Progress on the separation, purification and application of natural graphite

doi:10.16085/j.issn.1000-6613.2020-2348

Abstract

Abstract:

As a strategic non-metallic mineral resource, the unique structure of natural graphite makes it have excellent electrical conductivity (resistivity 8×10^-6~13×10^-6Ω·m), strong plasticity, low friction coefficient (0.08~0.16), high temperature resistance, stable chemical properties, good natural floatability and other properties, and thus it is a key raw material necessary for many industries. At the same time, natural graphite has a wide range of uses, high added value of deep-processed products and long industrial chain. In addition to being widely used in refractory, sealing, casting, conductive materials and other traditional industrial fields, natural graphite also has great application prospects in emerging fields such as new energy, new generation electronic information technology, new energy vehicles and high-end equipment manufacturing, which makes it well-known as “industrial black gold”. China is rich in graphite resources, but has not yet become a strong country in graphite resources. Based on the current status of graphite mineral resources, the international trade data and the structure of graphite consumption market, this article analyzed the comprehensive utilization of China's natural graphite. On this basis, the separation technology, purification method, preparation of deep-processed products and the application in the emerging strategic industry were discussed. The comprehensive utilization of graphite resources was systematically introduced, which mainly involved three important types of graphite deep processing products, such as graphite interlaminar compound, spherical graphite and graphene. Finally, the future direction of strengthening the development and utilization of graphite resources was proposed according to the trend of the graphite industry.

Key words: natural graphite, graphite purification, graphite deep processing, graphite application

摘要：

作为战略性非金属矿产资源，天然石墨独特的结构使得它具有导电性良好（电阻率8×10^-6~13×10^-6Ω·m）、可塑性强、摩擦系数小（0.08~0.16）、耐高温、化学性质稳定、天然可浮性好等物化特性，是多种工业必需的关键原料。同时天然石墨具有用途广泛、深加工产品附加值高、产业链条长等特点，除广泛应用于耐火材料、密封、铸造、导电材料等传统工业领域，在新能源、新一代电子信息技术、新能源汽车、高端装备制造业等新兴领域也有着极大的应用前景，被誉为“工业黑金”。我国石墨资源丰富，但尚未成为石墨资源强国，本文基于近年来我国石墨矿产资源开发现状、对外进出口贸易数据以及石墨消费市场结构，分析了天然石墨综合利用现状，并在此基础上对天然石墨分选工艺、提纯方法、深加工产品的制备及在新兴战略性产业领域的应用展开讨论，系统介绍了石墨资源的综合利用进展，其中主要涉及石墨层间化合物、球形石墨和石墨烯三类重要的石墨深加工产品。最后，基于石墨产业的发展趋势，给出加强石墨资源开发利用的发展方向。

关键词: 天然石墨, 石墨提纯, 石墨深加工, 石墨应用

CLC Number:

TD951

GUO Runnan, LI Wenbo, HAN Yuexin. Progress on the separation, purification and application of natural graphite[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6155-6172.

郭润楠, 李文博, 韩跃新. 天然石墨分选提纯及应用进展[J]. 化工进展, 2021, 40(11): 6155-6172.

Figures/Tables 13

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国家和地区	2014年	2015年	2016年	2017年	2018年	2019年
合计	110.77	109.87	109.61	86.84	103.95	116.23
巴西	8.70	7.51	8.50	8.50	9.50	9.60
加拿大	3.00	3.00	3.00	4.00	4.00	4.00
中国	78.00	78.00	78.00	62.50	63.00	70.00
印度	11.67	13.46	12.24	3.50	3.50	3.50
马达加斯加	0.53	0.81	0.92	1.33	4.81	4.81
墨西哥	0.92	0.65	0.38	0.17	0.42	0.42
莫桑比克	—	—	—	—	10.40	15.30
俄罗斯	1.76	1.59	1.94	2.52	1.78	1.66
斯里兰卡	0.40	0.42	0.40	0.35	0.40	0.40
乌克兰	1.38	1.45	1.46	1.49	1.50	1.50
津巴布韦	0.70	0.70	0.60	0.16	0.20	0.20
其他	3.71	2.28	2.16	2.29	4.44	4.84

国家和地区	2014年	2015年	2016年	2017年	2018年	2019年
合计	110.77	109.87	109.61	86.84	103.95	116.23
巴西	8.70	7.51	8.50	8.50	9.50	9.60
加拿大	3.00	3.00	3.00	4.00	4.00	4.00
中国	78.00	78.00	78.00	62.50	63.00	70.00
印度	11.67	13.46	12.24	3.50	3.50	3.50
马达加斯加	0.53	0.81	0.92	1.33	4.81	4.81
墨西哥	0.92	0.65	0.38	0.17	0.42	0.42
莫桑比克	—	—	—	—	10.40	15.30
俄罗斯	1.76	1.59	1.94	2.52	1.78	1.66
斯里兰卡	0.40	0.42	0.40	0.35	0.40	0.40
乌克兰	1.38	1.45	1.46	1.49	1.50	1.50
津巴布韦	0.70	0.70	0.60	0.16	0.20	0.20
其他	3.71	2.28	2.16	2.29	4.44	4.84

制备方法	优点	缺点
微机械剥离法	操作相对简单，可得到纯度高、结构完整、物化性能未被破坏的高质量产品，宜用于理论研究	产品尺寸较小、存在很大不确定性、对设备要求高、产量小、效率低、成本高、不宜大规模生产
外延生长法	控制温度可获得不同厚度的产品，所得石墨烯可以直接进行表征测试，适合理论研究	制备条件苛刻、成本高、产品厚度不均一、物化性质有破坏、不易从衬底分离、不宜大规模生产
CVD法	产量可观、产品尺寸较大、均匀性好、质量高、可控性好	设备要求高、工艺复杂、成本较高、石墨烯转移过程复杂、操作条件苛刻
氧化石墨-还原法	设备简单、产量高、成本较低、生产周期短、操作简单	产品结构有缺陷、物化性质有破坏、设备腐蚀严重、环境污染较大

制备方法	优点	缺点
微机械剥离法	操作相对简单，可得到纯度高、结构完整、物化性能未被破坏的高质量产品，宜用于理论研究	产品尺寸较小、存在很大不确定性、对设备要求高、产量小、效率低、成本高、不宜大规模生产
外延生长法	控制温度可获得不同厚度的产品，所得石墨烯可以直接进行表征测试，适合理论研究	制备条件苛刻、成本高、产品厚度不均一、物化性质有破坏、不易从衬底分离、不宜大规模生产
CVD法	产量可观、产品尺寸较大、均匀性好、质量高、可控性好	设备要求高、工艺复杂、成本较高、石墨烯转移过程复杂、操作条件苛刻
氧化石墨-还原法	设备简单、产量高、成本较低、生产周期短、操作简单	产品结构有缺陷、物化性质有破坏、设备腐蚀严重、环境污染较大