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Minerals Engineering 15 (2002) 755757

Technical Note

This article is also available online at: www.elsevier.com/locate/mineng

Preparation of high-purity and low-sulphur graphite from Woxna ne graphite concentrate by alkali roasting
X.J. Lu *, E. Forssberg
Division of Mineral Processing, Lule University of Technology, SE-971 87 Lule, Sweden a a Received 8 July 2002; accepted 13 August 2002

Abstract An alkali roasting process, which consists of roasting with caustic soda, water washing and sulphuric acid leaching, has been found to be an eective method for graphite purication even at low roasting temperature. With this process, a otation ne concentrate containing 8788% carbon could be puried to about 99.4% carbon when roasted with 25% NaOH at 250 C and leached by 10% H2 SO4 solution at room temperature. In addition to the successful removal of silicate impurities, the process was also found to be eective to eliminate sulphide impurities. For instance, the sulphur content in the end product could be reduced to below 0.05% from 0.6% by the process. Furthermore, the consumption of NaOH can be lowered by using high-grade feed. When using a feed of 95.9% carbon (upgraded by otation), the NaOH concentration could be reduced to 10% from 25% while the product purity could reach the same purity level of over 99%. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Industrial minerals; Roasting; Leaching

1. Introduction Graphite is the mineral which is easiest to oat as rougher concentrate, but very dicult to be upgraded further by otation or other mechanical processing methods. By the process of scrubbing and two-step cleaning otation (Lu and Forssberg, 2001a,b), a ne graphite concentrate containing 8788% carbon can be upgraded to about 95% carbon, but further upgrading by otation is dicult. So chemical purication is always essential to produce high purity graphite. Alkali roasting has been reported to be eective to eliminate silicate impurities from graphite ores and the alkali roasting process is always conducted at high temperatures ranging from 500 to 900 C (Liu et al., 2000; Sun and Cheng, 1995; Sun et al., 1995). But its eectiveness at low roasting temperatures of below 500 C and its eect on removal of other impurities remain uncertain. Therefore, it is interesting to study its eciency at low

roasting temperatures and its eect on removing other impurities.

2. Experimental The graphite sample used in this study is the ne otation concentrate ()80 lm) from Woxna Graphite AB (Sweden), and the reagents include NaOH (analytical reagent, purity 99%), H2 SO4 (analytical reagent, concentration 98%) and HCl (analytical reagent, concentration 35%). Mineralogical characterization of the raw material was conducted by thin-section and polished section optical microscopy coupled with XRD analysis and SEM analysis. The whole alkali roasting process including roasting, water washing, acid leaching and drying. First, mixtures of NaOH and raw graphite powder were roasted in a laboratory furnace. Then, the roasted materials were washed to neutral (pH 7) on a vacuum lter to remove the soluble roasting products and to remove the extra alkali, and the washed materials were treated with 10% H2 SO4 in a beaker to further remove the insoluble compounds, mainly hydroxides and oxides. Finally, the acid leached materials were washed to neutral (pH 7) on a vacuum lter and dried in a dryer.

* Corresponding author. Address: Department of Chemical & Environmental Engineering, Shandong University of Science & Technology, No. 17 Sheng Li Zhuang Road, Jinan, Shandong 250031, China. Tel.: +86-531-5903564; fax: +86-531-5903161. E-mail address: xianjun_lu@hotmail.com (X.J. Lu).

0892-6875/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 8 9 2 - 6 8 7 5 ( 0 2 ) 0 0 1 7 2 - 3

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X.J. Lu, E. Forssberg / Minerals Engineering 15 (2002) 755757

3. Results and discussion 3.1. Mineralogical properties The chemical composition of the raw material was analyzed as C 87.7%, S 0.6%, SiO2 5.25%, Al2 O3 2.93%, Fe2 O3 1.65%, CaO 0.35%, MgO 0.55%, MnO 0.02%, K2 O 0.65%, Na2 O 0.06%, P2 O5 0.01%, TiO2 0.13%, and trace elements 0.2%. And an estimate of the mineral composition was made as graphite 87.5%, clays 5.5%, mica 4.0%, feldspar and quartz 1.5%, and pyrrhotite (pyrite) 1.5%, which indicates that the major impurities are silicates, aluminosilicates and sulphides. 3.2. Eect of roasting temperature The eect of roasting temperatures was rst investigated and the procedure was as follows. First, the raw material was mixed with 25% NaOH solution in a liquidsolid ratio of 2:1 (w/w), and then roasted at dierent temperatures for 1 h. Then, the roasted mixtures were washed to neutral (pH 7) on a vacuum lter. Finally, the water washing residues were leached by 10% H2 SO4 solution at room temperature and the liquidsolid ratio was controlled as 4:1 (w/w). The results (Fig. 1) show that the material can be eectively puried even at low roasting temperatures. The product purity reaches 98.2% at 150 C and reaches the peak value of 99.4% at 250 C from a feed purity of 87.71%, and then the purity no longer increases at higher roasting temperatures. This indicates that to achieve a successful purication for this material the roasting temperature can be as low as 150 C. But, the best product purity can be achieved at 250350 C. 3.3. Eect of NaOH dosage Following the same procedure as the above tests, the eect of NaOH concentration was tested at the roasting temperature of 250 C and the roasting time of 1 h. The results (Fig. 2) show that along with the increase of NaOH concentration the product purity rises until the concentration reaches 25%, after that the purity curve becomes at. This suggests that the NaOH concentration should be kept at 25%. Besides, a higher purity can be observed at relative higher liquidsolid ratio of 2:1 (Fig. 2), which indicate that to acquire over 99% purity the liquidsolid ratio should be maintained as about 2:1. As the liquidsolid ratio inuences the mixing eect between NaOH solution and graphite powder, satisfactory mixing can only be achieved at a relative higher liquidsolid ratio of 2:1 concerning this ne graphite material. Also, the results (Fig. 2) show that to get a product purity of over 99% the NaOH concentration can be reduced to 10% from 25% when a feed of 95.9% carbon content (upgraded by scrubbing and otation) is used, in other words the dosage of NaOH can be reduced to 200 kg/t from 500 kg/t. Furthermore, the product purity can be improved with a high grade feed (see Fig. 2). It is clear that with a high-grade feed the NaOH consumption can be reduced and the product purity can also be further improved. 3.4. Eect of sulphur removal by alkali roasting process The sulphur content in the raw material reaches 0.6%, which is unacceptable in many applications. Direct roasting experiments (without NaOH) proved that roasting at high temperatures of over 500 C was eective to remove the sulphur in this material, but the efciency was poor at temperatures below 500 C (Fig. 3). When the material was treated by the alkali roasting process, it has been found that the process was eective to eliminate the sulphur in this material even at roasting temperatures much lower than 500 C (Fig. 3). A sulphur level of below 0.05% could be achieved within the roasting temperatures of 200350 C. This indicates that it is not necessary to keep a high roasting temperature when the alkali roasting process is applied. Thus, there must be some chemical reaction between NaOH and the

Fig. 2. Eect of NaOH concentration and feed purity on product purity.

Fig. 1. Eect of roasting temperature on product purity (raw material purity: 87.71%).

X.J. Lu, E. Forssberg / Minerals Engineering 15 (2002) 755757

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otation concentrate from Woxna Graphite AB can be puried to about 99.4% from 8788%, and the sulphur content in the product can be reduced to below 0.05% from 0.6%. Furthermore, with a high-grade graphite feed, the NaOH consumption can be reduced and the product purity can be further improved.

Acknowledgements This work was completed with the nancial support of China Scholarship Council and Woxna Graphite AB.
Fig. 3. Eect of roasting with and without NaOH on sulphur removal (roasting time: 1 h).

References sulphidespyrrhotite and pyrite. A possible reaction is suggested as: FeS 2NaOH O2 FeO Na2 SO4 H2 O 1
Liu, H.Q. et al., 2000. Study on purication technology of aphanitic graphite by calcining under high temperature and alkali. Carbon Techniques 1, 1214. Lu, X.J., Forssberg, E., 2001a. Study on the upgrading of Woxna ne graphite concentrate. In: Proceedings of New Developments in Mineral Processing Conference. Beril Ofset, Istanbul, Turkey, pp. 339352, ISBN 975 972 97277-6-5. Lu, X.J., Forssberg, E., 2001b. Flotation selectivity and upgrading of Woxna ne graphite concentrate. Minerals Engineering 14 (11), 15411543. Sun, B.Q. et al., 1995. Further Processing of Non-metallic Minerals. Metallurgical Industry Press, Beijing, pp. 3157. Sun, B.Q., Cheng, Z.B., 1995. Chemical purication of industrial minerals. In: Proceedings of the XIX IMPC, vol. 2. Society for Mining, Metallurgy, and Exploration, Inc, Littleton, CO, pp. 207 211.

4. Conclusions It has been found out that the alkali roasting purication process is an eective method both for the removal of silicate impurities and for the removal of sulphide impurities even at low roasting temperatures of 200300 C. After roasting with NaOH at 250 C, and followed by water washing and H2 SO4 leaching, the ne