction: it is supersound process 3～6h in 10%～15% the hydrochloric acid soln that carbon source is joined mass concentration; Adopt alkaline purification method pre-treatment carbon source to be undertaken by following reaction: it is to stir 0.5～4h in 10%～20% the KOH solution that carbon source is added mass concentration, hydrothermal treatment consists 2～5h again, be washed with distilled water to pH=6～8 of washing lotion, under 80～100 ℃ of conditions, dry again; Catalyzer described in the step 2 is that iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close a kind of or wherein several mixing in potassium ferrite, cobalt chloride, Xiao Suangu, rose vitriol, cobaltous acetate, nickelous chloride, nickelous nitrate, single nickel salt, the nickelous acetate.
2. the preparation method of graphitized carbon nano material according to claim 1 is characterized in that the solvent described in the step 2 is a kind of or wherein several mixing in water, methyl alcohol, ethanol, the Virahol.
3. the preparation method of graphitized carbon nano material according to claim 1 and 2, it is characterized in that the physically activated method described in the step 6 is as follows: under water vapour, carbonic acid gas, hydrogen or carbon monoxide atmosphere, and physically activated temperature be 200～500 ℃, the gas flow in physically activated is under 100～4000mL/min condition, with the physically activated 0.5～24h of the product of step 5.
4. the preparation method of graphitized carbon nano material according to claim 1 and 2, the method that it is characterized in that the chemical activation described in the step 6 is as follows: in activation temperature is under 80～180 ℃ of conditions, the product of step 5 is activated 3～12h in inorganic solution, wherein the mass concentration of inorganic solution is 10～45%, and inorganic solution is the solution of potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid or potassium permanganate.
5. the preparation method of graphitized carbon nano material according to claim 1 and 2 is characterized in that the drying described in the step 6 is to dry under 110～120 ℃ of conditions or vacuum-drying 6～8h under 60～80 ℃ of conditions.
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