CN107601493B - Method for preparing high-purity graphite by combining secondary acid leaching with thermal activation - Google Patents
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- 239000010439 graphite Substances 0.000 title claims abstract description 111
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- 238000002386 leaching Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000007725 thermal activation Methods 0.000 title claims abstract description 43
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 88
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 66
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- 229910052799 carbon Inorganic materials 0.000 description 15
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- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种高纯石墨制备方法，具体地说是涉及一种二次酸浸结合热活化制备高纯度石墨的方法，包括以下步骤：将石墨碾压和粉碎；一次酸浸：将石墨浸渍在氢氟酸和硫酸形成的混合酸中；热活化处理：混合酸中过滤出石墨，进行热活化处理；二次酸浸：热活化处理完毕，冷却后将石墨进行二次酸浸，所述二次酸浸溶液为氢氟酸和硫酸的混合酸；从酸浸溶液中过滤出石墨，洗涤干燥制得。采用该方法提纯的石墨纯度可达99.99%以上。The invention discloses a method for preparing high-purity graphite, in particular to a method for preparing high-purity graphite by secondary acid leaching combined with thermal activation, comprising the following steps: rolling and pulverizing the graphite; Immersion in the mixed acid formed by hydrofluoric acid and sulfuric acid; thermal activation treatment: the graphite is filtered out from the mixed acid and subjected to thermal activation treatment; secondary acid leaching: after the thermal activation treatment is completed, the graphite is subjected to secondary acid leaching after cooling. The secondary acid leaching solution is a mixed acid of hydrofluoric acid and sulfuric acid; graphite is filtered out from the acid leaching solution, washed and dried. The purity of graphite purified by this method can reach more than 99.99%.
Description
技术领域technical field
本发明涉及一种石墨提纯方法，具体涉及一种采用二次酸浸结合热活化制备高纯度石墨的方法。The invention relates to a method for purifying graphite, in particular to a method for preparing high-purity graphite by adopting secondary acid leaching combined with thermal activation.
背景技术Background technique
石墨是碳质元素的结晶矿物，由于其优良的导电性、导热性、可塑性、润滑性、耐高温性而被广泛应用于冶金、化工、石油、机械、国防尖端技术、航空业、轻工业等众多领域。在冶金业中石墨主要作为耐火材料；在化工行业中石墨主要用作生产电池、电极以及各类碳素制品的原材料；在石油领域石墨烯的问世和迅猛发展，加快了后石油时代的发展，解决了巨大的能源问题；在机械领域中石墨主要用作各种结构零件的碳—石墨材料；在国防尖端技术中石墨可作为原子反应堆的中子减速剂和防护材料；在航空业中石墨用作导弹和火箭的隔热、耐热材料以及无线电连接信号和导电结构的材料；在轻工业中石墨是用作制造铅笔、墨汁、油墨和人造金刚石的原料，也作为造纸和玻璃防锈剂和磨光剂。随着现代工业以及现代科学技术的发展，石墨已经更加广泛的应用于其他各个领域，但这些行业需要的石墨中的固定碳含量高达99.9%以上，目前经过天然开采通过选矿处理的石墨中的碳含量最高可达95%，难以满足国民生产的要求。因此提纯出高纯度石墨显得尤为重要。Graphite is a crystalline mineral of carbonaceous elements. Because of its excellent electrical conductivity, thermal conductivity, plasticity, lubricity, and high temperature resistance, it is widely used in metallurgy, chemical industry, petroleum, machinery, advanced defense technology, aviation industry, light industry, etc. field. In the metallurgical industry, graphite is mainly used as a refractory material; in the chemical industry, graphite is mainly used as a raw material for the production of batteries, electrodes and various carbon products; in the oil field, the advent and rapid development of graphene has accelerated the development of the post-oil era. Solve the huge energy problem; in the mechanical field, graphite is mainly used as carbon-graphite material for various structural parts; in the national defense cutting-edge technology, graphite can be used as a neutron moderator and protective material for atomic reactors; in the aviation industry, graphite is used for It is used as thermal insulation and heat-resistant materials for missiles and rockets, as well as materials for radio connection signals and conductive structures; in light industry, graphite is used as a raw material for the manufacture of pencils, inks, inks and synthetic diamonds, and as a rust inhibitor and abrasive for paper and glass. light agent. With the development of modern industry and modern science and technology, graphite has been widely used in other fields, but the fixed carbon content in graphite required by these industries is as high as 99.9% or more. The content can reach up to 95%, which is difficult to meet the requirements of national production. Therefore, it is particularly important to purify high-purity graphite.
目前提纯石墨的方法一般有酸碱法、高温焙烧法、氯气焙烧法、氢氟酸法等。酸碱法提纯石墨需要高温煅烧，所需时间长且能耗大；高温焙烧法提纯石墨需要的热量非常大，使得能耗大，成本高，并且对设备的耐高温性能极高，使得成本进一步增加；氯气焙烧法由于氯气强，腐蚀性强，对环境污染尤为严重；氢氟酸法提纯石墨是一种比较好的提纯方法，但是对石墨的提纯很难达到99.99%以上。At present, the methods for purifying graphite generally include acid-base method, high temperature roasting method, chlorine roasting method, hydrofluoric acid method, etc. The purification of graphite by acid-base method requires high temperature calcination, which takes a long time and consumes a lot of energy; the purification of graphite by high temperature roasting method requires a very large amount of heat, which makes the energy consumption and cost high, and the high temperature resistance of the equipment is extremely high, which makes the cost further Increase; the chlorine roasting method is particularly serious for environmental pollution due to the strong chlorine gas and strong corrosiveness; the hydrofluoric acid method to purify graphite is a relatively good purification method, but it is difficult to purify graphite above 99.99%.
发明内容SUMMARY OF THE INVENTION
本发明为了解决现有石墨提纯方法能耗大、用时久、污染环境的问题，提供了高纯度石墨的制备方法，采用该方法制备的石墨纯度达99.99%以上。In order to solve the problems of high energy consumption, long use time and environmental pollution in the existing graphite purification method, the present invention provides a preparation method of high-purity graphite, and the purity of graphite prepared by the method reaches more than 99.99%.
本发明为了实现上述目的，所采取的技术方案为：一种HAH法制备高纯度石墨的制备方法（一种二次酸浸结合热活化制备高纯度石墨的方法），该方法包括以下步骤：In order to achieve the above purpose, the technical solution adopted in the present invention is: a preparation method for preparing high-purity graphite by HAH method (a method for preparing high-purity graphite by secondary acid leaching combined with thermal activation), the method comprises the following steps:
（1）以天然石墨为原料，碾压和粉碎后将其在氢氟酸浓度为5%~10%，硫酸浓度为30%~50%的混合酸性溶液中浸泡，酸浸温度为70℃~75℃，酸浸时间为2h~4h，完成上述步骤后，对其进行热活化处理，将石墨装入带盖子的高纯石墨坩埚，置于箱式高温电阻炉中，对其进行热活化处理，热活化温度为700℃～800℃，活化时间为55min~65min。(1) Using natural graphite as raw material, after rolling and crushing, soak it in a mixed acid solution with a concentration of 5%~10% hydrofluoric acid and 30%~50% sulfuric acid, and the acid leaching temperature is 70℃~ 75 ℃, the acid leaching time is 2h~4h, after the above steps are completed, heat activation treatment is performed, the graphite is put into a high-purity graphite crucible with a lid, placed in a box-type high temperature resistance furnace, and heat activation treatment is carried out. , the thermal activation temperature is 700 ℃ ~ 800 ℃, and the activation time is 55min ~ 65min.
由于任何硅酸盐在一定条件下都可以被氢氟酸溶解，它利用石墨中的杂质和氢氟酸反应生成溶于水的氟化物及挥发物而达到提纯的目的。研究表明，当氢氟酸浓度小于2.5%时，石墨纯度随温度提高而不断提高，当氢氟酸浓度大于5%时，石墨纯度变化很小；一次酸浸硫酸浓度低于30%时，石墨纯度随硫酸浓度的增大而不断提高，当浓度大于30%后，石墨纯度变化不大；Since any silicate can be dissolved by hydrofluoric acid under certain conditions, it uses the impurities in graphite to react with hydrofluoric acid to generate water-soluble fluoride and volatiles to achieve the purpose of purification. Studies have shown that when the concentration of hydrofluoric acid is less than 2.5%, the purity of graphite increases continuously with the increase of temperature. When the concentration of hydrofluoric acid is greater than 5%, the purity of graphite changes very little; when the concentration of sulfuric acid in one acid leaching is less than 30%, graphite The purity increases with the increase of sulfuric acid concentration. When the concentration is greater than 30%, the purity of graphite does not change much;
酸浸溶液酸浸温度采用70℃~75℃，此温度能使石墨中杂质活性达到最高，从而有效减少酸浸时间，缩短操作耗时；The acid leaching temperature of the acid leaching solution is 70℃~75℃, which can make the activity of impurities in the graphite reach the highest level, thereby effectively reducing the acid leaching time and shortening the operation time;
一次酸浸溶液酸浸时间为2h~4h，当一次酸浸时间低于2h，石墨纯度随酸浸时间不断提高，随着时间继续增加，石墨纯度有小幅提升。The acid leaching time of an acid leaching solution is 2h~4h. When the acid leaching time is less than 2h, the graphite purity increases continuously with the acid leaching time, and the graphite purity increases slightly as the time continues to increase.
对经一次酸浸提纯后的石墨进行热活化处理，可以有效提高石墨中残余杂质的活性。与未经活化处理的样品相比，石墨纯度得到显著提高。其主要原因是一些粘土类矿物在700℃～800℃范围内会脱水分解形成的无定形的SiO2和Al2O3，这是其活性提高的主要来源。从热力学角度分析，杂质矿物经过活化处理，置于空气中高速冷却后，晶格结构的有序状态遭到破坏，这一点在杂质晶粒表面表现的更为明显，从而显著降低了其反应所需的活化能及进一步提纯的难度。实验表明，氢氟酸法提纯石墨时的氢氟酸用量是理论用量的3.15倍，而通过加入热活化处理工艺，其用量可以减少三分之二，比理论用量还略低，同时石墨固定碳含量可以从99.74%提高至99.98%，故热活化处理，使得杂质活性显著提高，其中活性提高较大的部分甚至可以与硫酸直接反应，从而减少氢氟酸的用量。The thermal activation treatment of the graphite purified by one acid leaching can effectively improve the activity of the residual impurities in the graphite. The graphite purity is significantly improved compared to the unactivated sample. The main reason is that some clay minerals will dehydrate and decompose in the range of 700℃～800℃ to form amorphous SiO 2 and Al 2 O 3 , which is the main source of their activity improvement. From the perspective of thermodynamics, after the impurity minerals are activated and cooled in the air at a high speed, the ordered state of the lattice structure is destroyed, which is more obvious on the surface of the impurity grains, thus significantly reducing the reaction time. The required activation energy and the difficulty of further purification. Experiments show that the amount of hydrofluoric acid used in the purification of graphite by the hydrofluoric acid method is 3.15 times the theoretical amount, and by adding a thermal activation process, the amount of hydrofluoric acid can be reduced by two-thirds, which is slightly lower than the theoretical amount. At the same time, graphite fixes carbon. The content can be increased from 99.74% to 99.98%, so the thermal activation treatment can significantly improve the activity of impurities, and the part with greater activity can even react directly with sulfuric acid, thereby reducing the amount of hydrofluoric acid.
（2）将经上述处理后的石墨取出快速冷却，再将其在氢氟酸浓度为1%~4%，硫酸浓度为20%~30%的混合酸性溶液中浸泡，酸浸温度为70℃~75℃，酸浸时间为2h~4h。(2) The graphite after the above treatment is taken out and rapidly cooled, and then immersed in a mixed acid solution with a hydrofluoric acid concentration of 1%~4% and a sulfuric acid concentration of 20%~30%, and the acid leaching temperature is 70 ℃ ~75℃, the acid leaching time is 2h~4h.
与一次酸浸的规律类似，石墨纯度随二次酸浸氢氟酸浓度的增加而不断提高，在2%处达到99.98%，之后基本不变。当单独使用硫酸进行提纯时，石墨纯度较低，仅为99.84%。加入少量氢氟酸，石墨纯度明显提高。虽然热火化提高了石墨中杂质的活性，但该活性必须在氢氟酸的参与下才能充分体现。Similar to the law of the primary acid leaching, the purity of graphite increases with the increase of the hydrofluoric acid concentration of the secondary acid leaching, reaching 99.98% at 2%, and then basically unchanged. When purified with sulfuric acid alone, the graphite purity is lower, only 99.84%. Adding a small amount of hydrofluoric acid, the purity of graphite is significantly improved. Although thermal cremation improves the activity of impurities in graphite, the activity must be fully manifested with the participation of hydrofluoric acid.
二次酸浸溶液浸泡时间2h~4h，当二次酸浸时间小于2h，石墨纯度随时间增加不断提高，在2h左右达到99.99%，之后不在有显著变化。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥即可得到固定碳含量达到99.99%以上的高纯度石墨。The immersion time of the secondary acid leaching solution is 2h~4h. When the secondary acid leaching time is less than 2h, the graphite purity increases continuously with the increase of time, reaching 99.99% in about 2h, and there is no significant change after that. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven to obtain high-purity graphite with a fixed carbon content of more than 99.99%.
本发明的有益效果是：与氢氟酸法相比，通过加入热活化工艺，使得氢氟酸浓度及用量都显著降低；与其他石墨提纯方法相比，具有操作简单，耗时短，能耗小，生产成本低，能有效去除石墨中的杂质，使提纯后的石墨固定碳含量达到99.99%以上。The beneficial effects of the present invention are: compared with the hydrofluoric acid method, by adding a thermal activation process, the concentration and consumption of hydrofluoric acid are significantly reduced; compared with other graphite purification methods, the invention has the advantages of simple operation, short time consumption and low energy consumption , the production cost is low, the impurities in the graphite can be effectively removed, and the fixed carbon content of the purified graphite can reach more than 99.99%.
具体实施方式Detailed ways
下面结合具体是实施例对本发明做进一步详细的解释说明，但应当理解本发明的保护范围并不受具体实施例的限制。以下实施例中氢氟酸或硫酸的浓度是指该酸在混合酸中的质量分数。The present invention will be further explained in detail below in conjunction with the specific embodiments, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. The concentration of hydrofluoric acid or sulfuric acid in the following examples refers to the mass fraction of the acid in the mixed acid.
实施例1Example 1
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为10%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.992%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 10% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.992% according to the method in Patent 201110056199.6.
实施例2Example 2
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为10%的氢氟酸、浓度为50%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.992%。Using natural graphite as raw material, the graphite was rolled and crushed, and then soaked in a mixed acid solution of hydrofluoric acid with a concentration of 10% and sulfuric acid with a concentration of 50%. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.992% according to the method in Patent 201110056199.6.
实施例3Example 3
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为8%的氢氟酸、浓度为40%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.992%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 8% hydrofluoric acid and 40% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.992% according to the method in Patent 201110056199.6.
实施例4Example 4
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为75℃，酸浸时间4h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.993%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.993% according to the method in Patent 201110056199.6.
实施例5Example 5
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为75℃，酸浸时间3h，再对其进行热活化处理，热活化温度为700℃，活化时间80min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.993%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 °C, and the activation time was 80 minutes; the graphite after the above treatment was taken out and rapidly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.993% according to the method in Patent 201110056199.6.
实施例6Example 6
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为800℃，活化时间90min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.995%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 800 °C, and the activation time was 90 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.995% according to the method in Patent 201110056199.6.
实施例7Example 7
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为4%、硫酸浓度为30%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.993%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 min; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 4% and a sulfuric acid concentration of 30%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.993% according to the method in Patent 201110056199.6.
实施例8Example 8
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为20%的混合酸性溶液中浸泡，酸浸温度为75℃，酸浸时间4h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.994%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 20%. Soak in medium, the acid leaching temperature is 75 ℃, and the acid leaching time is 4h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.994% according to the method in Patent 201110056199.6.
实施例9Example 9
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为3%、硫酸浓度为25%的混合酸性溶液中浸泡，酸浸温度为75℃，酸浸时间4h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.993%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 minutes; the graphite after the above treatment was taken out and rapidly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 3% and a sulfuric acid concentration of 25%. Soak in medium, the acid leaching temperature is 75 ℃, and the acid leaching time is 4h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.993% according to the method in Patent 201110056199.6.
实施例10Example 10
以天然石墨为原料，将石墨碾压和粉碎后将其在浓度为5%的氢氟酸、浓度为30%的硫酸混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h，再对其进行热活化处理，热活化温度为700℃，活化时间60min；将经上述处理后的石墨取出快速冷却，再将样品在氢氟酸浓度为2%、硫酸浓度为30%的混合酸性溶液中浸泡，酸浸温度为70℃，酸浸时间2h。最后从酸浸溶液中过滤出石墨，并用高纯水洗涤至PH约6.5~7.0，再置于干燥箱中干燥。经上述方法提纯后，按照专利201110056199.6中方法检测石墨中固定碳含量为99.996%。Using natural graphite as raw material, the graphite was rolled and pulverized, and then soaked in a mixed acid solution of 5% hydrofluoric acid and 30% sulfuric acid. It was subjected to thermal activation treatment, the thermal activation temperature was 700 ° C, and the activation time was 60 min; the graphite after the above treatment was taken out and quickly cooled, and then the sample was placed in a mixed acid solution with a hydrofluoric acid concentration of 2% and a sulfuric acid concentration of 30%. Soak in medium, the acid leaching temperature is 70 ℃, and the acid leaching time is 2h. Finally, the graphite is filtered out from the acid leaching solution, washed with high-purity water to a pH of about 6.5~7.0, and then dried in a drying oven. After purification by the above method, the content of fixed carbon in the graphite was detected as 99.996% according to the method in Patent 201110056199.6.
上述仅为本发明的优选实施例，本发明并不仅限于实施例的内容。对于本领域中的技术人员来说，在本发明的技术方案范围内可以有各种变化和更改，所作的任何变化和更改，均在本发明保护范围之内。The above are only preferred embodiments of the present invention, and the present invention is not limited to the contents of the embodiments. For those skilled in the art, various changes and modifications can be made within the scope of the technical solution of the present invention, and any changes and modifications made are within the protection scope of the present invention.
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