CN1294079C - Method for preparing nano graphite carbon powder from nano graphite carbon colloidal SOL - Google Patents

Method for preparing nano graphite carbon powder from nano graphite carbon colloidal SOL Download PDF

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CN1294079C
CN1294079C CNB031533612A CN03153361A CN1294079C CN 1294079 C CN1294079 C CN 1294079C CN B031533612 A CNB031533612 A CN B031533612A CN 03153361 A CN03153361 A CN 03153361A CN 1294079 C CN1294079 C CN 1294079C
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carbon
weight
colloidal sol
sulfonated lignin
nano
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CN1579933A (en
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刘键
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China (Tianjin) Co.,Ltd. nano science and technology
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Abstract

The present invention relates to a method for preparing nanometer graphite carbon powder from nanometer graphite carbon sol, which comprises: 0.05 to 0.15 wt% (preferably 0.05 to 0.1 wt%) of the total weight of the sol of lignosulphonate with the molecular weight of greater than 4000 (preferably 5000) daltons is added to the nanometer graphite carbon sol; the mixture is dried and milled to obtain the nanometer graphite carbon powder. The obtained nanometer graphite carbon powder can not produce agglomeration when stored in a dryer for a medium or long time.

Description

The method for preparing carbon powder from nano graphite by nano graphite carbon sol
Technical field
The present invention relates to preparation of nanomaterials, particularly relate to and utilize coating agent, prepare the method for carbon powder from nano graphite by nano graphite carbon sol.
Background technology
Nano material is meant that the bulk of the constituent of constituent material has at least one dimension to be in the material of nanoscale (0.1nm-100nm) scope, nano material is minimum because of its bulk, thereby specific surface area is big, the system surface energy is high and have the outstanding performance that many common size materials do not have, thereby be subjected to the extensive attention of scientific and technological circle, the preparation of nano material and utilisation technology become a fresh content of 21st century investigation of materials.
Studies show that when carbon is in the nanoscale scope, to have the property that many stock size carbon materials are not had in a large number.It is widely used in fields such as electric heating material, battery production, magnetic pipe recording material, agricultural, Aeronautics and Astronautics, and purposes is very extensive, is the bright spot in the nano materials research.But, because carbon is the element that is in the semi-metal state, when the nanometer state, has intensive and select adsorptivity, and have electronegativity, very easily reunite, make the manufacturing of nano-sized carbon very difficult.
The electrode that adopts carbon material is as anode, and this electrode is immersed in the water-based liquid medium, and the logical direct current of going up carries out electrolysis, just can produce the deposition of carbon colloid in this system.Thus, can prepare carbon colloid solution.This method is existing report in JP7008790.JP2000086220 discloses a kind of by the carbon dioxide process carbon electrode of electrolytic oxidation in water in ultrasound environments, obtains the method for ultra tiny carbon granule sol liquid.JP10006504 also provides a kind of electrode that is made of carbon material to be immersed in to be used for electrolytic water base liquid medium, to produce the method for the dispersion liquid of powder formed carbon.The document reports that the dispersion of the powder formed carbon that this method is produced has little granularity and homogeneous granules diameter.The carbon sol that adopts these methods to obtain can be used as the activator of battery, rust-preventive agent and the germination of promotion plant and the reagent of growth of water circulation system pipeline.But; in these known methods; carbon granule in the resulting ultra-fine carbon granule colloidal sol can be reunited again; and; though might obtain the nano-scale carbon particle that solation exists; but can't prepare ultra-fine carbon granule from ultra-fine carbon granule colloidal sol, its reason is if separate carbon granule by drying, and these particles can be reunited again again.
Xylogen is the timber main composition of (comprising bamboo, wheat straw, straw).Xylogen is not a kind of compound, but an individual system, and it forms different and different along with the difference of raw material and separation method.The relative molecular mass of separating lignin will generally be several thousand to several ten thousand far below the script xylogen.The height of relative molecular mass also depends on the separation method of xylogen.
As a kind of additive, lignin product is widely used in various chemical technologies and the composition.Xylogen is a kind of high-molecular weight polymer of complexity, is present in naturally in plant and the trees to combine with Mierocrystalline cellulose is close.In paper industry, xylogen can be used as two kinds of main wooden paste-making methods, and promptly the by product of the cellulose prods that obtains of sulphite process and sulphate process reclaims.In sulphite process, pass through Direct Sulfonation, be dissolved out in the Mierocrystalline cellulose part of xylogen from wood pulp, and sulphate process is based on the fracture that the degradation mechanism of alkali causes beta-aromatic ether connection in the polymeric xylogen, causes the chemical functional of phenol type and carboxyl type then.The sulphate process xylogen generally is to be lower than under the pKa of phenolic group at pH, by Acid precipitation xylogen is separated from the black liquor of pulping process.
Based on the precipitated condition of sulphate process xylogen, xylogen can be not acidiferous xylogen or lignin salt.If xylogen is sedimentary under high pH value, as about 9.5 to 10, xylogen just obtains with the form of salt.If this xylogen by further by washing, be acidified to low pH value, and then the processing of once washing reaches and is substantially free of salt and becomes grey component, then can obtain not acidiferous xylogen, is referred to as " A " xylogen.
Sulfonated lignin claim sulfonated lignin again, are the products of the wood pulp and the sulfur dichloride aqueous solution and sulphite reaction, are the by products of producing paper pulp.Be generally the polymer of 4-hydroxy 3-methoxybenzene.Since the kind difference of timber, the difference of sulfonation reaction, and the molecular weight of sulfonated lignin does not wait by 200 to 10000, also can reach about 30000.The chemical structure of sulfonated lignin is not determined as yet.In general, low molecule sulfonated lignin mostly are straight chain, associate together in solution; The high molecular sulfonated lignin mostly are side chain, demonstrate the behavior of polyelectrolye in water medium.Rough sulfonated lignin are used for the granulation of animal-feed in a large number, and refining sulfonated lignin are used for the dispersion agent of oil drilling slurry, mineral flotation agent; the dispersion agent of sludge, dyestuff, agricultural chemicals; to heavy metal, especially iron, copper, stannous ion have better sequestering power, are effective sequestrants.
But, still do not have sulfonated lignin to be applied to prepare the report of nano-scale particle at present.
Summary of the invention
The objective of the invention is to provide a kind of effect, by the method for preparing nano graphite carbon powder from nano graphite sol by coating agent.
The invention provides a kind of method for preparing carbon powder from nano graphite with nano graphite carbon sol, comprise in described nano graphite carbon sol adding and account for colloidal sol gross weight 0.05-0.15% (weight), molecular weight sulfonated lignin greater than 4000 dalton (4000 atomic mass unit), then, dry, grinding obtains carbon powder from nano graphite.
In a preferred embodiment, the nano graphite carbon sol of described colloidal sol for obtaining for anode electrolysis water with the carbon dioxide process carbon electrode, wherein, the content of carbon is 0.5-0.8% (weight) in the described colloidal sol.
When the molecular weight of described sulfonated lignin greater than 5000 dalton (5000 atomic mass unit), its add-on is that 0.05% (weight) of described colloidal sol gross weight is to 0.1% (weight) less than the colloidal sol gross weight; And when the molecular weight of described sulfonated lignin more than or equal to 6000 dalton (6000 atomic mass unit), its add-on is the 0.05-0.09% (weight) of described colloidal sol gross weight, is preferably the 0.07-0.08% (weight) of described colloidal sol gross weight.
Sulfonated lignin described in the present invention can make a choice in multiple sulfonated lignin, and what preferably use is sodium lignosulfonate.The sulfonated lignin that satisfy above-mentioned molecular weight requirement can be from the Polyfon of Westvaco TMAnd the Marasperse of Barregaard LignoTech Select in the series product.
The adding of described sulfonated lignin is earlier sulfonated lignin to be dissolved in the deionized water fully, and then joins in the described colloidal sol.Also can join again in the described colloidal sol with ethanol or acetone solution sulfonated lignin.
In described method, described drying is under 30-55 ℃, undertaken by spraying drying.
The carbon powder from nano graphite that adopts method of the present invention to obtain, its rate of recovery from solution is near 100%.
The present invention also provides a kind of carbon powder from nano graphite by method for preparing.
Below method of the present invention is elaborated:
According to the method for prior art, contain electrolytical water by the Graphite Electrodes electrolysis, can obtain the superfine graphite colloidal sol of graphite granule about 10nm.Generally speaking, when adopting the just very electrolyzer of graphite, at voltage is that 3-6V, electric current are when carrying out oxidization electrolysis under the direct current of 5-10A, through nearly 20 days or electrolysis for more time, in system, can access the carbon sol of collosol concentration about 0.5% (weight), wherein, the carbon granules in the resultant colloidal sol directly is a nano level.By improving electrolysis process, as the denomination of invention of submitting on the same day in the application according to the applicant is the method for " the pulsed electrode legal system is equipped with nano graphite carbon sol ", can obtain the carbon sol of 75% carbon granules footpath less than 10nm, wherein, by 15-20 days electrolysis, can access the sol solution that collosol concentration is 0.5-0.8% (weight).
With molecular weight greater than 4,000 dalton (4,000 atomic mass unit) sulfonated lignin, preferred molecular weight are greater than 5,000 dalton (5,000 atomic mass unit), more preferably molecular weight is more than or equal to 6,000 dalton (6,000 atomic mass unit) sulfonated lignin are preferably sodium lignosulfonate, are dissolved in the deionized water fully at normal temperatures.On demand, also can adopt ethanol or acetone to dissolve described sulfonated lignin.At normal temperatures, this lignosulfonic acid salts solution is accounted in the ratio adding nano graphite carbon sol that described colloidal sol gross weight is 0.05-0.15% (weight) in sulfonated lignin.Find that in actual applications the molecular weight of employed sulfonated lignin is big more, its parcel, dispersion effect are good more, and usage quantity is also few more.When the molecular weight of employed sulfonated lignin 5,000 dalton (5, when 000 atomic mass unit) above, its usage quantity is that described colloidal sol gross weight is 0.05 to less than 0.1% (weight), and when the molecular weight of employed sulfonated lignin during more than or equal to 6,000 dalton (6,000 atomic mass unit), its usage quantity is that described colloidal sol gross weight is 0.05 to 0.09% (weight), is preferably the 0.07-0.08% (weight) of described colloidal sol gross weight.
After having added sulfonated lignin, resulting carbon sol is sent into drying in the spray-drier, controlled temperature is below 55 ℃, generally at 30-55 ℃ when dry.
Detection shows, when most carbon granules footpath in the carbon sol as raw material when 15nm is following, the major part in the carbon dust that obtains by aforesaid method has the particle diameter of 15-50nm.
By method of the present invention, obtain nano level carbon dust the carbon sol that can obtain from the water electrolysis reaction that utilizes graphite anode, by continuing to optimize electrolysis process, as improve ionogen, electrolysis voltage and electric current in the electrolysis system, can obtain the nano carbon sol that different-grain diameter distributes, in conjunction with method of the present invention, just can access particle diameter even little graphite carbon dust to several nanometers.Such carbon powder from nano graphite long-term storage in moisture eliminator does not have agglomeration yet and takes place.
Describe the present invention by the following examples in detail, but be not to be used to limit the present invention.
Description of drawings
Fig. 1 and Fig. 2 are respectively the electron-microscope scanning figure of the carbon powder from nano graphite that obtains according to the inventive method.
Embodiment
Experimental example
Adopt 4 length and widths, (purity is greater than 99% for the thick high-purity graphite carbon that is respectively 200mm, 200mm and 50mm, carbon element factory, carbon element group Shanghai, Jilin) as anode, 4 length and widths, the thick stainless steel plate (commercially available) of 200mm, 200mm and 2mm that is respectively are as negative electrode, and these electrodes are immersed in the aqueous electrolyte liquid, contain the NaCl of 0.05% (weight) and 0.05% HNO in this aqueous electrolyte liquid 3(weight) adds between two electrodes and the direct current of 3V, 5A carries out electrolysis, just can produce the deposition of carbon colloid in this system.Electrolysis was carried out 25 days, obtained carbon sol concentration and be 0.5% graphite carbon sol, and the particle diameter that records graphite in the colloidal sol is a nano level.
Embodiment
Embodiment 1
Get 10 kilograms of the nano-graphite colloidal sols that above-mentioned experimental example obtains.
With molecular weight is that 6,000 dalton's (6,000 atomic mass unit) sodium lignosulfonate (available from BorregaardLignoTech) 9 gram is dissolved in the small amount of deionized water, adds at normal temperatures then in the above-mentioned nano-graphite colloidal sol, mixes.
The nano-graphite colloidal sol that has added sodium lignosulfonate is sent into spraying drying in the drying machine, control its temperature, obtain about 48 gram carbon powder from nano graphite below 55 ℃.
Embodiment 2
Get 10 kilograms of the nano-graphite colloidal sols that above-mentioned experimental example obtains.
With molecular weight is that 10,000 dalton's (10,000 atomic mass unit) sodium lignosulfonate (available from BorregaardLignoTech) 7 gram is dissolved in the small amount of deionized water, under agitation adds then in the above-mentioned nano-graphite colloidal sol.
The nano-graphite colloidal sol that has added sodium lignosulfonate is sent into spraying drying in the drying machine, control its temperature, obtain about 50 gram carbon powder from nano graphite below 55 ℃.
Test case
The carbon powder from nano graphite sample that embodiment 1 and 2 is obtained is dispersed in the water respectively, and drip on slide glass after ultrasonic 10 minutes, ion sputtering platinum after the seasoning, in the pattern and the granular size of JSM-6700F field emission scanning electron microscope observation sample, measurement result is as follows:
Most of pattern after two kinds of sample dispersion is a particulate state, and most of particle diameter is 15-20nm, and the part particle is 100-200nm.The scintigram of embodiment 1 and 2 sample respectively as depicted in figs. 1 and 2.
Respectively the carbon powder from nano graphite sample of embodiment 1 and 2 preparations was preserved in the moisture eliminator midium or long term, test shows does not have agglomeration to take place between the nano-graphite carbon granule.
Embodiments of the present invention are not limited to above-mentioned explanation, also should be considered as protection scope of the present invention not deviating from the improvement carried out on the basis that the invention is intended to and change.

Claims (8)

1. method for preparing carbon powder from nano graphite comprises adding in nano carbon sol accounting for colloidal sol gross weight 0.05-0.15 weight %, the molecular weight sulfonated lignin greater than 4000 atomic mass units, and is then, dry, grind and obtain nano-carbon powder.
2. the nano graphite carbon sol of the method for claim 1, wherein described colloidal sol for obtaining for anode electrolysis water with the Graphite Electrodes, wherein, the content of carbon is 0.5-0.8 weight % in the described colloidal sol.
3. the method for claim 1, wherein the molecular weight of described sulfonated lignin is greater than 5,000 atomic mass units, and its add-on is that 0.05 weight % of described colloidal sol gross weight arrives 0.1 weight % less than the colloidal sol gross weight.
4. the method for claim 1, wherein the molecular weight of described sulfonated lignin is more than or equal to 6,000 atomic mass units, and its add-on is the 0.05-0.09 weight % of described colloidal sol gross weight.
5. method as claimed in claim 4, wherein, the add-on of described sulfonated lignin is the 0.07-0.08 weight % of described colloidal sol gross weight.
6. the method for claim 1, wherein described sulfonated lignin are sodium lignosulfonate.
7. the method for claim 1, wherein the adding of described sulfonated lignin is earlier sulfonated lignin to be dissolved in the deionized water fully, and then joins in the described colloidal sol.
8. the method for claim 1, wherein described drying is under 30-55 ℃, undertaken by spraying drying.
CNB031533612A 2003-08-12 2003-08-12 Method for preparing nano graphite carbon powder from nano graphite carbon colloidal SOL Expired - Fee Related CN1294079C (en)

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CN101173107B (en) * 2007-10-23 2011-03-16 福州大学 Xylogen-inorganic nano composite material and producing process thereof
CN103395777B (en) * 2013-08-07 2014-07-30 大同市普朔科技有限责任公司 Preparation method of nano-graphite carbon powder
CN103482599B (en) * 2013-09-04 2015-10-21 贵州特力达纳米碳素科技有限公司 A kind of nano carbon sol and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078753C (en) * 1995-09-29 2002-01-30 藤田贤一 Electrolyte and lead accumulator using the same
CN1378976A (en) * 2002-05-17 2002-11-13 贵州航天纳米科技有限责任公司 Process for preparing nano graphite carbon powder from nano graphite sol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078753C (en) * 1995-09-29 2002-01-30 藤田贤一 Electrolyte and lead accumulator using the same
CN1378976A (en) * 2002-05-17 2002-11-13 贵州航天纳米科技有限责任公司 Process for preparing nano graphite carbon powder from nano graphite sol

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