亚硝酸与肼或羟胺的反应热测量及工艺验证

Measurement of Reaction Heat Between Nitrous Acid and Hydrazine/Hydroxylamine

采用C80微量热仪分别测定了亚硝酸与肼或羟胺的反应热,得到了亚硝酸与肼以不同摩尔比反应时的摩尔反应热:亚硝酸与肼的摩尔比大于2时,消耗单位摩尔肼的反应放热量ΔE 1=284.4 kJ/mol;亚硝酸与肼的摩尔比小于1时,消耗单位摩尔亚硝酸时的反应放热量ΔE 2=166.7 kJ/mol;亚硝酸与肼的摩尔比介于1和2之间时,消耗单位摩尔肼的反应放热量介于ΔE 1和ΔE 2之间。得到了亚硝酸与羟胺以不同浓度比进行反应时的反应热:亚硝酸过量时,消耗单位羟胺的反应放热量为ΔE 4=200.0 kJ/mol;羟胺过量时,消耗单位亚硝酸时的反应放热量为ΔE 5=194.9 kJ/mol。基于获得的亚硝酸与肼或羟胺的反应热数据,对核燃料后处理工艺流程中1BP调料过程中的温度升高情况进行了计算分析,并通过工艺实验进行了验证。

The reaction heats released by the reaction between nitrous acid and hydrazine and hydroxylamine were respectively investigated using micro calorimeter C80.The results show that the reaction heat per mole of nitrous acid with hydrazine depends on their proportions.While the concentration of nitrous acid is two times higher than that of hydrazine,the reaction heat per mole of hydrazine(ΔE 1)is 284.4 kJ/mol.The reaction heat per mole of nitrous acid(ΔE 2)is 166.7 kJ/mol when the concentration ratio of nitrous acid to hydrazine is less than 1.Additionally,when the concentration ratio is between 1 and 2,the reaction heat per mole of hydrazine is betweenΔE 1 andΔE 2.The reaction heat per mole of nitrous acid depends on nitrous acid/hydroxylamine proportions.When the concentration of nitrous acid is more than that of hydroxylamine,the reaction heat per mole of hydroxylamineΔE 4 is 200.0 kJ/mol;whereas the concentration of nitrous acid is less than that of hydroxylamine,the reaction heat per mole of nitrous acidΔE 5 is 194.9 kJ/mol.The temperature increment of feed adjustment for 1 BP in the spent fuel reprocessing process is also discussed and tested.