摘要
以混合丁烯和合成气(H_(2)/CO)为原料,铑/双膦配体作催化剂通过羰基化反应生成中间产品戊醛,戊醛再经缩合加氢制环保型增塑剂2-丙基庚醇,该工艺具有贵金属铑浓度低、产物正异比高、反应快、条件温和等特点,但反应液中铑浓度是影响低压羰基合成反应的重要因素。通过建立2-丙基庚醇含铑催化剂反应液的处理方法及其中铑含量测定方法,研究了萃取法分离铑的反应条件,对不同萃取条件下铑含量测定方法做了比较,并与传统消解法及原子吸收法直接测定有机液中铑的方法进行对比,具有反应条件温和、处理便捷、重现性好等特点。结果表明:80℃下,采用10.0 mL硝酸(1+4)、10.0 mL过氧化氢水溶液(H2O2质量分数为30%)、4.0 mL甲苯处理5.0000 g含铑废液1 h,分液后萃取分离,铑从油相转移至水相,定容后采用ICP-AES测定水相中铑含量,相对标准偏差(RSD,n=6)为0.6%,加标回收率为96.80%~101.19%。
Using a mixture of butene and synthesis gas(H_(2)/CO)as raw materials,rhodium/diphosphine ligand was used as a catalyst to generate the intermediate product valeraldehyde through carbonylation reaction.The valeraldehyde is then condensed and hydrogenated to produce the environmentally friendly plasticizer alcohol 2-propylheptanol.This process had the characteristics of low concentration of precious metal rhodium,high aspect ratio of the product,fast reaction,and mild conditions.However,the rhodium concentration in the reaction solution was an important factor affecting the lowpressure carbonylation synthesis reaction.By establishing a method for treating the reaction solution of 2-propylheptanol containing rhodium catalyst and determining the rhodium content in it,the reaction conditions for separating rhodium by extraction method were studied.The rhodium content determination methods under different extraction conditions were compared,and compared with the traditional digestion method and atomic absorption method for directly determining rhodium in organic liquids.The method had the characteristics of mild reaction conditions,convenient processing,and good reproducibility.The results showed that at 80℃,5.0000 g of rhodium containing waste liquid treated with 10.0 mL of nitric acid(1+4),10.0 mL of hydrogen peroxide aqueous solution(H2O2 mass fraction of 30%),and 4.0 mL of toluene for 1 hour,after separation,the rhodium was extracted and separated,and the rhodium was transferred from the oil phase to the water phase.After reaching a constant volume,the rhodium content in the water phase was determined by ICP-AES,with a relative standard deviation(RSD,n=6)of 0.6%and standard recovery rates ranging from 96.80%to 101.19%.
作者
王勇
李继霞
张桂生
王鹏飞
王本雷
WANG Yong;LI Jixia;ZHANG Guisheng;WANG Pengfei;WANG Benlei(Guoneng Baotou Coal Chemical Co.,Ltd.,baotou 014010,China;CNOOC Tianjin Chemical Research and Design Insititute Co.,Ltd.,Tianjin 300131,China)
出处
《无机盐工业》
CAS
CSCD
北大核心
2024年第9期142-146,共5页
Inorganic Chemicals Industry
关键词
分析化学
萃取方法
测定
含铑反应液
铑
analytical chemistry
extraction method
determination
reaction solution of rhodium compound
rhodium
作者简介
王勇(1969—),男,中级工程师,从事碳四装置工艺管理工作,E-mail:yongwang.s@chnenery.com.cn。;通讯作者:李继霞(1979—),女,高级工程师,从事烯烃氢甲酰化工艺研究及贵金属催化相关工作,E-mail:nkljxia@126.com。
