CN104340969A - High-stability graphite cleaning purification method - Google Patents
High-stability graphite cleaning purification method Download PDFInfo
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- CN104340969A CN104340969A CN201310318036.XA CN201310318036A CN104340969A CN 104340969 A CN104340969 A CN 104340969A CN 201310318036 A CN201310318036 A CN 201310318036A CN 104340969 A CN104340969 A CN 104340969A
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Abstract
The present invention provides a high-stability graphite cleaning purification method, wherein impurities in the graphite can be effectively removed through the method, the graphite with the carbon content of more than 65% is adopted as a raw material, and the purity of the purified graphite is more than 99.99%. According to the method, pressurization alkali leaching and normal pressure acid leaching are adopted to treat the graphite, the normal pressure acid leaching is performed under the ultrasonic wave field or/and the microwave field, 21-24% (calculated as the weight of the graphite) by weight of sulfuric acid and 13-28% (calculated as the weight of the graphite) by weight of hydrofluoric acid are added to the treated graphite powder to carry out leaching to obtain the high purity graphite product, the graphite oxide suspension is prepared under ultrasound, a dodecylamine chloroform solution is added, room temperature stirring is performed, and pressure reducing filtration, washing and drying are performed to obtain the stable graphite, wherein the high concentration alkali solution after the purification is recovered and then is recycled at the later stage, the high concentration waste acid is recovered, and the aluminum content in the waste acid is adjusted so as to be used for the synthesis of the polymeric aluminum PAC. The high-stability graphite cleaning purification method is the graphite purification method with characteristics of simple process, energy saving, emission reducing, safety, environmental protection, economy and high efficiency.
Description
Technical field
The present invention relates to a kind of method that high stability graphite cleans purification, purification purity is greater than the method for the high purity graphite of 99.99%, and improves the stability of graphite.
Background technology
High purity graphite is the graphite of content of graphite more than 99.99%, and it is a kind of non-renewable strategic resource, is important war preparedness resource indispensable in military project and modern crafts and hi-tech development always.
The production method of current high purity graphite is mainly based on the wet-process purification method of flotation process, acid-base method, hydrogen fluoride with based on the pyrogenic process method of purification of chlorinating roasting and pyroprocess.There is the deficiencies such as impurity-eliminating effect difference, energy consumption is high, environmental pollution is serious more or less in this several production method.
In addition, interpolation tensio-active agent and organic functional are the important method of modified graphite stability.Wherein, organic functional still occupies dominant position, comprises silanization, nucleophilic substitution and phase transfer of technology etc.Can hydrogen bond between disruptive oxidation graphite linings by the method for these modifications, make modified graphene oxide can have good dispersion in organic solvent.In the above-mentioned methods, temperature of reaction all higher (70 DEG C and 140 DEG C etc.), and synthesis step complex operation, be difficult to industrialization scale operation.Because the waste water of discharging in technological process, Solid state fermentation difficulty are large, to the murder by poisoning of biology and environmental pollution very serious, use hydrogen fluoride explained hereafter high purity graphite disaster infinite, this method is in fact disabled.
Summary of the invention
The invention provides a kind of method that high stability graphite cleans purification, effectively can remove the impurity in graphite, make the content of the fixed carbon of graphite reach 99.99%, reach the method for high purity graphite requirement.For the drawback that existing graphite purification technology exists, provide that a kind of technique is simple, energy-saving and emission-reduction, safety and environmental protection, economical and efficient graphite purification method.The better performances of product, its technique is simple, advanced, easy handling, and production efficiency is high, facility investment is few, energy consumption is low, and smaller on the impact of environment, cost is low, and graphite products purity is high, can meet the requirement of high purity graphite.In addition, the present invention is directed to the deficiencies such as high, the complex operation of temperature of reaction that prior art exists, a kind of method strengthening graphite stable is provided.
Solving the technical scheme that technical problem of the present invention adopts is: the graphite 500-600kg 1, getting carbon content > 65%, puts into reactor I, first adopts alkaline pressure of oxygen leaching and normal pressure acidleach to process graphite, LiCO used
3concentration is 10% ~ 35%, KOH concentration is 6% ~ 30%, NaHCO
3concentration is 7% ~ 28%; Wherein normal pressure acidleach is at ultrasonic wave field or/and carry out under microwave field, and the Graphite Powder 99 after process adds sulfuric acid 21%-24% by the weight percent of graphite again, hydrofluoric acid 13%-28% leaches, and obtains highly purified graphite products.High-concentration alkali liquor, reclaims later cycles and utilizes; High density spent acid, reclaims through adjusting wherein after aluminium content, for the synthesis of polymeric aluminum PAC.
2. the weight liquid-solid ratio of alkaline pressure of oxygen leaching is 1 ~ 9: 1, and temperature is 150 ~ 280 DEG C, and the treatment time is 1 ~ 11 hour; Adopt lime as reagent reclaiming alkali lye.
3. normal pressure acidleach is at ultrasonic wave field or/and carry out under microwave field, and the Graphite Powder 99 after process adds sulfuric acid 21%-24% by the weight percent of graphite again, hydrofluoric acid 13%-28% leaches, and obtains highly purified graphite products.The weight liquid-solid ratio of normal pressure acidleach is 1 ~ 9:1, and temperature is 35 ~ 85 DEG C, and the treatment time is 2h ~ 90h.
4. ultrasonic frequency range during normal pressure acidleach is at 20 ~ 70KHz, and microwave field range of frequency is at 280GHz ~ 5GHz.
5, prepare graphite oxide suspension under ultrasonic, the mass ratio of dodecyl amine molecule and graphite oxide is (10-20): 3, prepares amino dodecane chloroformic solution, adds in graphite suspension, stirring at room temperature 2 ~ 4 days; Namely graphene-based supramolecule hybrid material is obtained after filtration under diminished pressure, washing, drying.
The high-concentration alkali liquor of 6, described silicate impurity, way of recycling is as follows: after adding CaO reaction, isolate CaSiO3 sediment, and to reach mass concentration be 26%-30% to remaining caustic soda soln by concentrated, and later cycles utilizes; The high density spent acid of described metal ion, way of recycling is as follows: sent into distillation tower, by distillation obtain concentration of hydrochloric acid >=25% containing aluminium spent acid, through adjusting wherein after aluminium content, for the synthesis of polymeric aluminum PAC.
Above-mentioned alkaline pressure of oxygen leaching: the graphite after ore dressing drops in compressive reaction still, adds alkaline solution, controls reaction conditions, the impurity in graphite and alkali lye are reacted.After reaction terminates, realize solid-liquid separation.Solid adopts pure water to pH=7, and liquid adopts lime to carry out above-mentioned normal pressure acidleach: washing mixes to neutral graphite with the acid solution of above-mentioned condition sizes mixing, and controls reaction conditions, the impurity in graphite is reacted with acid further.Reaction process is carried out in ultrasonic wave field or microwave field.The acid waste water produced in washing process and alkaline waste water neutralize mutually, and add the F-in lime precipitation solution.Water after neutralization returns to system and washs.Whole technological process is free from environmental pollution.
The invention has the beneficial effects as follows: graphite obtains high purity graphite after alkaline pressure of oxygen leaching, acidleach process, and adds ultrasonic wave field or microwave field in acidleach process.Technical process is short, easily realizes suitability for industrialized production, and equipment is simple, and security is good, and energy consumption is low, and production cost is low, and environmental pollution is little; In the high purity graphite obtained, the content of fixed carbon is greater than 99.99%.The graphite thermal stability of synthesis improves a lot; Add synthesis step simple, efficient, can prepare in a large number, so have good application prospect and economic benefit.Have employed " causticization process ", the waste residue of generation is Calucium Silicate powder, is useful building materials raw material, is also the batching of brickmaking and cement; To acidified waste water process, make the spent acid Recycling of recovery; By spent acid residual remittance production polymeric aluminum, residual mixing is fully utilized.Be that a kind of technique is simple, energy-saving and emission-reduction, safety and environmental protection, economical and efficient graphite purification method.
Embodiment
Below by embodiment, the present invention is described in further detail.
Embodiment one
Get the graphite 500kg of carbon content > 65%, put into reactor I, first adopt alkaline pressure of oxygen leaching and normal pressure acidleach to process graphite, LiCO used
3concentration is 10%, KOH concentration is 6%, NaHCO
3concentration is 7%; The weight liquid-solid ratio controlling reaction alkaline pressure of oxygen leaching is 1 ~ 9: 1, and temperature is 150 DEG C, and the treatment time is 1 hour; Adopt lime as reagent reclaiming alkali lye.Reacted material realizes solid-liquid separation, and with pure water cleaning to pH=7.Wherein normal pressure acidleach carries out after the match at ultrasonic wave field; Graphite Powder 99 after process adds sulfuric acid 21%-24% by the weight percent of graphite again, hydrofluoric acid 13%-28% leaches, and the weight liquid-solid ratio controlling normal pressure acidleach is 1 ~ 9:1, and temperature is 35, and the treatment time is 2h.Ultrasonic frequency range during normal pressure acidleach, at 20KHz, obtains highly purified graphite products.Prepare graphite oxide suspension under ultrasonic, the mass ratio of dodecyl amine molecule and graphite oxide is 10: 3, prepares amino dodecane chloroformic solution, adds in graphite suspension, stirring at room temperature 2 days; Namely graphene-based supramolecule hybrid material is obtained after filtration under diminished pressure, washing, drying.The processing mode of above-mentioned waste lye is: after the CaO that waste lye adds 170kg fully reacts, and generate CaSiO3 sediment, the liquid separated is low concentration liquid caustic soda, can later cycles use through concentrated to reach after the concentration of 26%; The processing mode of above-mentioned waste lye is: spent acid solution distills, obtain concentration of hydrochloric acid 30% containing aluminium spent acid, by the content 20% of aluminium (Al) in the production technique adjustment spent acid of polymeric aluminum, return the synthesis for polymeric aluminum PAC after acidifying.
Embodiment two
Get the graphite 600kg of carbon content > 65%, put into reactor I, first adopt alkaline pressure of oxygen leaching and normal pressure acidleach to process graphite, LiCO used
3concentration is 35%, KOH concentration is 30%, NaHCO
3concentration is 28%; The weight liquid-solid ratio controlling alkaline pressure of oxygen leaching is 1 ~ 9: 1, and temperature is 280 DEG C, and the treatment time is 11 hours; Adopt lime as reagent reclaiming alkali lye.Wherein normal pressure acidleach carries out under microwave field, and the Graphite Powder 99 after process adds sulfuric acid 24% by the weight percent of graphite again, hydrofluoric acid 28% leaches, and the weight liquid-solid ratio controlling normal pressure acidleach is 1 ~ 9:1, and temperature is 85 DEG C, and the treatment time is 90h.Obtain highly purified graphite products.Microwave field range of frequency during control normal pressure acidleach is at 280GHz.Prepare graphite oxide suspension under ultrasonic, the mass ratio of dodecyl amine molecule and graphite oxide is 20: 3, prepares amino dodecane chloroformic solution, adds in graphite suspension, stirring at room temperature 4 days; Namely graphene-based supramolecule hybrid material is obtained after filtration under diminished pressure, washing, drying.The processing mode of above-mentioned waste lye is: after the CaO that waste lye adds 170kg fully reacts, and generate CaSiO3 sediment, the liquid separated is low concentration liquid caustic soda, can later cycles use through concentrated to reach after the concentration of 26%; The processing mode of above-mentioned waste lye is: spent acid solution distills, obtain concentration of hydrochloric acid 30% containing aluminium spent acid, by the content 20% of aluminium (Al) in the production technique adjustment spent acid of polymeric aluminum, return the synthesis for polymeric aluminum PAC after acidifying.
Claims (6)
1. a high stability graphite cleans the method for purification, it is characterized in that: the graphite adopting carbon content > 65% is raw material, increase its stability, purity > 99.99% after purifying, later stage waste water, Solid state fermentation, energy-saving and emission-reduction, safety and environmental protection, economical and efficient, step is as follows: the graphite 500-600kg getting carbon content > 65%, put into reactor I, alkaline pressure of oxygen leaching and normal pressure acidleach is first adopted to process graphite, LiCO used
3concentration is 10% ~ 35%, KOH concentration is 6% ~ 30%, NaHCO
3concentration is 7% ~ 28%; Wherein normal pressure acidleach is at ultrasonic wave field or/and carry out under microwave field, Graphite Powder 99 after process adds sulfuric acid 21%-24% by the weight percent of graphite again, hydrofluoric acid 13%-28% leaches, obtain highly purified graphite products, graphite oxide suspension is prepared under ultrasonic, add amino dodecane chloroformic solution, stirring at room temperature; Namely obtain stability graphite after filtration under diminished pressure, washing, drying, high-concentration alkali liquor, reclaim later cycles and utilize; High density spent acid, reclaims through adjusting wherein after aluminium content, for the synthesis of polymeric aluminum PAC.
2. clean the method for purification according to the high stability graphite described in claim 1, it is characterized in that the weight liquid-solid ratio of alkaline pressure of oxygen leaching is 1 ~ 9: 1, temperature is 150 ~ 280 DEG C, and the treatment time is 1 ~ 11 hour; Adopt lime as reagent reclaiming alkali lye.
3. clean the method for purification according to the high stability graphite described in claim 1, it is characterized in that wherein normal pressure acidleach is at ultrasonic wave field or/and carry out under microwave field; Graphite Powder 99 after process adds sulfuric acid 21%-24% by the weight percent of graphite again, hydrofluoric acid 13%-28% leaches, and obtains highly purified graphite products,
The weight liquid-solid ratio of normal pressure acidleach is 1 ~ 9:1, and temperature is 35 ~ 85 DEG C, and the treatment time is 2h ~ 90h.
4. clean the method for purification according to the high stability graphite described in claim 1, ultrasonic frequency range when it is characterized in that normal pressure acidleach is at 20 ~ 70KHz, and microwave field range of frequency is at 280GHz ~ 5GHz.
5. the method for purification is cleaned according to the high stability graphite described in claim 1, it is characterized in that ultrasonic under prepare graphite oxide suspension, the mass ratio of dodecyl amine molecule and graphite oxide is (10-20): 3, prepare amino dodecane chloroformic solution, add in graphite suspension, stirring at room temperature 2 ~ 4 days; Namely graphene-based supramolecule hybrid material is obtained after filtration under diminished pressure, washing, drying.
6. the method for purification is cleaned according to the high stability graphite described in claim 1, it is characterized in that the high-concentration alkali liquor of described silicate impurity, way of recycling is as follows: after adding CaO reaction, isolate CaSiO3 sediment, to reach mass concentration be 26%-30% to remaining caustic soda soln by concentrated, and later cycles utilizes; The high density spent acid of described metal ion, way of recycling is as follows: sent into distillation tower, by distillation obtain concentration of hydrochloric acid >=25% containing aluminium spent acid, through adjusting wherein after aluminium content, for the synthesis of polymeric aluminum PAC.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN108203092A (en) * | 2018-02-06 | 2018-06-26 | 青岛晶莹石墨有限公司 | Graphite powder impurity removal process and sewage treatment process |
| CN112093798A (en) * | 2020-10-29 | 2020-12-18 | 哈尔滨理工大学 | Outfield-assisted graphite rapid purification method |
-
2013
- 2013-07-26 CN CN201310318036.XA patent/CN104340969A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN108203092A (en) * | 2018-02-06 | 2018-06-26 | 青岛晶莹石墨有限公司 | Graphite powder impurity removal process and sewage treatment process |
| CN112093798A (en) * | 2020-10-29 | 2020-12-18 | 哈尔滨理工大学 | Outfield-assisted graphite rapid purification method |
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Application publication date: 20150211 |