硝酸氧锆溶液的制备研究
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- 英文论文题名：Study on preparation of zirconyl nitrate solution
- 论文作者：康武 ; 张嘉 ; 李佳 ; 卢长先
- 英文论文作者：KANG Wu ; ZANG Jia ; LI Jia ; LU Chang-xian ; Nuclear Power Institute of China
- 年：2015
- 作者机构：中国核动力研究设计院;
- 论文关键词：硝酸氧锆 ; 四氯化锆 ; 去氯
- 英文论文关键词：Zirconyl nitrate ; Zirconium tetrachloride ; dechlorination
- 会议召开时间：2015-09-21
- 会议录名称：中国核科学技术进展报告（第四卷）——中国核学会2015年学术年会论文集第6册（核化学与放射化学分卷、核化工分卷）
- 语种：中文
- 分类号：TL352.2
- 学会代码：EGVD
- 会议名称：中国核学会2015年学术年会
- 会议地点：中国四川绵阳
- 主办单位：中国核学会
- 学会名称：中国核学会
- 页数：6
- 文件大小：263k
- 原文格式：O
- 会议级别：全国
摘要
硝酸氧锆为制备含锆微球重要原材料之一,而目前市面上采购的硝酸氧锆产品铪含量均超标(约5 000 ppm),以其为原材料制备的燃料微球,其堆内行为必然会受到严重影响。通过对原材料的市场调研,选取了两种合适的原材料及相应的工艺过程,并对两种工艺进行实验比对,最终选择以四氯化锆为原料的工艺。该工艺包括水解、去氯、溶液沉淀、洗涤过滤、溶解浓缩等步骤。本文系统的研究了该工艺反应温度、过氧化氢加入量、反应时间等条件对除氯效果的影响;沉淀时溶液温度、搅拌速度、老化时间等因素对沉淀效果的影响,通过实验现象和分析结果,实验表明:采用该工艺制得的缺酸硝酸氧锆溶液,锆含量为180~220 g/L,NO_2~-/Zr(摩尔比)=1.7~1.9,Cl含量<10 ppm,满足项目要求。其适宜的工艺参数为:以100 g四氯化锆加入量计,水用量200 mL,过氧化氢溶液(30%)用量200 mL(过氧化氢溶液与四氯化锆质量比为1:2.2~2.5);去氯时加热温度为80℃,去氯反应时间2 h,整个去氯过程保证系统为微负压状态;沉淀时水解液温度75±5℃,老化时间5 min;沉淀过滤采用离心过滤的方式,洗涤次数3次以上;溶解时浓硝酸(65%)加入量为计算量的90%,以先向溶解容器内加入硝酸后加入沉淀物的方式进行。该工艺操作条件下制的的产品性质稳定,杂质元素含量合格。
Zirconyl nitrate is one of the important raw materials for preparing zirconium microspheres.However,hafnium contents in Zirconyl nitrate available on the procurement market are overweight(about 5 000 ppm).The in-pile behavior of fuel microspheres prepared by such raw materials will inevitably be affected by hafnium.Through market research on raw materials,the author selects two kinds of suitable raw materials and the corresponding technological processes,and conducts experiment comparison of two kinds of processes.Zirconium tetrachloride is chosen as raw material.Through hydrolysis,dechlorination,solution precipitation,washing,filtering,dissolution concentration and other steps,zirconyl nitrate solution lack of acid is prepared.Besides,the author does systematic research on the effect of reaction temperatures,the amount of hydrogen peroxide,reaction time and other conditions on dechlorination as well as the effect of solution temperatures,stirring speeds,aging time and other factors on precipitation results.The experiment and analysis results show that in zirconyl nitrate solution lack of acid,zirconium content is 180~220 g/L,NO_3~-/Zr(mole ratio) = 1.7~1.9 and Cl<10ppm,which meet the project requirement.The appropriate process parameters are as follows:100 g zirconium tetrachloride in the flow meter,200 mL water,200 mL hydrogen peroxide solution(30%)(The mass ratio of hydrogen peroxide solution and zirconium tetrachloride is 1:2.2~2.5);the heating temperature of 80 ℃ during dechlorination,dechlorination reaction time 2h,slightly negative pressure state;the hydrolysate temperature of 70~80 ℃ for precipitation,the aging time of 5 min;centrifugal filtration,washing for 3 times or more;90% of the calculated amount of concentrated nitric acid(65%) during dissolution,adding nitrate first into the dissolution container before adding sediment.The products prepared by this process show stable properties and the impurity element content meets the requirement.
Zirconyl nitrate is one of the important raw materials for preparing zirconium microspheres.However,hafnium contents in Zirconyl nitrate available on the procurement market are overweight(about 5 000 ppm).The in-pile behavior of fuel microspheres prepared by such raw materials will inevitably be affected by hafnium.Through market research on raw materials,the author selects two kinds of suitable raw materials and the corresponding technological processes,and conducts experiment comparison of two kinds of processes.Zirconium tetrachloride is chosen as raw material.Through hydrolysis,dechlorination,solution precipitation,washing,filtering,dissolution concentration and other steps,zirconyl nitrate solution lack of acid is prepared.Besides,the author does systematic research on the effect of reaction temperatures,the amount of hydrogen peroxide,reaction time and other conditions on dechlorination as well as the effect of solution temperatures,stirring speeds,aging time and other factors on precipitation results.The experiment and analysis results show that in zirconyl nitrate solution lack of acid,zirconium content is 180~220 g/L,NO_3~-/Zr(mole ratio) = 1.7~1.9 and Cl<10ppm,which meet the project requirement.The appropriate process parameters are as follows:100 g zirconium tetrachloride in the flow meter,200 mL water,200 mL hydrogen peroxide solution(30%)(The mass ratio of hydrogen peroxide solution and zirconium tetrachloride is 1:2.2~2.5);the heating temperature of 80 ℃ during dechlorination,dechlorination reaction time 2h,slightly negative pressure state;the hydrolysate temperature of 70~80 ℃ for precipitation,the aging time of 5 min;centrifugal filtration,washing for 3 times or more;90% of the calculated amount of concentrated nitric acid(65%) during dissolution,adding nitrate first into the dissolution container before adding sediment.The products prepared by this process show stable properties and the impurity element content meets the requirement.
引文
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[3]朱海涛,等.用两性与非离子混合表面活性剂合成ZrO2介孔材料[J].无机化学学报,2004,20(11):1284-1288.
[4]李文,等.制备条件对ZrO2晶相结构的影响[J].分子催化,1999,13(4):271-276.
[5]郭伟,等.超细氢氧化锆颗粒制备实验研究,材料导报,2006,20(7):176-179.
[6]唐勋海,等.氯氧化锆前躯体制备纳米氧化锆的机理探讨,无机盐工业,2004,36(3):13-15.