Preparation of high purity ruthenium nitrosyl nitrate from spent Ru-Zn/ZrO_(2)catalyst

以失效Ru-Zn/ZrO_(2)催化剂为原料制备高纯亚硝酰硝酸钌

Preparation of high purity ruthenium nitrosyl nitrate using spent Ru-Zn/ZrO_(2)catalyst was studied,including melting and leaching to obtain potassium ruthenate solution,reduction,dissolving,concentrating and drying to obtain ruthenium trichloride,nitrosation and hydrolysis to obtain ruthenium nitrosyl hydroxide,removing of K^(+)and Cl^(-),and neutralization with nitric acid.The effects of temperature,concentration,time and pH on the yield and purity of intermediates and final product were studied,and the optimum process conditions were obtained.The yield of ruthenium nitrosyl nitrate is 92%,the content of ruthenium in high purity product is 32.16%,and the content of Cl^(-)and K^(+)are much less than 0.005%.The reaction kinetics of ruthenium nitrosyl chloride to ruthenium nitrosyl hydroxide was studied.The reaction orders of Ru(NO)Cl_(3)at 40,55 and 70℃are 0.39,0.37 and 0.39,respectively,while those of KOH are 0.16,0.15 and 0.17,respectively.The activation energy is-2.33 k J/mol.

以失效Ru-Zn/ZrO_(2)催化剂为原料,经熔融浸出得到钌酸钾溶液,钌酸钾溶液经还原、溶解后,浓缩烘干得到三氯化钌,三氯化钌依次经亚硝酰化、氢氧化钾水解得到亚硝酰氢氧化钌,再经氯、钾等杂离子去除、硝酸中和,得到高纯亚硝酰硝酸钌。研究温度、浓度、时间和pH对中间产物和终产物产率和纯度的影响,得到了较优的工艺条件。在较优工艺条件下,亚硝酰硝酸钌产率为92%,高纯产品中钌含量为32.16%,Cl^(-)、K^(+)含量远低于0.005%。研究了亚硝酰氯化钌制亚硝酰氢氧化钌的反应动力学,得到在40℃、55℃和70℃的温度下,亚硝酰三氯化钌的反应级数分别为0.39、0.37和0.39,氢氧化钾的反应级数分别为0.16、0.15和0.17,活化能为-2.33 k J/mol。