CN101367517B - Method for preparing high pure graphite with steam heating - Google Patents
Method for preparing high pure graphite with steam heating Download PDFInfo
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- CN101367517B CN101367517B CN2008101572801A CN200810157280A CN101367517B CN 101367517 B CN101367517 B CN 101367517B CN 2008101572801 A CN2008101572801 A CN 2008101572801A CN 200810157280 A CN200810157280 A CN 200810157280A CN 101367517 B CN101367517 B CN 101367517B
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Abstract
The invention relates to a graphite purifying craftwork, in particular relates to a method for purifying the natural graphite with the heating of the vapor, which overcomes the weaknesses of the prior graphite purifying method that the craftwork is complicated, the energy consumption is large, the adopted devices are complicated, and the production cost is high, so that a method adopting the heating of the vapor to purify the graphite is provided. Through the heating of the vapor, the acid solution is reacted with the foreign matters in the graphite, and the foreign matters in the graphite are removed through the procedures such as washing, mixing, spin-dry, drying and the like. The method has low production cost, short flowing procedures, simple device and convenient operation; the content of the fixed carbon in the graphite that is purified can reach 99.99 percent to 99.995 percent.
Description
Technical field
The present invention relates to a kind of graphite purfying process, especially a kind of method of utilizing steam heating purification natural graphite.
Background technology
Graphite is as a kind of industrial raw material, in some special industries or high-tech technical field, critical role is arranged, as industry such as nuclear industry, automotive industry, spationautics, biotechnologys, the graphite that these industries are used must be that carbon content is at the high purity graphite more than 99.9%, can only reach 96% and the carbon content of the natural graphite after the general ore dressing is the highest, can't satisfy the requirement of using the high purity graphite industry far away, must purify to natural graphite for this reason.
The method of purification that natural graphite is commonly used is to improve graphite purity with the high-temperature electric heat method at present, the high-temperature electric heat method is to utilize the resistance to elevated temperatures of graphite, be placed in the high-temperature electric resistance furnace, secluding air is heated to more than 2500 ℃, make the ash volatilization in the graphite, thereby make the high purity graphite of fixed carbon more than 99.9%.Because its complex process needs to build large-scale electric furnace, power consumption is also quite big, and needs constantly to feed rare gas element, thereby with high costs.The more important thing is that when utilizing this method purification graphite, fixed carbon content is the highest can only reach 99.93% for it, and can't make fixed carbon content continue to improve.
Summary of the invention
The objective of the invention is to overcome that existing graphite method of purification complex process, power consumption are big, the equipment complexity of needs, thereby the defective that production cost is high, a kind of method of preparing high pure graphite with steam heating has been proposed, this method does not need to use electrically heated, and it is little to consume energy, and production cost is low, flow process is short, equipment is simple, and is easy to operate, and fixed carbon content can reach 99.9%-99.995%.
The present invention adopts following technical scheme to realize, a kind of method for preparing high pure graphite with steam heating, and this method may further comprise the steps:
(1) natural graphite with carbon content 90%-99% is a raw material, it is added in the PP retort, in retort, add simultaneously hydrofluoric acid, hydrochloric acid, nitric acid, sulphuric acid soln and water, graphite raw material, acid solution and water are prepared burden in proportion, and stirred 15-20 minutes, material is stirred into scattered paste shape;
(2) feed steam in the PP material retort, heating and sealing, the scattered paste shape material was reacted 12-24 hours under 60 ℃-100 ℃ condition, in reaction process, stirred once every 30 minutes, the each stirring 5-10 minutes adopted steam heating that the material in the retort is heated evenly, thereby made impurity and acid liquid reaction in the graphite more thorough;
(3) reaction finishes to add oxygenant in preceding 2-4 hours in PP material retort, and continues heated and stirred, and impurity and acid solution in the graphite raw material are fully reacted;
(4) abundant reacted material is put into PP material washing tank circulation cleaning, reached 6-7 until its pH value;
(5) pour in the circulation stirred pot through the material of washing, add pure water and stirring, constantly add pure water in the whipping process, in the circulation stirred pot, stirred 5-10 minutes, stir by circulation, reacted material is washed more completely, to increase the purity of graphite;
(6) through in the material suction automatic centrifuge that stirs, dry automatically, and automatic discharging;
(7) material after will dewatering is packed into and is dried in the steam heating drying machine, dry to moisture content less than 0.1%.
Described natural graphite, hydrofluoric acid, hydrochloric acid, nitric acid, sulphuric acid soln and water need batching in proportion, its weight ratio is 15:4-5:3-5:1-1.6:1.5-3:3-6, wherein the concentration of hydrofluoric acid solution is 40%, the concentration of hydrochloric acid soln is 30%, the concentration of salpeter solution is 40%, and the concentration of sulphuric acid soln is 98%.Described oxygenant is a fluoram, and the weight ratio of itself and the ratio material be made up of graphite, hydrofluoric acid, hydrochloric acid, sulphuric acid soln and water is between 1:6.5-1:14.5.
Reacted material washs by the mode that pure water at the uniform velocity permeates in the material washing tank in PP material retort, be about to add pure water after reacted material is poured the material washing tank into, make pure water pass through at the uniform velocity to permeate and mixing of materials, thereby degree of depth washing, this washing methods washing quality height, simple to operate and safe and power saving.By behind the above-mentioned circulation cleaning repeatedly, the acid solution that the washing back produces is recovered to the acid solution pond for recovering by pipeline, the recovery of purifying then.Material after the washing is then poured circulation stirring in the circulation stirred pot into.
Material after the oven dry is by ultrasonic vibration sieve screening removal of impurities, packing warehouse-in at last.
The invention has the beneficial effects as follows: at first, this method of purification adopts steam heating, replaced adopting in the electrothermal reaction still of prior art electrically heated, thermal oil to transmit the type of heating of heat, equipment cost and current consumption have been reduced, energy-saving consumption-reducing, it is more even that material in the retort is heated, thereby make graphite and acid liquid reaction thorough, improved the output of high purity graphite; Secondly, the washing methods that adopts pure water at the uniform velocity to permeate during reacted material washing has replaced the whizzer that adopts in the existing washing methods, and is safe and power saving, can not form barrier in jar simultaneously, improved washing quality; In addition, the agitating procedure after the washing can wash more up hill and dale to reacted material, so that improve the purity of graphite; At last, adopt the ultrasonic vibration sieve that the impurity in the material is sieved completely, thereby guaranteed the high purity of graphite.In a word, it is short to prepare the high purity graphite flow process by the present invention, and equipment is simple, and is easy to operate, and cost is low, and fixedly carbon content can reach 99.9%-99.995%.
Embodiment
Embodiment 1
In the PP retort, add natural graphite 1500kg, its carbon content is 90%, in the PP retort, add simultaneously concentration and be 40% hydrofluoric acid 400kg, concentration and be 30% hydrochloric acid soln 300kg, concentration and be 98% sulphuric acid soln 150kg and concentration and be 40% salpeter solution 100kg, adding an amount of about 400kg of water stirs the ratio material in the PP retort, stirred about 15 minutes, the ratio material in the retort is stirred.In the PP retort, feed steam and sealing then.Retort reacted 24 hours the ratio material by steam heating under 60 ℃ of conditions, stirred once every 30 minutes in the reaction process, stirred 5-10 minutes at every turn.When graphite and acid liquid reaction are about 22 hours, in the material that is reacting, add oxygenant fluoram 200kg, and continue to stir, so that graphite and acid liquid reaction are more thorough.After reaction finishes, to put into PP material washing tank through the material of fully reaction, by the method that pure water at the uniform velocity permeates material is carried out circulation cleaning, after soon material will be put into washing tank, feed pure water again, reach the degree of depth and wash thereby pure water is mixed with acid solution in the material by infiltration at the uniform velocity, reach 6-7 until the pH value of material.The acid solution that in the washing process washing is produced reclaims, and after washing finishes, material poured into adds pure water in the circulation stirred pot and stirs, constantly add pure water in the process that stirs, material is washed more completely,, do not contain Ca in the above-mentioned pure water to guarantee the purity of material
2+, Mg
2+, Cl
-Deng foreign ion.After in stirred pot, stirring 5-10 minutes, in material suction automatic centrifuge, material is dried automatically, dry back discharging automatically.Material after the drying is packed into and is dried in the steam heating drying machine, oven dry to its moisture content less than 0.1%.After the screening of ultrasonic vibration sieve, thoroughly removal of impurities, packing warehouse-in.After the aforesaid method purification, the fixed carbon content of graphite is 99.9%.
The effect of acid solution be at a certain temperature with graphite in impurity react and generate water-soluble material, and make its reaction more thorough by the oxygenant fluoram.Fully the reaction back is by washing and stirring, remove the impurity in the graphite, thereby the high purity of obtaining, the high purity graphite of low trace element, all toolings of this invention and flow process control all can not introduced any impurity, if contain micro-metals or other trace elements, itself bring into owing to the natural graphite raw material fully, so can make graphite fixed carbon content reach 99.9%-99.995% by method of the present invention, satisfy the application requiring of high-grade, precision and advanced industries such as high quality diamond, battery material fully.
Embodiment 2
Adding carbon content in the PP retort is natural graphite 1500kg, its carbon content is 90%, in the PP retort, add simultaneously concentration and be 40% hydrofluoric acid 450kg, concentration and be 30% hydrochloric acid soln 400kg, concentration and be 98% sulphuric acid soln 200kg and concentration and be 40% salpeter solution 120kg, adding an amount of about 400kg of water stirs the ratio material in the PP retort, stirred about 15 minutes, the ratio material in the retort is stirred.In the PP retort, feed steam and sealing then.Retort reacted 20 hours the ratio material by steam heating under 100 ℃ of conditions, stirred once every 30 minutes in the reaction process, stirred 5-10 minutes at every turn.When graphite and acid liquid reaction are about 18 hours, in the material that is reacting, add oxygenant fluoram 300kg, and continue to stir.After reaction finishes, material is put into PP material washing tank, and material is carried out circulation cleaning, reach 6-7 until the pH value of material by the method that pure water at the uniform velocity permeates.After washing finishes, the acid solution that washing is produced reclaims, then remaining material is poured into and added the pure water stirring in the circulation stirred pot, in the process that stirs, constantly add pure water, material is washed more completely, to guarantee the purity of material, after in stirred pot, stirring 5-10 minutes, in material suction automatic centrifuge, material is dried automatically, dry back discharging automatically.Material after the drying is packed into and is dried in the steam heating drying machine, oven dry to its moisture content less than 0.1%.After the screening of ultrasonic vibration sieve, thoroughly removal of impurities, packing warehouse-in.The graphite concentration of purifying through this method can reach 99.93%.
Other are with embodiment 1.
Embodiment 3
Adding carbon content in the PP retort is natural graphite 1500kg, its carbon content is 95%, in the PP retort, add simultaneously concentration and be 40% hydrofluoric acid 500kg, concentration and be 30% hydrochloric acid soln 500kg, concentration and be 98% sulphuric acid soln 300kg and concentration and be 40% salpeter solution 160kg, add an amount of about 300kg of water and the ratio material in the PP retort is stirred, stirred about 25 minutes, the material in the retort is stirred.In the PP retort, feed steam and sealing then.Retort reacted 20 hours the ratio material by steam heating under 80 ℃ of conditions, stirred once every 30 minutes in the reaction process, stirred 5-10 minutes at every turn.When graphite and acid liquid reaction are about 18 hours, in the material that is reacting, add oxygenant fluoram 300kg, and continue to stir.After reaction finishes, material is put into PP material washing tank, material is carried out circulation cleaning, reach 6-7 until the pH value of material by the method that pure water at the uniform velocity permeates.After washing finishes, the acid solution that washing is produced reclaims, material after the washing poured into add pure water in the circulation stirred pot and stir, constantly add pure water in the whipping process, material is washed more up hill and dale, to guarantee the purity of material, after in stirred pot, stirring 5-10 minutes, in material suction automatic centrifuge, material is dried automatically, dry back discharging automatically.The material that dries is packed into and is dried in the steam heating drying machine, oven dry to its moisture content less than 0.1%.After the screening of ultrasonic vibration sieve, thoroughly removal of impurities, packing warehouse-in.The graphite concentration of purifying through this method can reach 99.96%.
Other are with embodiment 1.
Embodiment 4
Adding carbon content in the PP retort is natural graphite 1500kg, its carbon content is 99%, in the PP retort, add simultaneously concentration and be 40% hydrofluoric acid 400kg, concentration and be 30% hydrochloric acid soln 450kg, concentration and be 98% sulphuric acid soln 150kg and concentration and be 40% salpeter solution 100kg, add an amount of about 600kg of water and the ratio material in the PP retort is stirred, stirred about 25 minutes, the material in the retort is stirred.In the PP retort, feed steam and sealing then.Retort reacted 12 hours the ratio material by steam heating under 100 ℃ of conditions, stirred once every 30 minutes in the reaction process, stirred 5-10 minutes at every turn.When graphite and acid liquid reaction are about 10 hours, in the material that is reacting, add oxygenant fluoram 500kg, and continue to stir.After reaction finishes, material is put into PP material washing tank, material is carried out circulation cleaning, reach 6-7 until the pH value of material by the method that pure water at the uniform velocity permeates.After washing finishes, the acid solution that washing is produced reclaims, material after the washing poured into add pure water in the circulation stirred pot and stir, constantly add pure water in the whipping process, material is washed more up hill and dale, to guarantee the purity of material, after in stirred pot, stirring 5-10 minutes, in material suction automatic centrifuge, material is dried automatically, dry back discharging automatically.Material after the drying is packed into and is dried in the steam heating drying machine, oven dry to its moisture content less than 0.1%.After the screening of ultrasonic vibration sieve, thoroughly removal of impurities, packing warehouse-in.The graphite concentration of purifying through this method can reach 99.995%.
Other are with embodiment 1.
Claims (2)
1. method for preparing high pure graphite with steam heating is characterized in that this technology may further comprise the steps:
(1) natural graphite with carbon content 90%-99% is a raw material, it is added in the PP retort, in retort, add simultaneously hydrofluoric acid, hydrochloric acid, nitric acid, sulphuric acid soln and water, graphite raw material, acid solution and water are prepared burden in proportion, and stirred 15-20 minute, material is stirred into scattered paste shape, described graphite, hydrofluoric acid, hydrochloric acid, nitric acid, the weight ratio of sulphuric acid soln and water is 15: 4-5: 3-5: 1-1.6: 1.5-3: 3-6, wherein the concentration of hydrofluoric acid solution is 40%, the concentration of hydrochloric acid soln is 30%, the concentration of salpeter solution is 40%, and the concentration of sulphuric acid soln is 98%;
(2) feed steam in the PP material retort, heating and sealing, the material that stirs reacted 12-24 hour under 60 ℃-100 ℃ condition, in the reaction process, stirred once every 30 minutes, stirred 5-10 minute at every turn;
(3) add oxygenant in 2-4 hour in PP material retort before reaction finishes, and continue heated and stirred, the oxygenant of adding is a fluoram, and the weight ratio of the ratio material that itself and graphite raw material, acid solution and water are formed is 1: 6.5-1: between 14.5;
(4) abundant reacted material is put into PP material washing tank circulation cleaning, reached 6-7 until its pH value;
(5) pour in the circulation stirred pot through the material of washing, add pure water and stirring, constantly add pure water in the whipping process, in the circulation stirred pot, stirred 5-10 minute;
(6) finish agitating procedure after, the material suction automatic centrifuge in the circulation stirred pot dries automatically, and automatic discharging;
(7) material that will dewater is packed into and is dried in the steam heating drying machine, dry to moisture content less than 0.1%.
2. method for preparing high pure graphite with steam heating according to claim 1, it is characterized in that: in the described material washing tank material is washed by the mode that pure water at the uniform velocity permeates, be about to add pure water after reacted material is poured the material washing tank into, make pure water pass through at the uniform velocity to permeate and mixing of materials, thus degree of depth washing.
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| CN2008101572801A CN101367517B (en) | 2008-09-24 | 2008-09-24 | Method for preparing high pure graphite with steam heating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437187A (en) * | 2018-11-28 | 2019-03-08 | 乌兰察布市大盛石墨新材料股份有限公司 | The preparation method of graphite material |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101559943B (en) * | 2009-04-10 | 2011-02-16 | 文中华 | Graphite purifying device |
| CN101983917B (en) * | 2010-11-02 | 2012-11-07 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Preparation method of high purity graphite |
| CN103373723A (en) * | 2012-04-17 | 2013-10-30 | 夏华松 | High-purity crystalline graphite purifying process |
| CN104556015B (en) * | 2015-01-19 | 2016-11-23 | 黑龙江科技大学 | A kind of method that floride-free low stain nitration mixture prepares high purity graphite |
| CN108654828A (en) * | 2017-03-28 | 2018-10-16 | 纳米石墨烯股份有限公司 | Liquid-based method and apparatus for graphite purification |
| CN111137883B (en) * | 2020-01-09 | 2022-06-24 | 成都理工大学 | Method for preparing high-purity graphite from natural graphite |
| CN112520733A (en) * | 2020-12-01 | 2021-03-19 | 萝北瑞喆烯碳新材料有限公司 | Chemical purification method for graphite |
| CN117466284B (en) * | 2023-12-28 | 2024-03-15 | 天津理工大学 | Surface modified hard carbon negative electrode material of sodium ion battery and preparation method thereof |
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| CN1557704A (en) * | 2004-01-21 | 2004-12-29 | 敏 岳 | Method for purifying natural crystalline flake graphite of high purity |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437187A (en) * | 2018-11-28 | 2019-03-08 | 乌兰察布市大盛石墨新材料股份有限公司 | The preparation method of graphite material |
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