CN104340970A - Method for removal of impurities SiO2 and Al2O3 and high-stability purification of graphite - Google Patents
Method for removal of impurities SiO2 and Al2O3 and high-stability purification of graphite Download PDFInfo
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- CN104340970A CN104340970A CN201310318056.7A CN201310318056A CN104340970A CN 104340970 A CN104340970 A CN 104340970A CN 201310318056 A CN201310318056 A CN 201310318056A CN 104340970 A CN104340970 A CN 104340970A
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Abstract
The present invention provides a method for removal of impurities SiO2 and Al2O3 and high-stability purification of graphite, wherein impurities in the graphite can be effectively removed through the method, the graphite is adopted as a raw material, the residual SiO2 content in the purified graphite is less than or equal to 30 MG/L, the residual Al2O3 content in the purified graphite is less than or equal to 0.3%, and the purity is more than 99.99%. According to the method, graphite with the carbon content of more than 65% is taken and placed into a reaction kettle I, 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, the obtained mixture is added to a reaction kettle, stirring heating is performed, cerium carbonate is added, an oxidizing agent is added slowly, stirring, heating boiling, standing clarification and filtration are performed to obtain the high purity graphite with no silicon and aluminum impurities, 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.
Description
Technical field
The present invention relates to a kind of removal of impurity SiO
2and Al
2o
3the method of high stability purification graphite, 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.Impurity SiO in graphite
2and Al
2o
3be modal, how thoroughly remove, can reduce costs again, alleviating environmental pollution is current problem demanding prompt solution.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.
Summary of the invention
The invention provides a kind of removal of impurity SiO
2and Al
2o
3the method of high stability purification graphite, effectively can remove the impurity in graphite, makes the content of the fixed carbon of graphite reach 99.99%, reaches the method for high purity graphite requirement.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: 1. the graphite adopting carbon content > 65% is raw material, after purifying, make SIO
2residual quantity≤28MG/L, AL
2o
3residual quantity≤0.2%, purity > 99.99%, step is as follows: the graphite 500-600kg getting carbon content > 65%, puts 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, join in reactor, stirring heating adds cerous carbonate, is slowly added by oxygenant, stirs, heated and boiled, leave standstill clarification, filter, highly purified graphite can be obtained.
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. 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. ultrasonic frequency range during normal pressure acidleach is at 20 ~ 70KHz, and microwave field range of frequency is at 280GHz ~ 5GHz.
5, graphite is joined in reactor, be heated with stirring to 75-85 DEG C, cerous carbonate is added in the 2-4% ratio of feed liquid TREO amount, by the amount of the 1-1.5% of TREO, oxygenant is slowly added afterwards, stir, heated and boiled more than 35 minutes, leave standstill clarification more than 10 hours, extract the feed liquid of supernatant liquor and band slag respectively, filter.
6, 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.
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%.By further purification, can obtain without silicon, the highly purified graphite of aluminium impurity.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.
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.Graphite is joined in reactor, is heated with stirring to 75 DEG C, add cerous carbonate in 2% ratio of feed liquid TREO amount, afterwards by TREO 1% amount oxygenant is slowly added, stir, heated and boiled 40 minutes, leave standstill clarification 11 hours, extract the feed liquid of supernatant liquor and band slag respectively, filter.
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.Graphite is joined in reactor, is heated with stirring to 85 DEG C, add cerous carbonate in 4% ratio of feed liquid TREO amount, afterwards by TREO 1.5% amount oxygenant is slowly added, stir, heated and boiled 55 minutes, leave standstill clarification 15 hours, extract the feed liquid of supernatant liquor and band slag respectively, filter.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.
Claims (6)
1. a removal of impurity SiO
2and Al
2o
3the method of high stability purification graphite, is characterized in that: the graphite adopting carbon content > 65% is raw material, increases its stability, after purifying, make SIO
2residual quantity≤28MG/L, AL
2o
3residual quantity≤0.2%, purity > 99.99%, step is as follows: the graphite 500-600kg getting carbon content > 65%, puts 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, 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 joins in reactor, stirring heating adds cerous carbonate, oxygenant is slowly added, stirs, heated and boiled, leave standstill clarification, filter, highly purified graphite can be obtained, under ultrasonic, prepare graphite oxide suspension, add amino dodecane chloroformic solution, stirring at room temperature; Namely stability graphite is obtained after filtration under diminished pressure, washing, drying.
2. according to the removal of impurity SiO described in claim 1
2and Al
2o
3the method of high stability purification graphite, 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. according to the removal of impurity SiO described in claim 1
2and Al
2o
3the method of high stability purification graphite, 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. according to the removal of impurity SiO described in claim 1
2and Al
2o
3the method of high stability purification graphite, 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. according to the removal of impurity SiO described in claim 1
2and Al
2o
3the method of high stability purification graphite, graphite is it is characterized in that to join in reactor, be heated with stirring to 75-85 DEG C, add cerous carbonate in the 2-4% ratio of feed liquid TREO amount, by the amount of the 1-1.5% of TREO, oxygenant is slowly added afterwards, stir, heated and boiled more than 35 minutes, leave standstill clarification more than 10 hours, extract the feed liquid of supernatant liquor and band slag respectively, filter.
6. according to the removal of impurity SiO described in claim 1
2and Al
2o
3the method of high stability purification graphite, 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, prepares 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.
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|---|---|---|---|
| CN201310318056.7A CN104340970A (en) | 2013-07-26 | 2013-07-26 | Method for removal of impurities SiO2 and Al2O3 and high-stability purification of graphite |
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|---|---|---|---|
| CN201310318056.7A CN104340970A (en) | 2013-07-26 | 2013-07-26 | Method for removal of impurities SiO2 and Al2O3 and high-stability purification of graphite |
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| CN104340970A true CN104340970A (en) | 2015-02-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2013-07-26 CN CN201310318056.7A patent/CN104340970A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |