CN101973545A - Method for purifying high-purity graphite - Google Patents
Method for purifying high-purity graphite Download PDFInfo
- Publication number
- CN101973545A CN101973545A CN 201010534852 CN201010534852A CN101973545A CN 101973545 A CN101973545 A CN 101973545A CN 201010534852 CN201010534852 CN 201010534852 CN 201010534852 A CN201010534852 A CN 201010534852A CN 101973545 A CN101973545 A CN 101973545A
- Authority
- CN
- China
- Prior art keywords
- graphite
- concentration
- acid
- high purity
- purity graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 70
- 239000010439 graphite Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012141 concentrate Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 12
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005188 flotation Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000013467 fragmentation Methods 0.000 claims 1
- 238000006062 fragmentation reaction Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 32
- 239000002253 acid Substances 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000005484 gravity Effects 0.000 abstract description 5
- 238000007873 sieving Methods 0.000 abstract description 5
- 150000004673 fluoride salts Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 salt sodium fluoride Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种提纯高纯石墨的方法，特别是由石墨原矿提纯纯度大于99.99％的高纯石墨的方法。The invention relates to a method for purifying high-purity graphite, in particular to a method for purifying high-purity graphite with a purity greater than 99.99 percent from graphite raw ore.
背景技术Background technique
高纯石墨是石墨含量在99.99％以上的石墨，它是一种不可再生的战略资源，一直是军工和现代工艺及高新技术发展中不可或缺的重要战备资源。High-purity graphite is graphite with a graphite content of more than 99.99%. It is a non-renewable strategic resource and has always been an indispensable resource for military industry, modern technology and high-tech development.
目前高纯石墨的生产方法主要以浮选法、酸碱法、氢氟酸法为主的湿法提纯方法和以氯化焙烧法和高温法为主的火法提纯法。这几种生产方法或多或少地存在除杂效果差、能耗高、环境污染严重等不足。At present, the production methods of high-purity graphite are mainly wet purification methods based on flotation, acid-base method, and hydrofluoric acid method, and fire purification methods based on chlorination roasting method and high-temperature method. These production methods more or less have the disadvantages of poor impurity removal effect, high energy consumption, and serious environmental pollution.
发明内容Contents of the invention
本发明提供一种提纯高纯石墨的方法，能有效去除石墨中的杂质，使石墨的固定碳的含量达到99.99％，达到高纯石墨要求的方法。产品的性能较好，其工艺简单、先进、易于操作，生产效率高、设备投资少、能耗低，对环境的影响比较小，成本低，石墨产品纯度高，能够满足高纯石墨的要求。The invention provides a method for purifying high-purity graphite, which can effectively remove impurities in graphite, make the fixed carbon content of graphite reach 99.99%, and meet the requirements of high-purity graphite. The performance of the product is good, the process is simple, advanced, easy to operate, high production efficiency, less equipment investment, low energy consumption, relatively small impact on the environment, low cost, high purity graphite products, can meet the requirements of high purity graphite.
解决本发明的技术问题所采用的技术方案为：石墨原矿经过破碎、球磨、筛分等工序后，采用浮选设备或重选设备对其进行选矿处理，得到石墨精矿。石墨精矿先在加压反应釜中进行碱浸处理，而后在超声波场或微波场中进行常压酸浸处理。最后石墨采用氢氟酸或者含氟盐的体系进行深度除杂，得到高纯度的石墨产品；反应后的各段的浸出废液经过回收处理后循环利用。技术特征如下：The technical solution adopted to solve the technical problem of the present invention is: after the raw graphite ore undergoes processes such as crushing, ball milling, and screening, it is beneficiated by flotation equipment or gravity separation equipment to obtain graphite concentrate. Graphite concentrate is first subjected to alkaline leaching treatment in a pressurized reactor, and then subjected to normal-pressure acid leaching treatment in an ultrasonic or microwave field. Finally, graphite is deeply removed by hydrofluoric acid or fluorine-containing salt system to obtain high-purity graphite products; the leaching waste liquid of each stage after the reaction is recycled and reused. The technical characteristics are as follows:
一种提纯高纯石墨的方法，以石墨原矿为原料，原料为鳞片石墨或隐晶石墨，特征在于：石墨原矿经过破碎机数次破碎后，投入球磨机中进行研磨，得到50目以下的石墨粉料，将粉碎后的石墨物料投入筛分机中进行石墨粉末分级，得到粒度为100～1000目的石墨粉料；而不合格的石墨粉则重新投入到球磨机中进行反复球磨；采用浮选设备或者重选设备对石墨粉料进行选矿处理得到石墨精矿；先后采用加压碱浸和常压酸浸对石墨精矿进行处理，其中常压酸浸是在超声波场或/和微波场下进行；处理后的石墨粉再用氢氟酸或含氟盐氟化钠进行浸出，得到高纯度的石墨产品。A method for purifying high-purity graphite, using graphite raw ore as raw material, the raw material is flake graphite or cryptocrystalline graphite, characterized in that: the graphite raw ore is crushed several times by a crusher, and then put into a ball mill for grinding to obtain graphite powder below 50 mesh Put the pulverized graphite material into the sieving machine for graphite powder classification to obtain graphite powder with a particle size of 100-1000 mesh; unqualified graphite powder is put back into the ball mill for repeated ball milling; use flotation equipment or heavy The graphite powder is beneficiated by the beneficiation equipment to obtain graphite concentrate; the graphite concentrate is processed by pressurized alkali leaching and atmospheric pressure acid leaching successively, and the atmospheric pressure acid leaching is carried out under the ultrasonic field or/and microwave field; The final graphite powder is leached with hydrofluoric acid or fluorine-containing salt sodium fluoride to obtain high-purity graphite products.
所述的浮选温度为20～60℃，浮选的重量液固比为1～20∶1。The flotation temperature is 20-60° C., and the weight-liquid-solid ratio of flotation is 1-20:1.
所述的加压碱浸的溶液是LiOH、NaOH、KOH、Na2CO3或氨水水溶液的任意一种或几种的混合；LiOH浓度为5％～40％，NaOH浓度为5％～35％，KOH浓度为5％～27％，Na2CO3浓度为5％～30％；加压碱浸的重量液固比为1～10∶1，温度为100～300℃，反应压强为0.3～30.0MPa，处理时间为0.5～12小时；采用石灰作为试剂回收再生碱液。The solution of the pressurized alkaline leaching is any one or a mixture of LiOH, NaOH, KOH, Na2CO3 or ammonia aqueous solution; the concentration of LiOH is 5% to 40 %, and the concentration of NaOH is 5% to 35%. , the KOH concentration is 5% to 27%, the Na2CO3 concentration is 5% to 30%; the weight-liquid-solid ratio of pressurized alkaline leaching is 1-10:1, the temperature is 100-300°C, and the reaction pressure is 0.3- 30.0MPa, the treatment time is 0.5-12 hours; lime is used as a reagent to recover and regenerate lye.
所述常压酸浸采用的溶液是盐酸、硫酸、硝酸或醋酸水溶液的任意一种或几种的混合；盐酸浓度为5％～35％，硫酸浓度为5％～80％，硝酸浓度为5％～60％，醋酸浓度为5％～100％；常压酸浸的重量液固比为1～8∶1，温度为30～90℃，处理时间为1h～100h。常压酸浸时的超声波频率范围在15～80KHz，微波场频率范围在300GHz～3GHz。The solution adopted in the atmospheric acid leaching is any one or a mixture of hydrochloric acid, sulfuric acid, nitric acid or acetic acid aqueous solution; the concentration of hydrochloric acid is 5% to 35%, the concentration of sulfuric acid is 5% to 80%, and the concentration of nitric acid is 5% % to 60%, the concentration of acetic acid is 5% to 100%; the weight-liquid-solid ratio of atmospheric acid leaching is 1-8:1, the temperature is 30-90°C, and the treatment time is 1h-100h. The ultrasonic frequency range during atmospheric pressure acid leaching is 15-80KHz, and the microwave field frequency range is 300GHz-3GHz.
所述的氢氟酸的浓度：1％～45％，含氟盐氟化钠NaF的浓度为1～20％；氢氟酸或氟化钠处理的重量液固比1～9∶1，温度为40～90℃，处理时间为1h～24h。The concentration of the hydrofluoric acid: 1%-45%, the concentration of the fluorine-containing salt sodium fluoride NaF is 1-20%; the weight-liquid-solid ratio of hydrofluoric acid or sodium fluoride treatment is 1-9:1, the temperature The temperature is 40~90℃, and the treatment time is 1h~24h.
上述加压碱浸：选矿后的石墨精矿投入加压反应釜中，添加碱溶液，控制反应条件，使石墨精矿中的杂质与碱液发生反应。反应结束后，实现固液分离。固体采用纯水洗涤至pH＝7为止，液体采用石灰进行碱液再生。The above-mentioned pressurized alkali leaching: put the graphite concentrate after ore dressing into a pressurized reaction kettle, add alkali solution, control the reaction conditions, and make the impurities in the graphite concentrate react with the alkali solution. After the reaction is over, solid-liquid separation is achieved. The solid is washed with pure water until pH = 7, and the liquid is regenerated with lime.
上述常压酸浸：洗涤至中性的石墨与上述条件的酸溶液混合调浆，控制反应条件，使石墨中的杂质进一步与酸发生反应。反应过程在超声波场或微波场中进行。反应后的石墨最后采用氢氟酸或含氟盐氟化钠进行深度除杂，以去除酸性条件下生成的硅酸。酸浸过程中产生的废酸采用离子交换树脂或萃取的方式进行酸液再生。The above atmospheric pressure acid leaching: the graphite washed to neutral is mixed with the acid solution of the above conditions to adjust the slurry, and the reaction conditions are controlled to make the impurities in the graphite further react with the acid. The reaction process is carried out in an ultrasonic field or a microwave field. The reacted graphite is finally deeply cleaned with hydrofluoric acid or fluorine-containing salt sodium fluoride to remove silicic acid generated under acidic conditions. The waste acid produced in the pickling process is regenerated by means of ion exchange resin or extraction.
洗涤过程中产生的酸性废水与碱性废水相互中和，并添加石灰沉淀溶液中的F。中和后的水重新返回系统进行洗涤。整个工艺过程不污染环境。The acidic wastewater and alkaline wastewater generated during the washing process neutralize each other, and F in the lime precipitation solution is added. The neutralized water returns to the system for washing. The whole process does not pollute the environment.
本发明的有益效果是：石墨原矿经浮选或重选、加压碱浸、酸浸处理后得到高纯石墨，并在酸浸过程中添加超声波场或微波场。工艺流程短，容易实现工业化生产，设备简单，安全性好，能耗低，生产成本低，环境污染小；获得的高纯石墨中固定碳的含量大于99.99％。The beneficial effect of the invention is that high-purity graphite can be obtained after the raw graphite ore undergoes flotation or gravity separation, pressurized alkali leaching, and acid leaching, and an ultrasonic field or microwave field is added in the acid leaching process. The technological process is short, the industrial production is easy to realize, the equipment is simple, the safety is good, the energy consumption is low, the production cost is low, and the environmental pollution is small; the content of fixed carbon in the obtained high-purity graphite is greater than 99.99%.
具体实施方式Detailed ways
下面通过实施例对本发明作进一步详细描述。The present invention will be described in further detail below by way of examples.
实施例一Embodiment one
使用含碳量10wt％的鳞片石墨为原料，将原料依次进破碎机破碎、球磨机球磨，并采用筛分机对石墨粉进行筛粉，得到粒度为150目的石墨粉料，然后采用浮选设备对其进行初步除杂，得到石墨精矿。Using flake graphite with a carbon content of 10wt% as raw material, the raw material is successively crushed by a crusher, ball milled by a ball mill, and the graphite powder is sieved by a sieving machine to obtain a graphite powder with a particle size of 150 mesh, and then use a flotation device for its Perform preliminary impurity removal to obtain graphite concentrate.
用浓度为5％的NaOH溶液按照液固比为1∶1的重量份对石墨精矿在加压反应釜中进行碱浸处理，控制反应温度为110～130℃，反应压强为25MPa，处理时间为12h。反应后的物料实现固液分离，并用纯水清洗至pH＝7。再将反应后的物料用浓度为10％的盐酸溶液按照液固比为8∶1的重量份进行酸浸出处理，控制反应条件为常压、反应温度为90℃，处理时间为50h；酸浸过程中添加微波场，微波频率为3GHz。反应后的石墨粉过滤后最后采用浓度为20％的氢氟酸溶液进行深度除杂浸出处理，氢氟酸处理的重量份液固比为5∶1，温度为60℃，处理时间为5h，处理后的产品采用常规技术经过洗涤至中性后干燥得到高纯度的石墨产品，其纯度为99.991％，产品总灰分为0.009％。其中Al2O3的残余量为18ppmw，Fe2O3的残余量为14ppmw，SiO2的残余量为23ppmw，其它杂质总量小于15ppmw。Use NaOH solution with a concentration of 5% to carry out alkali leaching treatment to graphite concentrate in a pressurized reactor according to the weight part of liquid-solid ratio of 1:1, control the reaction temperature to be 110-130°C, and the reaction pressure to be 25MPa. for 12h. The reacted material was separated from solid and liquid, and washed with pure water until pH=7. The material after the reaction is that the hydrochloric acid solution of 10% is carried out acid leaching treatment according to the weight portion of 8: 1 according to the liquid-solid ratio with the concentration of the material after the reaction, and the control reaction condition is normal pressure, and reaction temperature is 90 ℃, and the processing time is 50h; A microwave field is added during the process, and the microwave frequency is 3 GHz. After the graphite powder after the reaction is filtered, finally adopt the concentration of 20% hydrofluoric acid solution to carry out deep impurity removal leaching treatment, the weight part liquid-solid ratio of hydrofluoric acid treatment is 5: 1, the temperature is 60 ℃, and the treatment time is 5h, The processed product is washed to neutral by conventional technology and then dried to obtain a high-purity graphite product with a purity of 99.991% and a total ash content of 0.009%. Wherein the residual amount of Al 2 O 3 is 18ppmw, the residual amount of Fe 2 O 3 is 14ppmw, the residual amount of SiO 2 is 23ppmw, and the total amount of other impurities is less than 15ppmw.
以上各项反应后产生的各种废液经过回收处理循环利用，碱浸处理后的废液采用石灰进行碱液再生，酸浸处理后的废液采用萃取或离子交换树脂进行酸液再生。The various waste liquids produced after the above reactions are recycled and recycled. The waste liquid after alkali leaching treatment is regenerated with lime, and the waste liquid after acid leaching treatment is regenerated with acid liquid using extraction or ion exchange resin.
实施例二Embodiment two
使用含碳量15wt％的鳞片石墨为原料，将原料依次进破碎机破碎、球磨机球磨，并采用筛分机对石墨粉进行筛粉，得到粒度为250目的石墨粉料，然后采用重选设备对其进行初步除杂，得到石墨精矿。Using flake graphite with a carbon content of 15wt% as raw material, the raw material is successively crushed by a crusher, ball milled by a ball mill, and the graphite powder is sieved by a sieving machine to obtain a graphite powder with a particle size of 250 mesh, and then use a gravity separation device to Perform preliminary impurity removal to obtain graphite concentrate.
用浓度为30％的KOH与20％的Na2CO3混合溶液按照液固比为5∶1的重量份对石墨精矿在加压反应釜中进行碱浸处理，控制反应温度为180～200℃，反应压强为15MPa，处理时间为6h。反应后的物料实现固液分离，并使用纯水清洗至pH＝7。再将反应后的物料用浓度为15％的硝酸溶液按照液固比为1∶1的重量份进行酸浸出处理，控制反应条件为常压、反应温度为50℃，处理时间为20h，酸浸过程中添加超声波场，超声波频率为17KHz。反应后的石墨粉过滤后最后采用浓度为10％的氢氟酸溶液进行深度除杂浸出处理，氢氟酸处理的重量份液固比为2∶1，温度为40℃，处理时间为7h，处理后的产品采用常规技术经过洗涤至中性后干燥得到高纯度的石墨产品，其纯度为99.995％，产品总灰分为0.005％，其中Al2O3的残余量为10ppmw，Fe2O3的残余量为7ppmw，SiO2的残余量为11ppmw，其它杂质总量小于5ppmw。Use a mixed solution of 30% KOH and 20% Na2CO3 to carry out alkali leaching treatment on the graphite concentrate in a pressurized reaction kettle according to the liquid-solid ratio of 5:1 by weight, and control the reaction temperature to be 180-200 ℃, the reaction pressure is 15MPa, and the treatment time is 6h. The reacted material was separated from solid and liquid, and washed with pure water until pH=7. The material after reaction is that the nitric acid solution of 15% is carried out acid leaching treatment according to the weight part that liquid-solid ratio is 1: 1 with concentration again, and control reaction condition is normal pressure, and reaction temperature is 50 ℃, and the treatment time is 20h, acid leaching An ultrasonic field is added during the process, and the ultrasonic frequency is 17KHz. After the graphite powder after the reaction is filtered, finally adopt the concentration of 10% hydrofluoric acid solution to carry out deep impurity removal and leaching treatment, the weight part liquid-solid ratio of hydrofluoric acid treatment is 2: 1, the temperature is 40 ℃, and the treatment time is 7h, The processed product is washed to neutral by conventional technology and then dried to obtain a high-purity graphite product with a purity of 99.995%, a total ash content of 0.005%, and a residual content of Al 2 O 3 of 10ppmw, Fe 2 O 3 The residual amount is 7ppmw, the residual amount of SiO2 is 11ppmw, and the total amount of other impurities is less than 5ppmw.
实施例三Embodiment Three
使用含碳量30wt％的隐晶石墨为原料。将原料依次进破碎机破碎、球磨机球磨，并采用筛分机对石墨粉进行筛粉，得到粒度为350目的石墨粉料，然后采用重选设备对其进行初步除杂，得到石墨精矿。Cryptocrystalline graphite with a carbon content of 30wt% is used as a raw material. The raw materials are crushed in a crusher and ball milled in a ball mill in turn, and the graphite powder is sieved by a sieving machine to obtain a graphite powder with a particle size of 350 mesh, and then the gravity separation equipment is used for preliminary removal of impurities to obtain graphite concentrate.
用浓度为25％的LiOH和5％的KOH混合溶液按照液固比为8∶1的重量份对石墨精矿在加压反应釜中进行碱浸处理，控制反应温度为250～280℃，反应压强为20MPa，处理时间为4h。反应后的物料实现固液分离，并使用纯水清洗至pH＝7。再将反应后的物料用浓度为20％的盐酸溶液和15％的硫酸以及30％的醋酸混合溶液按照液固比为4∶1的重量份进行常压酸浸处理，控制反应温度为60℃，处理时间为80h。酸浸过程中先后添加微波场和超声波场，微波频率为50GHz，超声波的频率为50KHz，时间各是40小时。反应后的石墨粉过滤后最后采用浓度为10％的氟化钠NaF溶液按照液固比为4∶1的重量份进行浸出处理，处理后的产品采用常规技术经过洗涤至中性后干燥得到高纯度的石墨产品，其纯度为99.993％，产品总灰分为0.007％。其中Al2O3的残余量为12ppmw，Fe2O3的残余量为14ppmw，SiO2的残余量为23ppmw，其它杂质总量小于11ppmw。The concentration is 25% LiOH and 5% KOH mixed solution according to the liquid-solid ratio is 8: 1 weight portion carries out alkaline leaching treatment to graphite concentrate in the pressurized reaction kettle, and the control reaction temperature is 250～280 ℃, reaction The pressure is 20MPa, and the treatment time is 4h. The reacted material was separated from solid and liquid, and washed with pure water until pH=7. Then the reacted material is carried out normal pressure acid leaching treatment according to the weight portion of 4: 1 according to the weight portion of 20% hydrochloric acid solution and 15% sulfuric acid and 30% acetic acid mixed solution with concentration, and the control reaction temperature is 60 ℃. , the processing time is 80h. During the acid leaching process, a microwave field and an ultrasonic field were successively added, the frequency of the microwave was 50 GHz, and the frequency of the ultrasonic wave was 50 KHz, and the time was 40 hours each. After the graphite powder after the reaction is filtered, the sodium fluoride NaF solution with a concentration of 10% is finally used for leaching treatment according to a liquid-solid ratio of 4: 1 by weight, and the processed product is washed to neutral and then dried to obtain a high The pure graphite product has a purity of 99.993%, and the total ash content of the product is 0.007%. Wherein the residual amount of Al 2 O 3 is 12ppmw, the residual amount of Fe 2 O 3 is 14ppmw, the residual amount of SiO 2 is 23ppmw, and the total amount of other impurities is less than 11ppmw.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010534852A CN101973545B (en) | 2010-11-08 | 2010-11-08 | Method for purifying high-purity graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010534852A CN101973545B (en) | 2010-11-08 | 2010-11-08 | Method for purifying high-purity graphite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101973545A true CN101973545A (en) | 2011-02-16 |
| CN101973545B CN101973545B (en) | 2012-09-05 |
Family
ID=43573462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010534852A Expired - Fee Related CN101973545B (en) | 2010-11-08 | 2010-11-08 | Method for purifying high-purity graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101973545B (en) |
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583342A (en) * | 2012-02-05 | 2012-07-18 | 加拿大环球石墨有限公司 | Purification method of microcrystal graphite |
| CN102583360A (en) * | 2012-04-16 | 2012-07-18 | 丁慧贤 | Method for purifying graphite by using microwave |
| CN102649100A (en) * | 2012-04-21 | 2012-08-29 | 山东莱芜煤矿机械有限公司 | Equipment combination for fine flake graphite flotation technology |
| CN102702608A (en) * | 2012-06-29 | 2012-10-03 | 长沙理工大学 | Method for improving performance of aphanitic graphite/polymer composite wave-absorbing material |
| CN102861661A (en) * | 2012-09-24 | 2013-01-09 | 湛江市聚鑫新能源有限公司 | Beneficiation method and beneficiation equipment system for graphite ores |
| CN103072975A (en) * | 2012-12-28 | 2013-05-01 | 中南大学 | Low-grade aphanitic graphite dressing and purifying method |
| CN103373723A (en) * | 2012-04-17 | 2013-10-30 | 夏华松 | High-purity crystalline graphite purifying process |
| CN104003382A (en) * | 2014-06-17 | 2014-08-27 | 鸡西市同泰石墨制品有限公司 | Method for chemically purifying and continuously producing high-purity graphite |
| CN104098092A (en) * | 2014-08-03 | 2014-10-15 | 北京矿冶研究总院 | Method for purifying natural microcrystalline graphite |
| CN104229788A (en) * | 2014-09-24 | 2014-12-24 | 攀枝花学院 | Method for purifying high-purity graphite |
| CN104495803A (en) * | 2014-11-27 | 2015-04-08 | 林前锋 | Purification method of natural microcrystalline graphite |
| CN104888934A (en) * | 2015-05-13 | 2015-09-09 | 黑龙江科技大学 | Medium-carbon graphite mineral dressing process |
| CN105129783A (en) * | 2015-08-24 | 2015-12-09 | 莱芜大山资源利用环保科技有限公司 | Device for purifying graphite by taking desulfuration residues as raw materials and processing technology |
| CN105289835A (en) * | 2015-10-28 | 2016-02-03 | 武汉理工大学 | Purification technique for mineral separation of low-grade fine crystalline flake graphite |
| CN106077038A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant flotation alkaline pressure of oxygen leaching synthetical recovery aluminum electrolysis waste cathode carbon block |
| CN106077037A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant flotation pressurized acid leaching synthetical recovery aluminum electrolysis waste cathode carbon block |
| CN106077036A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant acidleach process aluminum electrolytic waste and old cathode carbon block |
| CN106077040A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant alkali leaching process aluminum electrolytic waste and old cathode carbon block |
| CN106180118A (en) * | 2016-06-30 | 2016-12-07 | 中南大学 | A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode |
| CN106517177A (en) * | 2016-11-04 | 2017-03-22 | 吉林吉恩镍业股份有限公司 | Method for purifying graphite by using high-pressure alkaline leaching |
| CN106663815A (en) * | 2014-11-03 | 2017-05-10 | 株式会社Lg 化学 | Conductive material manufacturing method, conductive material manufactured therefrom, and lithium secondary battery including same |
| CN106882804A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院上海应用物理研究所 | The preparation method and preparation facilities of a kind of fluorographite |
| CN107539982A (en) * | 2017-10-31 | 2018-01-05 | 湖南国盛石墨科技有限公司 | A kind of high-purity micro crystal graphite production system and its production technology |
| CN107601493A (en) * | 2017-11-01 | 2018-01-19 | 河海大学 | A kind of method that secondary pickling combination thermal activation prepares high purity graphite |
| CN107739029A (en) * | 2017-10-31 | 2018-02-27 | 中国地质科学院郑州矿产综合利用研究所 | Crystalline graphite flake protection and quality separation method |
| CN107930839A (en) * | 2017-11-24 | 2018-04-20 | 中国矿业大学 | A kind of method of the gravity-floatation combined separation of graphite and silicon |
| WO2018088636A1 (en) * | 2016-11-11 | 2018-05-17 | 주식회사 카보랩 | Method for recycling waste graphite powder and graphite powder manufactured by the same |
| US20180230014A1 (en) * | 2015-08-11 | 2018-08-16 | Metoxs Pte Ltd. | Method for cost-efficient industrial production of graphite oxide, graphene oxide and graphene |
| CN108529615A (en) * | 2018-06-01 | 2018-09-14 | 中钢集团新型材料（浙江）有限公司 | A kind of addition fluoride salt is the graphite purification method of impregnating agent |
| CN109647630A (en) * | 2018-12-28 | 2019-04-19 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of short route method of purification of graphite |
| CN109950539A (en) * | 2019-03-15 | 2019-06-28 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of preparation method of graphene coated carbon negative pole material |
| CN110028064A (en) * | 2019-04-17 | 2019-07-19 | 中南大学 | A kind of middle grade graphite raw ore method of purification |
| CN112093798A (en) * | 2020-10-29 | 2020-12-18 | 哈尔滨理工大学 | Outfield-assisted graphite rapid purification method |
| CN112678800A (en) * | 2020-12-23 | 2021-04-20 | 湘潭大学 | Preparation method of graphite fluoride micron sheet |
| CN112794322A (en) * | 2020-12-28 | 2021-05-14 | 萝北奥星新材料有限公司 | Purification method of graphite |
| CN113716559A (en) * | 2021-09-03 | 2021-11-30 | 黑龙江省宝泉岭农垦溢祥石墨有限公司 | Strong acid method scale graphite purification process and device |
| CN114873592A (en) * | 2022-06-10 | 2022-08-09 | 苏州中材非金属矿工业设计研究院有限公司 | Purification process of natural graphite |
| CN114956071A (en) * | 2022-07-12 | 2022-08-30 | 鞍山市五色石新材料科技有限公司 | Graphite ore purification method capable of recycling fluorine element |
| CN115246642A (en) * | 2022-07-05 | 2022-10-28 | 北京科技大学 | A kind of high-purity crystalline graphite and preparation method thereof |
| CN115557495A (en) * | 2021-07-01 | 2023-01-03 | 中国科学院过程工程研究所 | A kind of low-fluorine purification method of natural graphite spherical tailings |
| CN115611278A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院过程工程研究所 | A graphite purification method and device |
| US11702342B2 (en) | 2020-05-18 | 2023-07-18 | Ecograf Limited | Method of producing purified graphite |
| CN117819541A (en) * | 2024-03-04 | 2024-04-05 | 矿冶科技集团有限公司 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
| CN118579776A (en) * | 2024-08-06 | 2024-09-03 | 陕西汉唐森源实业发展集团有限责任公司 | A two-step alkali-acid purification method for natural graphite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337669A (en) * | 2008-08-12 | 2009-01-07 | 云南冶金集团总公司技术中心 | Method for preparing high pure carbon for industrial carbon |
| CN101654244A (en) * | 2009-09-11 | 2010-02-24 | 云南冶金集团总公司技术中心 | Method for preparing high-purity graphite from high-carbon graphite |
-
2010
- 2010-11-08 CN CN201010534852A patent/CN101973545B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337669A (en) * | 2008-08-12 | 2009-01-07 | 云南冶金集团总公司技术中心 | Method for preparing high pure carbon for industrial carbon |
| CN101654244A (en) * | 2009-09-11 | 2010-02-24 | 云南冶金集团总公司技术中心 | Method for preparing high-purity graphite from high-carbon graphite |
Non-Patent Citations (2)
| Title |
|---|
| 《金属矿山》 20101031 葛鹏等 石墨提纯方法进展 38-43 1-7 , 第10期 2 * |
| 《非金属矿》 20020331 李常清等 液相化学法制取高纯石墨研究 35-36,38 1-7 第25卷, 第2期 2 * |
Cited By (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583342A (en) * | 2012-02-05 | 2012-07-18 | 加拿大环球石墨有限公司 | Purification method of microcrystal graphite |
| CN102583360A (en) * | 2012-04-16 | 2012-07-18 | 丁慧贤 | Method for purifying graphite by using microwave |
| CN103373723A (en) * | 2012-04-17 | 2013-10-30 | 夏华松 | High-purity crystalline graphite purifying process |
| CN102649100A (en) * | 2012-04-21 | 2012-08-29 | 山东莱芜煤矿机械有限公司 | Equipment combination for fine flake graphite flotation technology |
| CN102702608A (en) * | 2012-06-29 | 2012-10-03 | 长沙理工大学 | Method for improving performance of aphanitic graphite/polymer composite wave-absorbing material |
| CN102702608B (en) * | 2012-06-29 | 2014-07-02 | 长沙理工大学 | Method for improving performance of aphanitic graphite/polymer composite wave-absorbing material |
| CN102861661A (en) * | 2012-09-24 | 2013-01-09 | 湛江市聚鑫新能源有限公司 | Beneficiation method and beneficiation equipment system for graphite ores |
| CN102861661B (en) * | 2012-09-24 | 2014-08-27 | 湛江市聚鑫新能源有限公司 | Beneficiation method and beneficiation equipment system for graphite ores |
| CN103072975A (en) * | 2012-12-28 | 2013-05-01 | 中南大学 | Low-grade aphanitic graphite dressing and purifying method |
| CN104003382B (en) * | 2014-06-17 | 2016-10-05 | 鸡西市同泰石墨制品有限公司 | A kind of high purity graphite chemical purification continuous producing method |
| CN104003382A (en) * | 2014-06-17 | 2014-08-27 | 鸡西市同泰石墨制品有限公司 | Method for chemically purifying and continuously producing high-purity graphite |
| CN104098092A (en) * | 2014-08-03 | 2014-10-15 | 北京矿冶研究总院 | Method for purifying natural microcrystalline graphite |
| CN104229788A (en) * | 2014-09-24 | 2014-12-24 | 攀枝花学院 | Method for purifying high-purity graphite |
| CN106663815A (en) * | 2014-11-03 | 2017-05-10 | 株式会社Lg 化学 | Conductive material manufacturing method, conductive material manufactured therefrom, and lithium secondary battery including same |
| US10637064B2 (en) | 2014-11-03 | 2020-04-28 | Lg Chem, Ltd. | Method for manufacturing conductor, conductor manufactured thereby and lithium secondary battery including the same |
| CN104495803A (en) * | 2014-11-27 | 2015-04-08 | 林前锋 | Purification method of natural microcrystalline graphite |
| CN104888934A (en) * | 2015-05-13 | 2015-09-09 | 黑龙江科技大学 | Medium-carbon graphite mineral dressing process |
| CN108473318A (en) * | 2015-08-11 | 2018-08-31 | 梅多克斯私人投资有限公司 | The economical and practical industrial process of graphite oxide, graphene oxide and graphene |
| US20180230014A1 (en) * | 2015-08-11 | 2018-08-16 | Metoxs Pte Ltd. | Method for cost-efficient industrial production of graphite oxide, graphene oxide and graphene |
| CN105129783A (en) * | 2015-08-24 | 2015-12-09 | 莱芜大山资源利用环保科技有限公司 | Device for purifying graphite by taking desulfuration residues as raw materials and processing technology |
| CN105129783B (en) * | 2015-08-24 | 2019-01-22 | 莱芜大山资源利用环保科技有限公司 | It is a kind of using desulfurization slag as the processing technology of feedstock purification graphite |
| CN105289835A (en) * | 2015-10-28 | 2016-02-03 | 武汉理工大学 | Purification technique for mineral separation of low-grade fine crystalline flake graphite |
| CN106882804A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院上海应用物理研究所 | The preparation method and preparation facilities of a kind of fluorographite |
| CN106882804B (en) * | 2015-12-16 | 2019-11-22 | 中国科学院上海应用物理研究所 | A kind of preparation method and preparation device of fluorinated graphite |
| CN106180118A (en) * | 2016-06-30 | 2016-12-07 | 中南大学 | A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode |
| CN106077040A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant alkali leaching process aluminum electrolytic waste and old cathode carbon block |
| CN106077036A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant acidleach process aluminum electrolytic waste and old cathode carbon block |
| CN106077037A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant flotation pressurized acid leaching synthetical recovery aluminum electrolysis waste cathode carbon block |
| CN106077038A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant flotation alkaline pressure of oxygen leaching synthetical recovery aluminum electrolysis waste cathode carbon block |
| CN106077038B (en) * | 2016-06-30 | 2018-11-06 | 中南大学 | A kind of method of ultrasonic wave secondary flotation alkaline pressure of oxygen leaching synthetical recovery cathode carbon pieces |
| CN106517177A (en) * | 2016-11-04 | 2017-03-22 | 吉林吉恩镍业股份有限公司 | Method for purifying graphite by using high-pressure alkaline leaching |
| WO2018088636A1 (en) * | 2016-11-11 | 2018-05-17 | 주식회사 카보랩 | Method for recycling waste graphite powder and graphite powder manufactured by the same |
| CN107739029A (en) * | 2017-10-31 | 2018-02-27 | 中国地质科学院郑州矿产综合利用研究所 | Crystalline graphite flake protection and quality separation method |
| CN107539982A (en) * | 2017-10-31 | 2018-01-05 | 湖南国盛石墨科技有限公司 | A kind of high-purity micro crystal graphite production system and its production technology |
| CN107601493A (en) * | 2017-11-01 | 2018-01-19 | 河海大学 | A kind of method that secondary pickling combination thermal activation prepares high purity graphite |
| CN107930839A (en) * | 2017-11-24 | 2018-04-20 | 中国矿业大学 | A kind of method of the gravity-floatation combined separation of graphite and silicon |
| CN107930839B (en) * | 2017-11-24 | 2020-12-29 | 中国矿业大学 | A method for the combined separation of graphite and silicon by gravity and flotation |
| CN108529615A (en) * | 2018-06-01 | 2018-09-14 | 中钢集团新型材料（浙江）有限公司 | A kind of addition fluoride salt is the graphite purification method of impregnating agent |
| CN109647630B (en) * | 2018-12-28 | 2021-03-23 | 中建材蚌埠玻璃工业设计研究院有限公司 | Short-process purification method of graphite |
| CN109647630A (en) * | 2018-12-28 | 2019-04-19 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of short route method of purification of graphite |
| CN109950539A (en) * | 2019-03-15 | 2019-06-28 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of preparation method of graphene coated carbon negative pole material |
| CN110028064A (en) * | 2019-04-17 | 2019-07-19 | 中南大学 | A kind of middle grade graphite raw ore method of purification |
| US11702342B2 (en) | 2020-05-18 | 2023-07-18 | Ecograf Limited | Method of producing purified graphite |
| CN112093798A (en) * | 2020-10-29 | 2020-12-18 | 哈尔滨理工大学 | Outfield-assisted graphite rapid purification method |
| CN112678800A (en) * | 2020-12-23 | 2021-04-20 | 湘潭大学 | Preparation method of graphite fluoride micron sheet |
| CN112794322A (en) * | 2020-12-28 | 2021-05-14 | 萝北奥星新材料有限公司 | Purification method of graphite |
| CN115557495A (en) * | 2021-07-01 | 2023-01-03 | 中国科学院过程工程研究所 | A kind of low-fluorine purification method of natural graphite spherical tailings |
| CN113716559A (en) * | 2021-09-03 | 2021-11-30 | 黑龙江省宝泉岭农垦溢祥石墨有限公司 | Strong acid method scale graphite purification process and device |
| CN114873592A (en) * | 2022-06-10 | 2022-08-09 | 苏州中材非金属矿工业设计研究院有限公司 | Purification process of natural graphite |
| CN115246642A (en) * | 2022-07-05 | 2022-10-28 | 北京科技大学 | A kind of high-purity crystalline graphite and preparation method thereof |
| CN115246642B (en) * | 2022-07-05 | 2024-01-30 | 北京科技大学 | High-purity crystalline graphite and preparation method thereof |
| CN114956071A (en) * | 2022-07-12 | 2022-08-30 | 鞍山市五色石新材料科技有限公司 | Graphite ore purification method capable of recycling fluorine element |
| CN115611278A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院过程工程研究所 | A graphite purification method and device |
| CN115611278B (en) * | 2022-10-31 | 2024-03-22 | 中国科学院过程工程研究所 | A kind of graphite purification method and device |
| CN117819541A (en) * | 2024-03-04 | 2024-04-05 | 矿冶科技集团有限公司 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
| CN117819541B (en) * | 2024-03-04 | 2024-06-04 | 矿冶科技集团有限公司 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
| CN118579776A (en) * | 2024-08-06 | 2024-09-03 | 陕西汉唐森源实业发展集团有限责任公司 | A two-step alkali-acid purification method for natural graphite |
| CN118579776B (en) * | 2024-08-06 | 2024-10-22 | 陕西汉唐森源实业发展集团有限责任公司 | Two-step alkali acid purification method of natural graphite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101973545B (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101973545A (en) | Method for purifying high-purity graphite | |
| CN103667710B (en) | Technology for clean production of vanadium pentoxide employing high-calcium vanadium slag | |
| CA2797561C (en) | Method for preparing metallurgical-grade alumina by using fluidized-bed fly ash | |
| JP5702453B2 (en) | Process for treating slag for silica and magnesia extraction | |
| CN104876250B (en) | Method for extracting lithium and removing aluminum by treating lepidolite with sulfuric acid | |
| CN103088205B (en) | Beryllium oxide production process | |
| CN110526250B (en) | A comprehensive utilization method for directly extracting lithium from silicate lithium-containing ores by acid method | |
| CN104261445A (en) | Method for harmlessly treating aluminum ash and preparing sandy alumina | |
| CN106077040A (en) | A kind of method of ultrasonic assistant alkali leaching process aluminum electrolytic waste and old cathode carbon block | |
| CN102153070A (en) | Method for purifying calcined petroleum coke | |
| CN107500325B (en) | A kind of method for producing nano alumina powder from coal gangue | |
| CN110526264A (en) | A kind of method that natural α spodumene directly mentions lithium by-product zeolite | |
| CN103663505B (en) | Method for treating potassium feldspar according to sub-molten salt method to prepare potassium carbonate | |
| CN106219594A (en) | A kind of preparation method of nano zine oxide | |
| CN111792650A (en) | Full-element recycling process of coal ash or coal gangue by hot-melt salt method | |
| CN103950961A (en) | Method for preparing aluminum hydroxide from industrial waste residue generated in aluminum alloy surface treatment | |
| CN105502426A (en) | Method for preparing water glass through extracting silicon oxide from chrysotile tailings by strong-base roasting method | |
| US9676635B2 (en) | Method for producing aqueous zirconium chloride solution | |
| CN103803981B (en) | A kind of method preparing silicon carbide in submicro level powder | |
| CN103834814B (en) | A kind of method preparing red iron oxide with copper nickel slag | |
| CN104340967A (en) | High stability graphite purification method | |
| CN114534706B (en) | Method for preparing titanium-silicon carrier by recycling waste denitration catalyst | |
| CN111268747B (en) | A method and system for recycling cathode material of waste ternary battery based on hydrochloric acid regeneration cycle | |
| CN111893327B (en) | A method for efficiently preparing tungsten oxide by using mixed acid to decompose scheelite concentrate in a short process | |
| CN114195408A (en) | Method for preparing active lime by deep treatment of carbide slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20181108 |