Production of high purity rare earth mixture from iron-rich spent fluid catalytic cracking (FCC) catalyst using acid leaching and two-step solvent extraction process

Le-Phuc Nguyen; Yen Thi Hai Pham; Phuong Thuy Ngo; Tri Van Tran; Loc Vinh Tran; Nam Thi Hoai Le; Luong Huu Nguyen; Tung Thanh Dang; Duc Anh Nguyen; Marco Wenzel; David Hartmann; Karsten Gloe; Jan J. Weigand; Klaus Kretschmer

Korean Journal of Chemical Engineering, Vol.35, No.5, 1195-1202, May, 2018

DOI10.1007/s11814-018-0022-z Export Citation

Production of high purity rare earth mixture from iron-rich spent fluid catalytic cracking (FCC) catalyst using acid leaching and two-step solvent extraction process

Le-Phuc Nguyen^{1, †}, Yen Thi Hai Pham¹, Phuong Thuy Ngo¹, Tri Van Tran¹, Loc Vinh Tran^{1, 2}, Nam Thi Hoai Le², Luong Huu Nguyen¹, Tung Thanh Dang¹, Duc Anh Nguyen¹, Marco Wenzel³, David Hartmann³, Karsten Gloe³, Jan J. Weigand^{3, †}, and Klaus Kretschmer⁴

¹Catalysis Research Department, Vietnam Petroleum Institute, Saigon Hi-Tech Park, District 9, Ho Chi Minh City, Vietnam
²Vietnam Academy of Science and Technology, Vietnam
³Department of Chemistry and Food Chemistry, TU Dresden, 01062 Dresden, Germany
⁴Delta Engineering & Chemistry GmbH, 14476 Groβglienicke, Germany

E-mail:,

Acid leaching and a two-step solvent extraction procedure were developed to produce high purity mixture of La and Ce from iron-rich spent FCC catalyst discharged from Dzung Quat refinery (Vietnam). Acid leaching of the spent catalyst with 2M HNO3 and a solid-to-liquid ratio of 1/3 at 80 °C in 1 h dissolved almost 90% of La while 12% of Al and 25% of Fe were transferred to the leachate. The extraction of RE metals and main impurities such as Al and Fe by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) was investigated. Experiments showed that it was necessary to remove Fe before extracting RE and the optimum extraction conditions for a high recovery of RE while 0% of Al extraction were pH≤1, contact time=10min, and D2EHPA/TBP volume ratio= 4 : 1. At these conditions, the extraction yields of La(III) and Ce(III) were 72% and 89%, respectively. A two-step solvent extraction was developed to achieve a high purity of RE mixture, which included (1) the removal of impurity Fe by 25% (v/v) diisooctyl phosphinic acid (DiOPA) in n-octane for 140 min, (2) the extraction of rare earths by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) in n-octane for 10 min without the need for adjusting the pH of the leaching solution.

Keywords:Spent FCC Catalyst;Rare Earth;Leaching;Solvent Extraction;Dzung Quat Refinery;Iron

[References]

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[2] Chou MIM, Chen LM, Chou SFJ, Int. J. Environ. Sust., 8, 19 (2013)

[3] Ferella F, Innocenzi V, Maggiore F, Res. Conserv. Recy., 108, 10 (2016)

[4] Nguyen CT, Nguyen HM, Ta MQ, PetroVietnam J., 11, 43 (2013)

[5] Gao X, Owens WT, US Patent, US20120156116 A1 (2012).

[6] Jordens A, Cheng YP, Waters KE, Miner. Eng., 41, 97 (2013)

[7] Binnemans K, Jones PT, Blanpain B, Gerven TV, Yang Y, Waltone A, Buchertf M, J. Clean Prod., 51, 1 (2013)

[8] Duby PF, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons Inc. (2000).

[9] Li L, Xu S, Ju Z, Wu F, Hydrometallurgy, 100, 41 (2009)

[10] Zhang PW, Yokoyama T, Itabashi O, Wakui Y, Suzuki TM, Inoue K, J. Power Sources, 77(2), 116 (1999)

[11] Pietrelli L, Bellomo B, Fontana D, Montereali MR, Hydrometallurgy, 66, 135 (2002)

[12] Zhang P, Yokoyama T, Itabashi O, Wakui Y, Suzuki TM, Inoue K, Hydrometallurgy, 50, 61 (1998)

[13] Jiang Y, Shibayama A, Liu K, Fujita T, Hydrometallurgy, 76, 1 (2005)

[14] Jiang Y, Shibayama A, Liu K, Fujita T, Can. Metall. Q., 43, 431 (2004)

[15] Lee CH, Yen HY, Liao CH, Popuri SR, Cadogan EI, Hsu CJ, J. Mater. Cycles Waste Manage., 19, 102 (2017)

[16] Lee CH, Chen YJ, Liao CH, Popuri SR, Tsai SL, Hung CE, Metall. Mater. Trans. A-Phys. Metall. Mater. Sci., 44, 5825 (2013)

[17] Innocenzi V, Ferella F, Michelis ID, Veglio F, J. Ind. Eng. Chem., 24, 92 (2015)

[18] Zhao Z, Qiu Z, Jang J, Lu S, Cao L, Zhang W, Xu Y, Hydrometallurgy, 167, 183 (2016)

[19] Wenzel M, Schnaars K, Kelly N, et al., Rare Metal Technology, John Wiley & Sons Inc., NJ (2016).

[20] ASTM D7085, Standard Guide for Determination of Chemical Elements in Fluid Catalytic Cracking Catalysts by X-ray Fluorescence Spectrometry (XRF) (2010).

[21] Wang J, Xu Y, Wang L, Zhao L, Wang Q, Cui D, Long Z, Huang X, J. Environ. Chem. Eng., 5, 3711 (2017)

[22] Moeller T, The Chemistry of the Lanthanides, Reinhold Publishing, New York (1963).

[23] Xia C, Canad. Institute of Mining, Metallurgy and Petroleum, Westmont (2013).

[24] Gupta CK, Krishnamurthy N, Extractive metallurgy of rare earths, CRC Press, Florida (2005).

[25] Roddy JW, Coleman CF, Arai S, J. Inorg. Nucl. Chem., 33, 1099 (1971)

[26] Sato T, Nakamura T, Ikeno M, Hydrometallurgy, 15, 209 (1985)

[27] Matsuyama H, Miyake Y, Izumo Y, Teramoto M, Hydrometallurgy, 24, 37 (1990)

[28] Silberberg MS, Principles of general chemistry, McGraw-Hill, U.S.A. (2010).

[29] Avgouropoulos G, Environmental Catalysis over Gold-Based Materials, RSC (2013).

[30] Reger DL, Goode SR, Ball DW, Chemistry: Principles and Practice, Brooks/Cole, U.S.A. (2010).

[31] Snoeyink VL, Jenkins D, Water Chemistry, John Wiley & Sons, New York (1980).

[32] Seo EY, Cheong YW, Yim GJ, Min KW, Geroni JN, Catena, 148, 11 (2017)

[33] Tian J, Chi R, Zhu G, Xu S, Zhang Z, Nonferrous Met., 2, 57 (2000)

[34] Liu K, Wang Y, Wei M, Tang X, Zhang P, China Patent, CN 107130120 A (2017).

[35] Maeda M, Narita H, Tokoro C, Tanaka M, Motokawa R, Shiwaku H, Yaita T, Sep. Purif. Technol., 177, 176 (2017)

[36] Liu M, Zhou Y, The Chinese J. Nonferrous Met., 15(10), 1648 (2005)

[37] Yu S, Chen J, Hydrometallurgy, 22, 183 (1989)

[38] Osaka AF, Nara IM, Osaka MT, US Patent, US 4582691 A (1986).

[39] Nucciarone D, Jakovljevic B, Medeiros BAF, Hill-house J, DePalo M, Sole, et al., Proceedings of the International Solvent Extraction Conference ISEC,, 1, 402 (2002)

[40] Lin-yan L, Sheng-ming X, Zhong-jun J, Zhang Z, Fu-hui L, Guo-bao L, Trans. Nonferrous Met. Soc. China, 20, 205 (2010)