vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2021-11-3-340-348vuzbiochemi-638Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESСинтез и исследование экстракционных свойств новых фосфорсодержащих экстрагентов тяжелых металловSynthesis and study of the extraction properties ofnew phosphorus-containing extractants of heavy metalsБишимбаеваГ. K.BishimbayevaG K.

Бишимбаева Гаухар Козыкеевна, д.т.н., профессор, главный научный сотрудник

050010, г. Алматы, ул. Д. Кунаева, 142

Gaukhar K. Bishimbayeva, Dr. Sci. (Engineering), Professor, Chief Researcher

142, Kunaev St., Almaty, 050010

g.bishimbayeva@ifce.kzНалибаеваА. М.NalibayevaA. M.

Налибаева Арайлым Муратовна, научный сотрудник

050010, г. Алматы, ул. Д. Кунаева, 142

Arailym M. Nalibayeva, Researcher

142, Kunaeva St., Almaty, 050010

a.nalibayeva@ifce.kzСайдуллаеваС. А.SaidullayevaS. A.

Сайдуллаева Сабина Абдикаримовна, начальник лаборатории исследований и анализа материалов

050012, г. Алматы, ул. Богембай батыра, 168

Sabina A. Saidullayeva, Head of the Materials Research and Analysis Laboratory

168, Bogembay batyr St., Almaty, 050012

ssabina81@mail.ruЖанабаеваА. К.ZhanabaevaA. K.

Жанабаева Асем Калдыбеккызы, младший научный сотрудник

050010, г. Алматы, ул. Д. Кунаева, 142

Asem K. Zhanabaeva, Junior Researcher

142, Kunaev St., Almaty, 050010

a.zhanabayeva@ifce.kzБолдА.BoldA.

Болд Амангуль, научный сотрудник

050010, г. Алматы, ул. Д. Кунаева, 142

Amangul Bold, Researcher

142, Kunaev St., Almaty, 050010

a.bold@ifce.kzАбдикалыковЕ. Н.AbdikalykovY. N.

Абдикалыков Ерлан Нуржанулы, ведущий инженер

050010, г. Алматы, ул. Д. Кунаева, 142

Yerlan N. Abdikalykov, Leading Engineer

142, Kunaev St., Almaty, 050010

y.abdikalykov@ifce.kzИнститут топлива, катализа и электрохимии им. Д.В. СокольскогоКазахстанD.V. Sokolskiy Institute of Fuel, Catalysis and Electrochemistry, AlmatyKazakhstanИнститут топлива, катализа и электрохимии им. Д.В. СокольскогоКазахстанD.V. Sokolskiy Institute of Fuel, Catalysis and ElectrochemistryKazakhstanТОО «Институт высоких технологий»РоссияInstitute of High TechnologiesRussian FederationТОО «Институт высоких технологий»РоссияD.V. Sokolskiy Institute of Fuel, Catalysis and ElectrochemistryRussian Federation202105102021113340348Copyright © Бишимбаева Г.K., Налибаева А.М., Сайдуллаева С.А., Жанабаева А.К., Болд А., Абдикалыков Е.Н., 20212021Бишимбаева Г.K., Налибаева А.М., Сайдуллаева С.А., Жанабаева А.К., Болд А., Абдикалыков Е.Н.Bishimbayeva G.K., Nalibayeva A.M., Saidullayeva S.A., Zhanabaeva A.K., Bold A., Abdikalykov Y.N.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/638

Резюме: Металлургическая отрасль является одним из краеугольных камней, лежащих в фундаменте современной химической науки и промышленности, и интенсивно развивается во многих странах. Широкое внедрение экстракционных методов извлечения, концентрирования и разделения металлов как наиболее продуктивных влечет за собой необходимость поиска и создания новых эффективных экстрагентов металлов. Среди соединений, пригодных для использования в качестве экстрагентов, наибольшее распространение получили органические фосфиты и фосфаты, которые позволяют проводить экстракционные процессы с хорошей избирательностью и эффективностью. Цель данного исследования – отработка оптимальных условий синтеза и наработка укрупненных партий 4,5-диметил-2-(2,2,2-трифторэтокси)-1,3,2-диоксафосфолана и 5,5-диметил-2-(2,2,3,3,4,4,5,5-октафторпентокси)-1,3,2-диоксафосфоринана, изучение экстракционных свойств полученных фосфорсодержащих гетероциклических соединений при выделении урана из товарного десорбата. Синтез новых представителей указанных полифторалкилированных пяти- и шестичленных гетероциклических соединений фосфора реализован взаимодействием 2-хлор-1,3,2-диоксафосфолана с трифторэтанолом и реакцией замещения-циклизации полифторалкилированного дихлорфосфита с 2,2-диметил-1,3-пропандиолом. Реакции легко протекают в системах триэтиламин–гексан или пиридин–диэтиловый эфир при температуре от минус десяти до комнатной, выход целевых гетероциклов составляет 53–57%. Изучены экстракционные свойства синтезированных полифторалкилированных диоксафосфолана и диоксафосфоринана и показано, что применение указанных фосфорсодержащих гетероциклических соединений в качестве экстрагентов позволяет извлекать технически ценного металла до 12,4 и 15,2% соответственно. В качестве исходного сырья в процессе экстракции использовали азотнокислые и сернокислые растворы товарного десорбата гидрометаллургического производства Казахстана.

Abstract: The metallurgical industry is one of the cornerstones of contemporary chemical science and industry and it is developing rapidly in many countries. The widespread introduction of metal extraction, concentration and separation as the most productive methods entails the need to search for and create new effective metal extractants. Among the compounds, suitable for use as extractants, the most widespread are organic phosphites and phosphates, which allow performing extraction processes with good selectivity and efficiency. The purposes of this article include finalizing the optimal synthesis conditions and developing larger batches of 4,5-dimethyl-2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane and 5,5-dimethyl-2-(2,2,3,3,4,4,5,5- octafluoropentoxy)-1,3,2-dioxaphosphorinane, and study of the extraction properties of the obtained phosphorus- containing heterocyclic compounds in the separation of uranium from the commercial desorbate. The synthesis of new representatives of the indicated polyfluoroalkylated five- and six-membered heterocyclic phosphorus compounds was conducted using the interaction of 2-chloro-1,3,2-dioxaphospholane with trifluoroethanol and the substitution–cyclization reaction of polyfluoroalkylated dichlorophosphite with 2,2-dimethyl- 1,3-propanediol. Reactions easily proceed in triethylamine–hexane or pyridine–diethyl ether systems at temperatures ranging between minus ten to room temperature, with the output of target heterocycles of 53–57%. The studies of extraction properties of synthesized poly-fluorinealkylated dioxaphospholane and dioxaphosphorinane show that the use of these phosphorus-containing heterocyclic compounds as extractants allows extracting a technically valuable metal up to 12.4 and 15.2%, respectively. Nitric and sulfuric acid solutions of commercial desorbate of hydrometallurgical production in Kazakhstan were used as feedstock in the extraction process.

2-полифторалкокси-132-диоксафосфоланы2-полифтор-алкокси-132-диоксафосфоринанытяжелые металлыэкстрагентыэкстракция2-polyfluoroalkoxy-132-dioxaphospholans2-polyfluoro-alkoxy-132-dioxaphosphorinansheavy metalsextractantsextractionРабота выполнена при финансовой поддержке Комитета науки Министерства образования и науки Республики Казахстан (грант № AP08856550). Авторы выражают благодарность сотрудникам лаборатории непредельных гетератомных соединений Иркутского института химии им. А.Е. Фаворского СО РАН академику Б.А. Трофимову, д.х.н., проф. Н.К. Гусаровой, к.х.н. С.И. Верхотуровой, к.х.н. С.Н. Арбузовой за консультации по проведению синтеза фосфорорганических соединений и помощь в интерпретации спектральных данных.The research was funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant no. AP08856550). The authors are grateful to the staff of the Laboratory of unsaturated heteroatomic compounds of A.E. 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The authors declare that there are no conflicts of interest present.