ipolytechiPolytech JournaliPolytech Journal2782-40042782-6341Irkutsk National Research Technical University10.21285/1814-3520-2024-1-178-189UHVJQTipolytech-806Research ArticleМЕТАЛЛУРГИЯMETALLURGYКинетические закономерности выщелачивания цинка из промпродуктовKinetics of zinc leaching from intermediate feedstocksЯкорновС. А.YakornovS. A.

Якорнов Сергей Александрович, к.т.н., первый заместитель технического директора

624091, г. Верхняя Пышма, пр. Успенский, 1

Sergey A. Yakornov, Cand. Sci. (Eng.), First Deputy Technical Director

1 Uspensky pr., Verkhnyaya Pyshma, 624091

info@uralmine.comМальцевГ. И.MaltsevG. I.

Мальцев Геннадий Иванович, д.т.н., старший научный сотрудник, главный специалист Исследовательского центра

624091, г. Верхняя Пышма, пр. Успенский, 1

Gennady I. Maltsev, Dr. Sci. (Eng.), Senior Researcher, Chief Specialist of the Research Center

1 Uspensky pr., Verkhnyaya Pyshma, 624091

maltsewg@yandex.ruВоинковР. С.VoinkovR. S.

Воинков Роман Сергеевич, к.т.н., начальник Исследовательского центра; доцент кафедры металлургии; 

624091, г. Верхняя Пышма, пр. Успенский, 1

624091, г. Верхняя Пышма, пр. Успенский, 3

Roman S. Voinkov, Cand. Sci. (Eng.), Head of the Research Center; Associate Professor of the Metallurgy Department

1 Uspensky pr., Verkhnyaya Pyshma, 624091

3 Uspensky pr., Verkhnyaya Pyshma, 624091

r.voinkov@uralcopper.comГребневаА. А.GrebnevaA. A.

Гребнева Анна Александровна,  к.х.н., ведущий инженер-технолог Исследовательского центра

624091, г. Верхняя Пышма, пр. Успенский, 1

Anna A. Grebneva, Cand. Sci. (Chem.), Leading Engineer of the Research Center

1 Uspensky pr., Verkhnyaya Pyshma, 624091

vs_finder@mail.ruОАО «Уральская горно-металлургическая компания»РоссияUral Mining & Metallurgical CompanyRussian FederationАО «Уралэлектромедь»РоссияJSC UralelectromedRussian FederationАО «Уралэлектромедь»; Технический университет Уральской горно-металлургической компанииРоссияJSC Uralelectromed; Technical University of the Ural Mining and Metallurgical CompanyRussian Federation202430032024281178189Copyright © Якорнов С.А., Мальцев Г.И., Воинков Р.С., Гребнева А.А., 20242024Якорнов С.А., Мальцев Г.И., Воинков Р.С., Гребнева А.А.Yakornov S.A., Maltsev G.I., Voinkov R.S., Grebneva A.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://ipolytech.elpub.ru/jour/article/view/806

Целью работы являлось изучение кинетических закономерностей выщелачивания цинка из соединения CaO. ZnO, образующегося при спекании пыли электродуговых печей с известняком, а также выявление механизмов, по которым протекают химические взаимодействия. Объектом исследования служил спек пыли электродуговых печей с известняком, полученный на Челябинском цинковом заводе. Установлено, что цинк в спеке содержится в виде легкорастворимого CaO. ZnO. Элементный состав исходных пылей и спека с известняком определяли спектральным атомно-эмиссионным способом с использованием различных источников возбуждения спектра: индуктивно-связанной плазмы на оптико-эмиссионном приборе «Spectroblue»; искровой спектрометрии. Фазовый состав материалов изучали на рентгенофазовом дифрактометре «Bruker D8 Advance». Исходный спек измельчали до порошкообразного состояния с размером частиц ~0,04 мм и выходом ~97%-го состава, %: 11,9 Zn; 28,5 Ca; 16,6 Fe; 0,38 Mg; 0,14 Pb; ˂ 0,05 Cl. Опыты по выщелачиванию Zn раствором едкого натра проводили при следующих параметрах: исходная концентрация цинка в пульпе была 0,202 г-ион/дм3; концентрация щелочи ‒ 5‒9 моль/дм3 NaOH; Ж:Т = 9:1; скорость перемешивания пульпы ‒ 10‒20 рад. с-1; температура ‒ 333‒363 К; продолжительность ‒ 0,5–2,5 ч. Показано, что цинк из спека переходит в раствор в виде тетрагидроксоцинката натрия Na2[Zn(OH)4], а кальций остается в кеке, в основном в виде малорастворимого гидроксида Ca(OH)2, который взаимодействует с углекислым газом с образованием нерастворимого карбоната кальция CaСO3. Установлено, что процесс выщелачивания цинка из спека соответствует внешнедиффузионному режиму взаимного переноса исходных реагентов и продуктов реакции через поверхностный слой жидкости на границе раздела фаз «жидкость‒твердое» с величиной энергии активации равной 12,44 кДж/моль. Таким образом, при исследованных параметрах выщелачивания цинка раствором NaOH процесс протекает во внешнедиффузионном режиме. Представляет интерес выявление условий, соответствующих внутридиффузионному и кинетическому режимам выщелачивания цинка.

The aim of the work was to study the leaching kinetics of zinc from the compound CaO. ZnO, formed during the sintering of dust from electric arc furnaces with limestone, as well as to identify the mechanisms by means which such chemical interactions occur. The object of the study was the dust sinter of electric arc furnaces with limestone obtained at the Chelyabinsk Zinc Plant. It was found that zinc is contained in sinter in the form of readily soluble CaO. ZnO. The elemental composition of the initial dusts and sinter was determined by the spectral atomic emission method using inductively coupled plasma on a Spectroblue optical emission device and spark spectrometry. The phase composition of the materials was studied on a Bruker D8 Advance X-ray diffractometer. The initial sinter was milled to apowder state having a particle size of ~0.04 mm and with a yield of ~97% of the composition, %: 11.9 Zn; 28.5 Ca; 16.6 Fe; 0.38 Mg; 0.14 Pb; 0.05 Cl. Experiments on the leaching of Zn with NaOH solution were carried out at the following parameters: the initial concentration of zinc in the pulp was 0.202 g-ion/dm3 ; alkali concentration – 5‒9 mol/dm3 NaOH; L:S = 9:1; pulp mixing rate – 10‒20 rad. c-1; temperature – 333‒363 K; duration – 0.5–2.5 hours. It has been shown that zinc from sinter passes into solution as sodium tetrahydroxozincate Na2[Zn(OH)4], while calcium remains in the cake, mainly as insoluble Ca(OH)2, which reacts with carbon dioxide to form insoluble calcium carbonate CaCO3. The process of dissolving zinc from the sinter corresponds to the external diffusion mode of mutual transfer of the initial reagents and reaction products through the surface layer of the liquid at the interface of the “liquid–solid” phases with an activation energy value equal to 12.44 kJ/mol. Thus, with the studied parameters of zinc leaching with NaOH solution, the process proceeds in an external diffusion mode. The results are of interest when identifying conditions corresponding to the intradiffusion and kinetic modes of zinc leaching.

пыли электродуговых печейизвестнякобжигцинквыщелачиваниеедкий натрelectric arc furnace dustlimestoneroastingzincleachingcaustic sodaReferencesРастянникова Е.В. Вторичное использование ресурсов в металлургической промышленности в России и Китае // Инновации и инвестиции. 2019. № 7. С. 81‒85. EDN: XNRAZG.Rastiannikova E.V. Resource recycling in metallurgical industry of Russia and China. Innovatsii i investitsii. 2019;7: 81–85. (In Russ.). EDN: XNRAZG.Казанбаев Л.А., Козлов П.А., Кубасов В.Л., Колесников А.В. Гидрометаллургия цинка. Очистка растворов и электролиз. М.: Руда и Металлы, 2006. 176 с.Kazanbaev L.A., Kozlov P.A., Kubasov V.L., Kolesnikov A.V. Hydrometallurgy of zinc. Solution purification and electrolysis. Moscow: Ruda i Metally; 2006, 176 p. (In Russ.). 3. Cardoso D., Narcy A., Durosoy S., Chevalier Y. The pH dependence of dissolution kinetics of zinc oxide. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2022; 650:129653. https://doi.org/10.1016/j.colsurfa.2022.129653.Cardoso D., Narcy A., Durosoy S., Chevalier Y. The pH dependence of dissolution kinetics of zinc oxide // Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2022. Vol. 650. Р. 129653. https://doi.org/10.1016/j.colsurfa.2022.129653.Cardoso D., Narcy A., Durosoy S., Bordes C., Chevalier Y. Dissolution kinetics of zinc oxide and its relationship with physicochemical characteristics. Powder Technology. 2021;378(B):746-759. https://doi.org/10.1016/j.powtec.2020.10.049.Cardoso D., Narcy A., Durosoy S., Bordes C., Chevalier Y. Dissolution kinetics of zinc oxide and its relationship with physicochemical characteristics // Powder Technology. 2021. Vol. 378. Part B. P. 746‒759. https://doi.org/10.1016/j.powtec.2020.10.049.Huang Yukun, Duan Zhuo, Bai Ningning, Wang Huijuan, Cao Yijun, Song Xiangyu, Peng Weijun, et al. Highly selective dissolution and synchronous extraction of zinc from zinc-cobalt slag by an ionic liquid [Hbet][Tf2N]–H2O system: а novel method for separating zinc and cobalt. Journal of Cleaner Production. 2021;315:128301. https://doi.org/10.1016/j. jclepro.2021.128301.Huang Yukun, Duan Zhuo, Bai Ningning, Wang Huijuan, Cao Yijun, Song Xiangyu, Peng Weijun, et al. Highly selective dissolution and synchronous extraction of zinc from zinc-cobalt slag by an ionic liquid [Hbet][Tf2N]–H2O system: а novel method for separating zinc and cobalt // Journal of Cleaner Production. 2021. Vol. 315. Р. 128301. https://doi.org/10.1016/j.jclepro.2021.128301.Kromm V., Hanreich A., Romeo A. 23. Dissolution kinetics of zinc, copper, and manganese sources in rumen fluid. Animal ‒ science proceedings. 2022;13(1):14-15. https://doi.org/10.1016/j.anscip.2022.03.024.Kromm V., Hanreich A., Romeo A. 23. Dissolution kinetics of zinc, copper, and manganese sources in rumen fluid // Animal ‒ science proceedings. 2022. Vol. 13. Iss. 1. P. 14‒15. https://doi.org/10.1016/j.anscip.2022.03.024.Al-Harahsheh M., Altarawneh S., Al-Omari M. Selective dissolution of zinc and lead from electric arc furnace dust via oxidative thermolysis with polyvinyl chloride and water-leaching process. Hydrometallurgy. 2022;212:105898. https://doi.org/10.1016/j.hydromet.2022.105898.Al-Harahsheh M., Altarawneh S., Al-Omari M. Selective dissolution of zinc and lead from electric arc furnace dust via oxidative thermolysis with polyvinyl chloride and water-leaching process // Hydrometallurgy. 2022. Vol. 212. Р. 105898. https://doi.org/10.1016/j.hydromet.2022.105898.Wu Hangmi, Li Jiangling, Teng Wenxin, Chen Yangfan, Liu Weizao, Ren Shan, et al. One-step extraction of zinc and separation of iron from hazardous electric arc furnace dust via sulphating roasting-water leaching. Journal of Environmental Chemical Engineering. 2023;11(6):111155. https://doi.org/10.1016/j.jece.2023.111155.Wu Hangmi, Li Jiangling, Teng Wenxin, Chen Yangfan, Liu Weizao, Ren Shan, et al. One-step extraction of zinc and separation of iron from hazardous electric arc furnace dust via sulphating roasting-water leaching // Journal of Environmental Chemical Engineering. 2023. Vol. 11. Iss. 6. Р. 111155. https://doi.org/10.1016/j.jece.2023.111155.Ye Fu, Li Minting, Su Song, Xia Haitao, Wei Chang, Li Xingbin, et al. Separation and recovery of zinc from blast furnace dust via coordination leaching of Cl− and hydrolysis of NH4 +. Separation and Purification Technology. 2024;330(B):125361. https://doi.org/10.1016/j.seppur.2023.125361.Ye Fu, Li Minting, Su Song, Xia Haitao, Wei Chang, Li Xingbin, et al. Separation and recovery of zinc from blast furnace dust via coordination leaching of Cl− and hydrolysis of NH4 + // Separation and Purification Technology. 2024. Vol. 330. Part B. Р. 125361. https://doi.org/10.1016/j.seppur.2023.125361.Luo Xingguo, Wang Chenyu, Shi Xianguo, Li Xingbin, Wei Chang, Minting Li, et al. Selective separation of zinc and iron/ carbon from blast furnace dust via a hydrometallurgical cooperative leaching method. Waste Management. 2022;139:116-123. https://doi.org/10.1016/j.wasman.2021.12.007.Luo Xingguo, Wang Chenyu, Shi Xianguo, Li Xingbin, Wei Chang, Minting Li, et al. Selective separation of zinc and iron/carbon from blast furnace dust via a hydrometallurgical cooperative leaching method // Waste Management. 2022. Vol. 139. P. 116‒123. https://doi.org/10.1016/j.wasman.2021.12.007.YangXue, Xiaoming Liu, Na Zhang, Song Guo, ZhiqingXie, ChunbaoXu. Anovel process forthe treatment of steelmaking converter dust: Selective leaching and recovery of zinc sulfate and synthesis of iron oxides@HTCC photocatalysts by carbonizing carbohydrates. Hydrometallurgy. 2023;217:106039. https://doi.org/10.1016/j.hydromet.2023.106039.Yang Xue, Xiaoming Liu, Na Zhang, Song Guo, Zhiqing Xie, Chunbao Xu. A novel process for the treatment of steelmaking converter dust: Selective leaching and recovery of zinc sulfate and synthesis of iron oxides@HTCC photocatalysts by carbonizing carbohydrates // Hydrometallurgy. 2023. Vol. 217. Р. 106039. https://doi.org/10.1016/j.hydromet.2023. 106039.Xin Chunfu, Xia Hongying, Jiang Guiyu, Zhang Qi, Zhang Libo, Xu Yingjie, et al. Mechanism and kinetics study on ultrasonic combined with oxygen enhanced leaching of zinc and germanium from germanium-containing slag dust. Separation and Purification Technology. 2022;302:122167. https://doi.org/10.1016/j.seppur.2022.122167.Xin Chunfu, Xia Hongying, Jiang Guiyu, Zhang Qi, Zhang Libo, Xu Yingjie, et al. Mechanism and kinetics study on ultrasonic combined with oxygen enhanced leaching of zinc and germanium from germanium-containing slag dust // Separation and Purification Technology. 2022. Vol. 302. P. 122167. https://doi.org/10.1016/j.seppur.2022.122167.Ding Wei, Bao Shenxu, Zhang Yimin, Xiao Junhui. Mechanism and kinetics study on ultrasound assisted leaching of gallium and zinc from corundum flue dust. Minerals Engineering. 2022;183:107624. https://doi.org/10.1016/j.mineng.2022.107624.Ding Wei, Bao Shenxu, Zhang Yimin, Xiao Junhui. Mechanism and kinetics study on ultrasound assisted leaching of gallium and zinc from corundum flue dust // Minerals Engineering. 2022. Vol. 183. Р. 107624. https://doi.org/10.1016/j.mineng.2022.107624.Zhang Limin, Wang Yunyan, Ke Yong, Sun Zhumei, Li Yun, Peng Cong, et al. Facile and complete sulfuric acid leaching of zinc ferrite assisted by copper powder: leaching mechanism and kinetics investigation. Separation and Purification Technology. 2024;328:125090. https://doi.org/10.1016/j.seppur.2023.125090.Zhang Limin, Wang Yunyan, Ke Yong, Sun Zhumei, Li Yun, Peng Cong, et al. Facile and complete sulfuric acid leaching of zinc ferrite assisted by copper powder: leaching mechanism and kinetics investigation // Separation and Purification Technology. 2024. Vol. 328. Р. 125090. https://doi.org/10.1016/j.seppur.2023.125090.Wang Xin, Zhong Yiwei, Kang Yuzheng, Gao Jintao, Guo Zhancheng. Promoted acid leaching of Zn from hazardous zinc-containing metallurgical dusts: focusing on transformation of Zn phases in selective reduction roasting. Process Safety and Environmental Protection. 2022;163:353-361. https://doi.org/10.1016/j.psep.2022.05.046.Wang Xin, Zhong Yiwei, Kang Yuzheng, Gao Jintao, Guo Zhancheng. Promoted acid leaching of Zn from hazardous zinc-containing metallurgical dusts: focusing on transformation of Zn phases in selective reduction roasting // Process Safety and Environmental Protection. 2022. Vol. 163. P. 353‒361. https://doi.org/10.1016/j.psep.2022.05.046.Xin Chunfu, Xia Hongying, Zhang Qi, Zhang Libo, Zhang Wei. Leaching of zinc and germanium from zinc oxide dust in sulfuric acid-ozone media. Arabian Journal of Chemistry. 2021;14(12):103450. https://doi.org/10.1016/j.arabjc.2021.103450.Xin Chunfu, Xia Hongying, Zhang Qi, Zhang Libo, Zhang Wei. Leaching of zinc and germanium from zinc oxide dust in sulfuric acid-ozone media // Arabian Journal of Chemistry. 2021. Vol. 14. Iss. 12. Р. 103450. https://doi.org/10.1016/j.arabjc.2021.103450.Lijuan Jia, ZhongYingying, Li Kai, Li Bin, Gao Jiyun, Liu Tiancheng, et al. Recovery of zinc resources from secondary zinc oxide via composite ammonia leaching: аnalysis of Zn leaching behavior. Chemical Engineering Journal. 2023;472:144930. https://doi.org/10.1016/j.cej.2023.144930.Lijuan Jia, Zhong Yingying, Li Kai, Li Bin, Gao Jiyun, Liu Tiancheng, et al. Recovery of zinc resources from secondary zinc oxide via composite ammonia leaching: аnalysis of Zn leaching behavior // Chemical Engineering Journal. 2023. Vol. 472. Р. 144930. https://doi.org/10.1016/j.cej.2023.144930.Khodaei H., Haghshenas D.F., Firoozi S. Selective leaching of zinc from carbonate source using glycine as an ecofriendly lixiviant. Minerals Engineering. 2022;185:107680. https://doi.org/10.1016/j.mineng.2022.107680.Khodaei H., Haghshenas D.F., Firoozi S. Selective leaching of zinc from carbonate source using glycine as an ecofriendly lixiviant // Minerals Engineering. 2022. Vol. 185. P. 107680. https://doi.org/10.1016/j.mineng.2022.107680.Fan Yangyang, Liu Yan, Niu Liping, Zhang Weiguang, Zhang Zimu. Reductive leaching of indium from zinc-leached residue using galena as reductant. Minerals Engineering. 2021;163:106777. https://doi.org/10.1016/j.mineng.2021.106777.Fan Yangyang, Liu Yan, Niu Liping, Zhang Weiguang, Zhang Zimu. Reductive leaching of indium from zincleached residue using galena as reductant // Minerals Engineering. 2021. Vol. 163. Р. 106777. https://doi.org/10.1016/j.mineng.2021.106777.Zhang Tianfu, Liu Wei, Han Junwei, Wu Guiting, Jiao Fen, Qin Wenqing. Selective separation of calcium from zinc-rich neutralization sludge by sulfidation roasting and HCl leaching. Separation and Purification Technology. 2021;259:118064. https://doi.org/10.1016/j.seppur.2020.118064.Zhang Tianfu, Liu Wei, Han Junwei, Wu Guiting, Jiao Fen, Qin Wenqing. Selective separation of calcium from zinc-rich neutralization sludge by sulfidation roasting and HCl leaching // Separation and Purification Technology. 2021. Vol. 259. Р. 118064. https://doi.org/10.1016/j.seppur.2020.118064.Roshanfar M., Khanlarian M., Rashchi F., Motesharezadeh B. Phyto-extraction of zinc, lead, nickel, and cadmium from a zinc leach residue. Journal of Cleaner Production. 2020;266:121539. https://doi.org/10.1016/j.jclepro.2020.121539.Roshanfar M., Khanlarian M., Rashchi F., Motesharezadeh B. Phyto-extraction of zinc, lead, nickel, and cadmium from a zinc leach residue // Journal of Cleaner Production. 2020. Vol. 266. Р. 121539. https://doi.org/10.1016/j.jclepro.2020.121539.Zhou Siyu, Liao Xiaojian, Li Shoupeng, Fang Xiaodi, Guan Zhijie, Ye Maoyou, et al. A designed moderately thermophilic consortia with a better performance for leaching high grade fine lead-zinc sulfide ore. Journal of Environmental Management. 2022;303:114192. https://doi.org/10.1016/j.jenvman.2021.114192.Zhou Siyu, Liao Xiaojian, Li Shoupeng, Fang Xiaodi, Guan Zhijie, Ye Maoyou, et al. A designed moderately thermophilic consortia with a better performance for leaching high grade fine lead-zinc sulfide ore // Journal of Environmental Management. 2022. Vol. 303. Р. 114192. https://doi.org/10.1016/j.jenvman.2021.114192.Li Changbin, Zhang Guofan, Zheng Hong, Zhang Feng, Liu Kun. Study on glass-ceramic prepared by zinc leaching residue and solidification mechanism of heavy metals. Journal of Cleaner Production. 2023;426:139021. https://doi. org/10.1016/j.jclepro.2023.39021.Li Changbin, Zhang Guofan, Zheng Hong, Zhang Feng, Liu Kun. Study on glass-ceramic prepared by zinc leaching residue and solidification mechanism of heavy metals // Journal of Cleaner Production. 2023. Vol. 426. Р. 139021. https://doi.org/10.1016/j.jclepro.2023.39021.KasymovaA.S., Abisheva Z.S., Zhumartbaev E.U., Ponomareva E.I. Kinetics of gallium leaching with sulfuric acid from a phosphorus-containing product. IzvestiyaVuzov. Tsvetnaya Metallurgiya = Izvestiya. Non-Ferrous Metallurgy. 1990;6:72-75. (In Russ.).Касымова А.С., Абишева З.С., Жумартбаев Э.У., Пономарева Е.И. Кинетика выщелачивания галлия серной кислотой из фосфорсодержащего продукта // Известия вузов. Цветная металлургия. 1990. № 6. С. 72‒75.Chirkst D.E., Cheremisina O.V., Chistyakov A.A., Balyan G.A. Kinetics of lixiviation of Zn from slag of Pb-Cu production. Izvestiya vysshikh uchebnykh zavedenii khimiya i khimicheskaya tekhnologiya = ChemChemTech. 2006;49(10):35-38. (In Russ.). EDN: HVODQD.Чиркст Д.Э., Черемисина О.В., Чистяков А.А., Балян Г.А. Кинетика выщелачивания цинка из шлака свинцово-медного производства // Известия вузов. Химия и химическая технология. 2006. Т. 49. № 10. С. 35‒38. EDN: HVODQD.Чиркст Д.Э., Черемисина О.В., Чистяков А.А., Балян Г.А. Кинетика выщелачивания цинка из шлака свинцово-медного производства // Известия вузов. Химия и химическая технология. 2006. Т. 49. № 10. С. 35‒38. EDN: HVODQD.

The authors declare that there are no conflicts of interest present.