离子膜烧碱生产中高盐卤水体系微量碘净化的热力学与热动力学研究

项目来源

国家自然科学基金(NSFC)

项目主持人

邓天龙

项目受资助机构

天津科技大学

项目编号

21773170

立项年度

2017

立项时间

未公开

研究期限

未知 / 未知

项目级别

国家级

受资助金额

65.00万元

学科

化学科学-化学理论与机制-化学热力学

学科代码

B-B03-B0303

基金类别

面上项目

关键词

热动力学 ; 热力学 ; 量热法 ; 卤水体系 ; 离子膜烧碱 ; ionic membrane caustic soda ; brine system ; thermodynamics ; thermal kinitics ; calorimetry

参与者

余晓平;郭亚飞;张思思;刘元会;李珑;徐青;崔琬晶;陈尚清;廖英

参与机构

天津科技大学;成都大学;中国科学院过程工程研究所

项目标书摘要:离子膜法是目前最先进的烧碱生产方法,但该法对电解用盐水的质量要求甚高(碘含量≤0.2 mg/L),高盐卤水中碘含量超标将严重影响离子膜的使用寿命,从而增加生产成本,是制约我国氯碱行业快速发展的瓶颈问题。本项目在前期研究工作的基础上,以BT2.15绝热量热仪、Nano ITC滴定量热仪、IC/LC-ICP-MS、SEM-EDS、NMR为主要测试分析和表征手段,应用形态分析、水盐体系相平衡、溶液化学、电化学和量热学的理论和方法,开展离子膜烧碱高盐卤水体系溶液热力学与高盐卤水中微量碘形态转化及其树脂吸附净化热动力学创新研究,探索高盐卤水体系多温相平衡、近饱和氯化钠盐水体系碘形态Eh-pH图及其不同形态碘转化过程,揭示盐水中微量碘的树脂吸附净化过程与机制,为离子膜烧碱高盐卤水中微量碘的吸附净化提供重要热力学基础数据,这对于促进离子膜烧碱行业盐水除碘问题的解决、推动我国氯碱行业快速发展具有重大意义。

Application Abstract: Ionic membrane electrolysis is the most advanced technology for the production of caustic soda,but it has high demands for the quality of electrolyzed brine(the concentration of iodine in brine ≤ 0.2 mg/L),in which excessive iodine will seriously influence the service life of ionic membrane and thereby increase the production cost and restrict the development of chlor-alkali industry.Based on our previous research works,the advanced BT2.15 adiabatic micro-calorimeter,Nano ITC-type of titration micro-calorimeter,IC/LC-ICP-MS,SEM-EDS,NMR will be used as the powerful tools of determination and characterizing analysis in this proposed project,and the innovative research approaches of chemical speciation analysis,salt-water phase equilibrium and phase diagram,solution chemistry,electrochemistry and micro-calorimetry will be used to carry out the aqueous phase equilibrium of the high-salinity salt-water system,predominance diagram of Eh-pH,adsorption mechanism and adsorption thermal-kinetic study of the trace iodine by resin ion-exchanging and to reveal the existing forms and transformation rules of iodine in brine.This study will provide important basic data for the purification of the trace iodine in brine and thus have great theoretical significance to promote the solution of iodine problem in ionic membrane caustic soda enterprises and impel the development of chlor-alkali industry.

项目受资助省

天津市

项目结题报告(全文)

据发改委《产业结构调整指导目录(2011)》要求,隔膜法至2015 年末其已被全部淘汰。离子膜法单位产品能耗低30%、产品成本低15%,且烧碱产品质量好、污染低,是目前最先进的烧碱生产方法。但是,离子膜法烧碱生产系统对盐水质量要求较高,当盐水中碘含量大于0.2 mg/L时,在离子膜碱性环境,碘可被氧化为高价态并生成难溶性沉淀,导致电流效率降低,离子膜的使用寿命大大降低。因此,本项目在建立痕量超痕量不同形态碘LC-ICP-MS分析基础上,系统地开展了氯碱化工卤水体系多温多体系相平衡与相图、溶液化学和热力学性质研究,揭示了卤水体系离子相互作用、溶液pH、Eh及其温度关联关系,采用原位微量热技术,明确了不同形态碘的树脂吸/脱碘的过程与机制,探明了离子膜烧碱生产碘净化中试验技术方案和工艺参数。本项目出版中英文学术论著各1部(其中,2021年获中国石油和化学工业优秀出版物教材二等奖1部)。在国际溶液化学热力学与化工领域,发表SCI学术论文25篇(2篇IF大于10,JCRQ1论文14篇、Q2论文5篇)、中文核心2篇、国际会议1篇。授权国家发明专2项。建立水盐体系溶解度特色数据库。承办国际会议2次(第36届国际溶液化学大会,中国西宁,2019;第十四届国际盐湖线上会议,西班牙穆尔希,2021)、全国会议1次(盐类科学高端论坛,北京,2021);参加境外会议1次(第十八届溶解及热力学性质国际研讨会,ISSP-18)、全国会议3次(第十九届中国化学会化学热力学和热分析大会,辽宁沈阳,2019;第二十届中国化学会化学热力学大会,四川绵阳,2021;第七届全国热分析动力学与热动力学会议,安徽合肥,2019)。培养青年教师2名入选省部级人才计划,毕业获博士学位1名、硕士学位毕业3名,考入或硕博连读3名。获天津市自然科学二等奖1项,天津市科技进步成果二等奖1项。博士生获IUPAC青年论坛优秀报告奖、第二十届全国化学化学热力学和热分析学术会议青年论坛优秀报告奖和3项国际国内学术会议最佳Poster奖。2020客座主编《Pure and Applied Chemistry》庆祝IUPAC100周年国际溶液化学专辑。这些研究成果,为离子膜烧碱高盐卤水中微量碘的吸附净化提供了重要的基础数据,对于推动我国氯碱行业可持续发展具有重要意义。

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