盐酸法磷酸萃取相的洗涤和磷酸反萃取过程初探
收稿日期: 2020-10-12
网络出版日期: 2021-08-11
基金资助
国家重点研发计划项目“固废资源化”(2018YFC1900202)
Preliminary study on scrubbing and stripping operation of the extracted organic phase in wet phosphoric acid process by hydrochloric acid route
Received date: 2020-10-12
Online published: 2021-08-11
研究了从以磷酸三丁酯（TBP）为主的萃取相中反萃取磷酸的过程,考察了一步法流程（以硫酸溶液通过沉淀反应去除磷酸萃取有机相中氯化钙的同时反萃取磷酸）以及二步法流程（先以硫酸沉淀反应去除氯化钙,后用去离子水反萃取磷酸）所得的反萃磷酸的净化效果。结果表明,采用一步法时,反萃取磷酸的品质受到硫酸钙溶解平衡的影响,钙含量较高;而采用二步法时,反萃磷酸中氯化钙的质量分数可降低至0.002 7%以下,n（磷酸）/n（钙离子）提升了65倍以上,但有机相中磷酸的洗损为20%左右;利用聚焦光反射测量技术（FBRM）对洗涤过程中硫酸钙在有机相中的结晶过程进行了在线监测,通过扫描电镜（SEM）和X射线衍射（XRD）等手段对副产硫酸钙的晶体形貌和物相组成进行了分析,结果表明实验条件下洗涤10 min时,体系中的Ca2+生成半水石膏（CaSO4·0.5H2O）。计算表明,该盐酸法磷酸工艺洗涤过程中副产石膏值（以二水硫酸钙计）仅为二水硫酸法的8.7%,显著降低了湿法磷酸过程中的石膏处理量。
张少杰 , 唐盛伟 , 王杨 , 郑东钥 , 钟本和 , 陈彦逍 . 盐酸法磷酸萃取相的洗涤和磷酸反萃取过程初探[J]. 无机盐工业, 2021 , 53(8) : 36 -43 . DOI: 10.19964/j.issn.1006-4990.2020-0545
The process of back extraction of phosphoric acid from tributyl phosphate（TBP） was studied.The quality of the different stripped phosphoric acid obtained by the one-step process（simultaneously precipitating CaCl2 and stripping H3PO4 with H2SO4 solution） and by the two-step process（firstly precipitating and removing CaCl2 with H2SO4,then stripping H3PO4 with deionized water） was investigated.The results showed that in the one-step process the purity of the stripped phosphoric acid was affected by the dissolution balance of calcium sulfate with high content of calcium,while in the two-step process,the contents of CaCl2 in the stripped reduced to below 0.002 7%,and the value of n（H3PO4）/n（Ca2+） increased by more than 65 times,but the H3PO4 loss in organic phase caused by scrubbing process was about 20%.The focused beam reflectance measurement（FBRM） technology was used to monitor the crystallization of calcium sulfate on line in the organic phase during the scrubbing process.The morphology and phase composition of the calcium sulfate were analyzed by scanning electron microscope（SEM） and X-ray diffraction（XRD） methods.The results showed that after scrubbing for 10 min under the experimental conditions,Ca2+ in the system basically generated hemihydrate gypsum（CaSO4·0.5H2O）.Theoretical calcula-tion indicated that the production of the by-product gypsum（calculated as CaSO4·2H2O） in scrubbing step of the wet phosp-horic acid process by hydrochloric acid route was only equivalent to 8.7% of that by sulfuric acid route,significantly reduces the amount of gypsum treated in the wet process phosphoric acid process.
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