Bishimbayeva Gaukhar K, Gusarova Nina K, Nalibayeva Arailym M, Verkhoturova Svetlana I, Bold Amangul, Chernysheva Natalya A, Zhangabayeva Assem K, Arbuzova Svetlana N, Abdikalykov Yerlan N, Zhumabayeva Dinara S
D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Kunayev, 142, Almaty 050010, Kazakhstan.
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch Russian Academy of Sciences, St. Favorskogo, 1, 664033 Irkutsk, Russia.
Materials (Basel). 2023 Apr 26;16(9):3394. doi: 10.3390/ma16093394.
In order to obtain sulfur-containing organophosphorus compounds that are promising as extractants of heavy metals, the interaction of elemental phosphorus and sulfur with alkyl bromides catalyzed using strong bases was studied. According to the task, the reaction of non-toxic and non-flammable red phosphorus with alkyl bromides under conditions of phase transfer catalysts (PTC), followed by the introduction of elemental sulfur into the reaction medium, were studied. It is shown that alkyl bromides interact with red phosphorus when heated (95-105 °C, 5-8 h) under conditions of phase transfer catalysts (PTC) in a two-phase system: a 60% aqueous solution of KOH-toluene-benzyltriethylammonium chloride (BTEAC) forming a mixture of organophosphorus compounds along with alkylphosphines (57-60%), are the main reaction products; alkylphosphine oxides are also formed (40-43%). The introduction of elemental sulfur (solution in toluene) at the final stage of the process into the reaction mass cooled to 40-60 °C leads to the expected alkylphosphine sulfides, which are the result of the interaction of alkylphosphines with sulfur. The formation of complex mixtures of products prevents the release of target alkylphosphine sulfides in individual form. However, the synthesized mixture of alkylphosphine sulfides and alkylphosphine oxides without separation into individual components is promising for studying its extraction properties in relation to heavy metals. Testing of the extraction properties of synthesized mixtures of alkylphosphine sulfides and alkylphosphine oxides in relation to heavy metals (Ni, Co, Zn, Pb) and noble metals (Ag) showed that the resulting mixtures of tertiary phosphine oxides and phosphine sulfides are highly effective extractants. The degree of extraction in relation to Ni, Co, Zn, and Pb varies from 99.90 to 99.99%, and for Ag from 99.56 to 99.59%.
为了获得有望作为重金属萃取剂的含硫有机磷化合物,研究了元素磷和硫与在强碱催化下的烷基溴之间的相互作用。根据任务要求,研究了在相转移催化剂(PTC)条件下无毒且不可燃的红磷与烷基溴的反应,随后将元素硫引入反应介质中。结果表明,在相转移催化剂(PTC)条件下,于两相体系(60%氢氧化钾水溶液 - 甲苯 - 苄基三乙基氯化铵(BTEAC))中加热(95 - 105°C,5 - 8小时)时,烷基溴与红磷发生相互作用,形成有机磷化合物与烷基膦(57 - 60%)的混合物,这是主要反应产物;同时也会形成烷基膦氧化物(40 - 43%)。在该过程的最后阶段,将元素硫(甲苯溶液)引入冷却至40 - 60°C的反应物料中,会生成预期的烷基膦硫化物,这是烷基膦与硫相互作用的结果。产物形成复杂混合物阻碍了目标烷基膦硫化物以单一形式分离出来。然而,未经分离成单个组分的合成烷基膦硫化物和烷基膦氧化物混合物在研究其对重金属的萃取性能方面具有前景。对合成的烷基膦硫化物和烷基膦氧化物混合物针对重金属(镍、钴、锌、铅)和贵金属(银)的萃取性能测试表明,所得叔膦氧化物和膦硫化物的混合物是高效萃取剂。对镍、钴、锌和铅的萃取率在99.90%至99.99%之间,对银的萃取率在99.56%至99.59%之间。