[논문]석유화학공정 폐촉매에 함유된 희유금속의 유기산 침출

르민난; 이만승

doi:10.7844/kirr.2019.28.6.36

석유화학공정 폐촉매에 함유된 희유금속의 유기산 침출
Leaching of Rare Metals from Spent Petroleum Catalysts by Organic Acid Solution 원문보기

資源리싸이클링 = Journal of the Korean Institute of Resources Recycling, v.28 no.6, 2019년, pp.36 - 45

르민난 (목포대학교 공과대학 신소재공학과) , 이만승 (목포대학교 공과대학 신소재공학과)

초록
AI-Helper

석유화학공정에서 발생하는 폐촉매는 바나듐, 몰리브덴, 니켈, 코발트와 같은 희유금속을 함유하고 있다. 유기산에 의한 상기 금속의 침출에 대해 연구하였다. 본 논문에서 사용한 유기산에 의한 금속의 침출률은 옥살산 > 타르타르산 > 구연산 > 말레산 > 오스코브르산 순서이었다. 상기 유기산은 바나듐과 몰리브덴의 침출에 선택성이 있으며 옥살산에 의한 침출률이 가장 높았다. 옥살산의 농도, 반응온도, 광액밀도, 교반속도를 변화시켜 옥살산에 의한 바나듐의 최적침출조건을 얻었다. 옥살산에 의한 바나듐의 침출에 대한 속도식을 조사한 결과 Avrami식과 잘 맞았으며 활성화에너지는 8.76 kJ/mol로 물질전달에 의해 침출반응이 율속되었다.

Abstract ▼ AI-Helper

The spent petroleum catalysts contain rare metals such as vanadium, nickel, molybdenum, and cobalt. Therefore, the leaching of these rare metals from spent petroleum catalysts by organic acid was investigated in the present study. The leaching efficiency of metals by organic acid was in the following order: oxalic acid > tartaric acid > citric acid > maleic acid > ascorbic acid. Among the organic acids employed in this work, oxalic acid can be considered to be superior to the other acids in terms of metals leaching efficiency. The effect of several leaching conditions such as temperature, acid concentration, pulp density, stirring speed, and reaction time on the leaching of metals was investigated. Vanadium and molybdenum were selectively dissolved by oxalic acid from the spent catalysts. The leaching kinetics of vanadium by oxalic acid was also investigated. An activation energy of 8.76 kJ/mol indicated that the leaching kinetics of vanadium by oxalic acid solution was controlled by mass transfer.

주제어

표/그림 (11)

그림 Fig. 1. Leaching percentage of metals from the spent catalyst by organic acids.
표 Table 1. Stability constants for metal complexes of oxalic acid
그림 Fig. 2. Effect of temperature on the dissolution of metals.
그림 Fig. 3. Effect of oxalic acid concentration on the dissolution of metals.
그림 Fig. 4. Effect of pulp density on the dissolution of metals.
그림 Fig. 5. Effect of stirring speed on the dissolution of metals.
그림 Fig. 6. Effect of leaching time on the dissolution of metals.
표 Table 2. A summary of the optimal conditions for the leaching of spent catalysts by oxalic acid
표 Table 3. Kinetic models tested in the leaching of metals from various materials
그림 Fig. 7. Plot of ln(-ln(1-x)) vs. leaching time at various (a) temperatures, (b) oxalic acid concentrations, and (c) pulp densities.
그림 Fig. 8. Arrhenius plot for the activation energy of vanadium leaching by oxalic acid solution.

AI 본문요약
AI-Helper

* AI 자동 식별 결과로 적합하지 않은 문장이 있을 수 있으니, 이용에 유의하시기 바랍니다.

문제 정의

Therefore, oxalic acid was selected for further leaching experiments to investigate the effect of some factors on the dissolution behavior of metals from the spent catalyst. The aim was to find the optimal conditions for the leaching of metals from spent catalysts. Since sulfur was removed from the spent catalysts by calcination, the leaching of metals results from the dissolution of metal oxides.

제안 방법

In order to investigate the leaching behavior of some rare metals from the spent petroleum catalysts, several organic acids such as oxalic acid, tartaric acid, citric acid, maleic acid, ascorbic acid, and methanesulfonic acid were employed. Among these acid solutions, oxalic acid shows the best selectivity for the dissolution of vanadium and molybdenum.
Therefore, the dissolution of rare metals from spent petroleum catalysts by organic acids has been investigated in this work. The effect of some variables such as the nature of organic acids, reaction temperature, reactant concentration, pulp density, leaching time and the stirring speed on the dissolution of metals was investigated. The leaching kinetics of vanadium was also studied by employing some kinetic models and the corresponding leaching model was reported.
Meanwhile, the leaching percentage of other metals was less than 10%. Therefore, oxalic acid was selected for further leaching experiments to investigate the effect of some factors on the dissolution behavior of metals from the spent catalyst. The aim was to find the optimal conditions for the leaching of metals from spent catalysts.

대상 데이터

The spent petroleum catalysts were collected from a Korean refinery. The soluble organic matters of spent catalysts were removed by washing with acetone and then the residues were dried overnight in an oven at 80°C.
The structure of the spent catalysts was analyzed by XRD (X’Pert-PRO, The Netherlands) and XRF (M1MISTRAL, Germany).

후속연구

In the present work, although the leaching efficiency of vanadium by organic acids was not high, it was selectively dissolved over the other metals by oxalic acid from the spent catalysts. Further studies on improving the leaching of vanadium with organic acids are needed. In addition, after the leaching of vanadium from spent catalysts is improved, the separation of metals in the leaching solution can be investigated by employing some processes such as solvent extraction, precipitation, and ion exchange.

참고문헌 (38)

Banda, R., Nguyen, T. H., Sohn, S. H., and Lee, M. S., 2013 : Recovery of valuable metals and regeneration of acid from the leaching solution of spent HDS catalysts by solvent extraction, Hydrometallurgy, 133, pp.161-167.

상세보기
Mishra, D., Chaudhury, G. R., Kim, D. J., and Ahn, J. G., 2010 : Recovery of metal values from spent petroleum catalyst using leaching-solvent extraction technique, Hydrometallurgy, 101(1-2), pp.35-40.

상세보기
Barik, S. P., Park, K. H., Parhi, P. K., and Park, J. T., 2012 : Direct leaching of molybdenum and cobalt from spent hydrodesulphurization catalyst with sulphuric acid, Hydrometallurgy, 111-112(1), pp.46-51.
Marafi, M. and Stanislaus, A., 2008 : Spent catalyst waste management: A review. Part I-developments in hydroprocessing catalyst waste reduction and use, Resour. Conserv. Recycl., 52(6), pp.859-873.

상세보기
Kalantar, M., Najafi, H., and Afshar, M. R., 2019 : Comparison between vanadium and niobium effects on the mechanical properties of intercritically heat treated microalloyed cast steels, Met. Mater. Int., 25(1), pp.229-237.

상세보기
Huang, Y., Peng, X., Yang, Y., Wu, H., Sun, X., and Han, X., 2018 : Electroless Cu/Ni plating on graphite flake and the effects to the properties of graphite flake/Si/Al hybrid composites, Met. Mater. Int., 24(5), pp.1172-1180.

상세보기
Nguyen, T. T. N. and Lee, M. S., 2019 : Improvement of alumina dissolution from the mechanically activated dross using ultrasound-assisted leaching, Korean J. Met. Mater., 57(3), pp.154-161.

상세보기
Park, K. H., Mohapatra, D., and Reddy, B. R., 2006 : Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method, J. Hazard. Mater., 138(2), pp.311-316.

상세보기
Kim, S. J., Lee, J. Il., Han, K. S., Byun, S. Y., Tran, T., and Kim, M. J., 2018 : Recovery of fine aluminum hydroxide with high whiteness index from low quality bauxite using caustic roasting and water leaching, Korean J. Met. Mater., 56(1), pp.49-58.

상세보기
Mazurek, K., 2013 : Recovery of vanadium, potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching, precipitation and ion exchange processes, Hydrometallurgy, 134-135, pp.26-31.
Erust, C., Akcil, A., Bedelova, Z., Anarbekov, K., Baikonurova, A., and Tuncuk, A., 2016 : Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids: Laboratory and semipilot tests, Waste Manag., 49, pp.455-461.

상세보기
Marafi, M. and Stanislaus, A., 2011 : Waste catalyst utilization: Extraction of valuable metals from spent hydroprocessing catalysts by ultrasonic-assisted leaching with acids, Ind. Eng. Chem. Res., 50(16), pp.9495-9501.

상세보기
Ilhan, S., Kalpakli, A. O., Kahruman, C., and Yusufoglu, I., 2013 : The use of oxalic acid as a chelating agent in the dissolution reaction of calcium molybdate, Metall. Mater. Trans. B, 44(3), pp.495-505.

상세보기
Marafi, M., Stanislaus, A., and Absi-Halabi, M., 1994 : Heavy oil hydrotreating catalyst rejuvenation by leaching of foulant metals with ferric nitrate-organic acid mixed reagents, Appl. Catal. B Environ., 4(1), pp.19-27.

상세보기
Le, M. N. and Lee, M. S., 2019 : Selective dissolution of vanadium (V) from spent petroleum catalysts by oxalic acid solution. J. Min. Metall. Sect. B Metall., (under review).
Lide, D. R., 2007 : CRC Handbook of Chemistry and Physics, 87th ed., Taylor and Francis, Boca Raton, FL, pp.842-846.
Guthrie, J. P., 1978 : Hydrolysis of esters of oxy acids: $pK_a$ values for strong acids; Bronsted relationship for attack of water at methyl; free energies of hydrolysis of esters of oxy acids; and a linear relationship between free energy of hydrolysis and pKa holding over a range of 20 pK units, Can. J. Chem., 56(17), pp.2342-2354.

상세보기
Kakumoto, T., Saito, K., and Imamura, A., 1987 : Unimolecular decomposition of oxalic acid, J. Phys. Chem., 91(9), pp.2366-2371.

상세보기
Lindsay, J. G., McElcheran, D. E., and Thode, H. G., 1949 : The isotope effect in the decomposition of oxalic acid, J. Chem. Phys., 17(6), pp.589-589.

상세보기
Szymczycha-Madeja, A., 2011 : Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide, J. Hazard. Mater., 186(2-3), pp.2157-2161.

상세보기
Mulak, W., Szymczycha, A., Lesniewicz, A., and Zyrnicki, W., 2006 : Preliminary results of metals leaching from a spent hydrodesulphurization (HDS) catalyst, Physicochem. Probl. Miner. Process., 40(1), pp.69-76.
Lee, J. Y., Rao, S. V., Kumar, B. N., Kang, D. J., and Reddy, B. R., 2010 : Nickel recovery from spent Raneynickel catalyst through dilute sulfuric acid leaching and soda ash precipitation, J. Hazard. Mater., 176(1-3), pp.1122-1125.

상세보기
Parhi, P. K., Park, K. H., and Senanayake, G., 2013 : A kinetic study on hydrochloric acid leaching of nickel from Ni- $Al_2O_3$ spent catalyst, J. Ind. Eng. Chem., 19(2), pp.589-594.

상세보기
Li, Q., Liu, Z., and Liu, Q., 2014 : Kinetics of vanadium leaching from a spent industrial $V_2O_5/TiO_2$ catalyst by sulfuric acid, Ind. Eng. Chem. Res., 53(8), pp.2956-2962.

상세보기
Sokic, M. D., Markovic, B., and Zivkovic, D., 2009 : Kinetics of chalcopyrite leaching by sodium nitrate in sulphuric acid, Hydrometallurgy, 95(3), pp.273-279.

상세보기
Gao, H., Jiang, T., Xu, Y., Wen, J., and Xue, X., 2018 : Leaching kinetics of vanadium and chromium during sulfuric acid leaching with microwave and conventional calcification-roasted high chromium vanadium slag, Miner. Process. Extr. Metall. Rev., pp.1-10. DOI:10.1080/08827508.2018.1538985.

상세보기
Peng, H., Liu, Z., and Tao, C., 2016 : Leaching kinetics of vanadium with electro-oxidation and $H_2O_2$ in alkaline medium, Energy and Fuels, 30(9), pp.7802-7807.

상세보기
Martell, A. E. and Smith, R. M., 1977 : Critical Stability Constants, Vol. 3., Springer Science + Business Media, New York, pp.92-98.
Beltran, A., Caturla, F., Cervilla, A., and Beltran, J., 1981 : Mo(VI) oxalate complexes, J. Inorg. Nucl. Chem., 43, pp.3277-3282.

상세보기
Martell, A. E. and Smith, R. M., 1982 : Critical Stability Constants, Vol 5., Springer Science + Business Media, New York, pp.307-309.
Panias, D., Taxiarchou, M., Douni, I., Paspaliaris, I., and Kontopoulos, A., 2014 : Thermodynamic analysis of the reactions of iron oxides: Dissolution in oxalic acid, Can. Metall. Q., 35, pp.363-373.
Sjoberg, S. and Ohman, L. O., 1985 : Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. Part 13. A potentiometric and 27Al nuclear magnetic resonance study of speciation and equilibria in the aluminium(III)-oxalic acid-hydroxide system, J. Chem. Soc. Dalt. Trans., 12, pp.2665-2669.
Poulson, S. R., Drever, J. I., and Stillings, L. L., 1997 : Aqueous Si-oxalate complexing, oxalate adsorption onto quartz, and the effect of oxalate upon quartz dissolution rates, Chem. Geol., 140, pp.1-7.

상세보기
Peng, H., Liu, Z., and Tao, C., 2015 : Selective leaching of vanadium from chromium residue intensified by electric field, J. Environ. Chem. Eng., 3(2), pp.1252-1257.

상세보기
Lozano, L. J. and Juan, D., 2001 : Leaching of vanadium from spent sulphuric acid catalysts, Miner. Eng., 14(5), pp.543-546.

상세보기
Dickinson, C. F. and Heal, G. R., 1999 : Solid-liquid diffusion controlled rate equations, Thermochim. Acta, 340-341, pp.89-103.
Li, M., Wei, C., Qiu, S., Zhou, X., Li, C., and Deng, Z., 2010 : Kinetics of vanadium dissolution from black shale in pressure acid leaching, Hydrometallurgy, 104(2), pp.193-200.

상세보기
Ramos-Cano, J., Gonzalez-Zamarripa, G., Carrillo-Pedroza, F. R., Soria-Aguilar, M. D. J., Hurtado-Macias, A., and Cano-Vielma, A., 2016 : Kinetics and statistical analysis of nickel leaching from spent catalyst in nitric acid solution, Int. J. Miner. Process., 148, pp.41-47.

상세보기

저자의 다른 논문 :

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증