Production of Nickel Oxalate Dihydrate from Spent Ni-Mo Hydrodesulfurization Catalyst

Öz

Spent Ni-Mo HDS catalyst is one of the most important secondary resources for the recovery of valuable metals. Recovery processes are important from the economical and environmental point of view. Ni content of Ni-Mo HDS catalyst was determined as 5.27 % after oxidative roasting. Production of NiC₂O₄∙2H₂O from roasted HDS catalyst was investigated in this work. It is seen from the ICP-OES analysis that nickel concentration in the solution was increased to a maximum value at the beginning of the experiment and then decreased. NiC₂O₄∙2H₂O was formed in a consecutive reaction in two steps. NiC₂O₄∙2H₂O was produced with efficiency of 99.1 % from the experiment carried out using 1/10 solid/liquid ratio, 40 ^oC temperature, 1 M oxalic acid, 300 rpm stirring speed and 480 minutes reaction duration. TG-DTA analysis performed in dry air atmosphere showed that NiC₂O₄∙2H₂O produced decomposed in two steps and formed NiO after second decomposition step at about 350 ^oC.

Anahtar Kelimeler

• Nickel oxalate,hydrodesulfurization catalyst,nickel oxide,recovery,nickel oxide

Kullanılmış Ni-Mo Hidrodesülfürizasyon Katalizöründen Nikel Okzalat Dihidrat Üretimi

Öz

Kullanılmış Ni-Mo HDS katalizörü, değerli metallerin geri kazanımı için önemli ikincil kaynaklardan biridir. Geri kazanım prosesleri hem çevresel hem de ekonomik açıdan önem arzetmektedir. Oksitleyeci kavurma sonrasında Ni-Mo HDS katalizörünün % 5.27 Ni içerdiği belirlenmiştir. Bu çalışmada oksitleyici kavurmaya tabi tutulan Ni-Mo HDS katalizöründen okzalik asitli çözeltilerde NiC₂O₄∙2H₂O üretimi incelenmiştir. ICP-OES analizinden çözeltideki nikel konsantrasyonunun deneyin başında arttığı, bir maksimum değere ulaştıktan sonra azalmaya başladığı görülmüştür. NiC₂O₄∙2H₂O’ın iki adımda konsekütif reaksiyon sonucunda oluştuğu tespit edilmiştir. 1/10 katı/sıvı oranı ile 40 ^oC sıcaklık, 1 M okzalik asit çözeltisi, 300 rpm karıştırma hızı kullanılarak 480 dakika süre ile gerçekleştirilen deney sonucunda % 99.1 verimle NiC₂O₄∙2H₂O üretilmiştir. Kuru hava atmosferinde gerçekleştirilen TG-DTA analizi, üretilen NiC₂O₄∙2H₂O’ın iki kademede bozunduğunu ve 350 ^oC civarında tamamlanan ikinci bozunma kademesinden sonra tamamen NiO’e dönüştüğünü göstermiştir.

Anahtar Kelimeler

• Nikel okzalat,hidrodesülfürizasyon katalizörü,nikel oksit,geri kazanım

Kaynakça

1. 1. Dufresne, P., "Hydroprocessing catalysts regeneration and recycling", Applied Catalysis A: General, 322: 67-75, (2007)
2. 2. EPA, U., "Hazardous waste management system; identification and listing of hazardous waste: Spent catalysts from dual-purpose petroleum hydroprocessing reactors", Federal register, 35379-35384, (2001)
3. 3. Park, K.H., D. Mohapatra, and B.R. Reddy, "Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method", Journal of Hazardous Materials, 138 (2): 311-316, (2006)
4. 4. Siemens, R.E., B.W. Jong, and J.H. Russell, "Potential of spent catalysts as a source of critical metals", Conservation & Recycling, 9 (2): 189-196, (1986)
5. 5. Hyatt, D.E., "Value recovery from spent alumina-base catalyst", Google Patents, (1987)
6. 6. Lai, Y.-C., et al., "Metal recovery from spent hydrodesulfurization catalysts using a combined acid-leaching and electrolysis process", Journal of Hazardous Materials, 154 (1–3): 588-594, (2008)
7. 7. Rabah, M.A., I.F. Hewaidy, and F.E. Farghaly, "Recovery of Molybdenum and Cobalt Powders from Spent Hydrogenation Catalyst", Powder Metallurgy, 40 (4): 283-288, (1997)
8. 8. Mulak, W., et al., "Preliminary results of metals leaching from a spent hydrodesulphurization (HDS) catalyst", Physicochemical Problems of Mineral Processing, 40: 69-76, (2006)

9. 9. Szymczycha-Madeja, A., "Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide", Journal of Hazardous Materials, 186 (2–3): 2157-2161, (2011)
10. 10. Villarreal, M.S., et al., "Recovery of Vanadium and Molybdenum from Spent Petroleum Catalyst of PEMEX", Industrial & Engineering Chemistry Research, 38 (12): 4624-4628, (1999)
11. 11. Kim, H.-I., K.-H. Park, and D. Mishra, "Sulfuric acid baking and leaching of spent Co-Mo/Al2O3 catalyst", Journal of Hazardous Materials, 166 (2–3): 1540-1544, (2009)
12. 12. Park, K.H., D. Mohapatra, and C.-W. Nam, "Two stage leaching of activated spent HDS catalyst and solvent extraction of aluminium using organo-phosphinic extractant, Cyanex 272", Journal of Hazardous Materials, 148 (1–2): 287-295, (2007)
13. 13. Toyabe, K., et al., "Process for recovering valuable metal from waste catalyst", Google Patents, (1995)
14. 14. Valverde, I.M., J.F. Paulino, and J.C. Afonso, "Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium", Journal of Hazardous Materials, 160 (2): 310-317, (2008)
15. 15. Sun, D.D., et al., "Recovery of heavy metals and stabilization of spent hydrotreating catalyst using a glass–ceramic matrix", Journal of Hazardous Materials, 87 (1–3): 213-223, (2001)
16. 16. Coman, V., B. Robotin, and P. Ilea, "Nickel recovery/removal from industrial wastes: A review", Resources, Conservation and Recycling, 73: 229-238, (2013)
17. 17. Giannopoulou, I. and D. Panias, "Copper and nickel recovery from acidic polymetallic aqueous solutions", Minerals Engineering, 20 (8): 753-760, (2007)
18. 18. Giannopoulou, I. and D. Panias, "Differential precipitation of copper and nickel from acidic polymetallic aqueous solutions", Hydrometallurgy, 90 (2): 137-146, (2008)
19. 19. Sist, C. and G.P. Demopoulos, "Nickel hydroxide precipitation from aqueous sulfate media", JOM, 55 (8): 42-46, (2003)
20. 20. Subbaiah, T., et al., "Electrochemical precipitation of nickel hydroxide", Journal of Power Sources, 112 (2): 562-569, (2002)
21. 21. Agrawal, A., et al., "Recovery of nickel powder from copper bleed electrolyte of an Indian copper smelter by electrolysis", Powder Technology, 177 (3): 133-139, (2007)
22. 22. Agrawal, A., et al., "Extractive separation of copper and nickel from copper bleed stream by solvent extraction route", Minerals Engineering, 21 (15): 1126-1130, (2008)
23. 23. Nyirenda, R.L. and W.S. Phiri, "The removal of nickel from copper electrorefining bleed-off electrolyte", Minerals Engineering, 11 (1): 23-37, (1998)
24. 24. Zhang, P., et al., "Hydrometallurgical process for recovery of metal values from spent nickel-metal hydride secondary batteries", Hydrometallurgy, 50 (1): 61-75, (1998)
25. 25. Zhang, P., et al., "Recovery of metal values from spent nickel–metal hydride rechargeable batteries", Journal of Power Sources, 77 (2): 116-122, (1999)
26. 26. Rydh, C.J. and M. Karlström, "Life cycle inventory of recycling portable nickel–cadmium batteries", Resources, Conservation and Recycling, 34 (4): 289-309, (2002)
27. 27. Bernardes, A.M., D.C.R. Espinosa, and J.A.S. Tenório, "Recycling of batteries: a review of current processes and technologies", Journal of Power Sources, 130 (1): 291-298, (2004)
28. 28. Sahu, K.K., A. Agarwal, and B.D. Pandey, "Nickel recovery from spent nickel catalyst", Waste Management & Research, 23 (2): 148-154, (2005)
29. 29. Chaudhary, A.J., et al., "Heavy metals in the environment. Part II: a hydrochloric acid leaching process for the recovery of nickel value from a spent catalyst", Hydrometallurgy, 34 (2): 137-150, (1993)
30. 30. Alex, P. and A. Suri, "Processing of spent nickel catalyst", Transactions of the Indian Institute of Metals (India), 51 (1): 55-67, (1998)
31. 31. Alex, P., T. Mukherjee, and M. Sundaresan, "Reduction Roasting--Sulphuric Acid Leaching of Nickel From a Spent Catalyst", Metals Materials and Processess (India), 3 (2): 81-91, (1991)
32. 32. Tilley, G.L.," Recovery of metal values from spent catalysts", Google Patents, (1988)
33. 33. Al-Mansi, N.M. and N.M. Abdel Monem, "Recovery of nickel oxide from spent catalyst", Waste Management, 22 (1): 85-90, (2002)
34. 34. Ilhan, S., et al., "The Use of Oxalic Acid as a Chelating Agent in the Dissolution Reaction of Calcium Molybdate", Metallurgical and Materials Transactions B, 44 (3): 495-505, (2013)
35. 35. Ilhan, S. "Leaching of Spent Ni–Mo Hydrodesulphurization (HDS) Catalyst in Oxalic Acid Solutions", Cham: Springer International Publishing, (2017)
36. 36. Yao, Y.-l., et al., "Thermodynamics analysis of Ni2+−C2H8N2−C2O42−−H2O system and preparation of Ni microfiber", Transactions of Nonferrous Metals Society of China, 23 (11): 3456-3461, (2013)
37. 37. Mompean, F.J., M. Illemassène, and J. Perrone, "Chemical thermodynamics of compounds and complexes of U, Np, Pu, Am, Tc, Se, Ni and Zr with selected organic ligands", Vol. 9, Elsevier, (2005)
38. 38. Allen, J.A., "The Precipitation of Nickel Oxalate", The Journal of Physical Chemistry, 57 (7): 715-716, (1953)
39. 39. Rakshit, S., et al., "Morphology control of nickel oxalate by soft chemistry and conversion to nickel oxide for application in photocatalysis", RSC Advances, 3 (17): 6106-6116, (2013)