Guo Lei, Niu Yifan, Hu Jianjun, Ju Shaohua, Gu Yongwan, Tan Wenjin
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China.
Key Laboratory of Unconventional Metallurgy, Ministry of Education, Kunming 650093, China.
Materials (Basel). 2023 Sep 19;16(18):6271. doi: 10.3390/ma16186271.
Triphenylphosphine acetylacetone carbonyl rhodium (ROPAC) is an important catalyst in the petrochemical industry, and its deactivated waste catalyst holds significant value for recovery. This study focuses on the existing forms of rhodium (Rh) in waste catalysts and the current status of traditional processes. A green, efficient, and continuous recovery technique was developed using a sealed stainless steel microchannel reactor. The influence of reaction temperature, reaction time, and phase ratio on the Rh recovery rate was investigated, and the process parameters were optimized using response surface methodology (RSM). The results indicate that the magnitude of the impact on the Rh recovery rate follows the order: reaction temperature > reaction time > phase ratio. The optimized process parameters were determined as follows: a reaction time of 29 min, a reaction temperature of 110 °C, and a phase ratio of 1:1, with a corresponding maximum recovery rate of Rh of 66.06%. Furthermore, secondary treatment was performed on the organic phase after primary recovery using the same process conditions, resulting in an overall Rh recovery rate of 95.6%, indicating satisfactory recovery efficiency. Moreover, the application of FTIR and ICP-OES analysis provided definitive evidence that the oxidative dissociation of the rhodium-phosphine chemical bond by HO within ROPAC leads to the conversion of Rh into Rh. Subsequently, Rh forms chloroaquorhodium (III) complexes that enter the aqueous phase, enabling effective recovery of Rh.
三苯基膦乙酰丙酮羰基铑（ROPAC）是石油化工行业中的一种重要催化剂，其失活后的废催化剂具有显著的回收价值。本研究聚焦于废催化剂中铑（Rh）的存在形式以及传统工艺的现状。采用密封不锈钢微通道反应器开发了一种绿色、高效且连续的回收技术。研究了反应温度、反应时间和相比对Rh回收率的影响，并使用响应面法（RSM）对工艺参数进行了优化。结果表明，对Rh回收率的影响程度依次为：反应温度＞反应时间＞相比。优化后的工艺参数确定如下：反应时间29分钟、反应温度110℃、相比1:1，相应的Rh最大回收率为66.06%。此外，在一次回收后的有机相上使用相同工艺条件进行二次处理，Rh的总回收率为95.6%，表明回收效率令人满意。而且，傅里叶变换红外光谱（FTIR）和电感耦合等离子体发射光谱（ICP - OES）分析的应用提供了确凿证据，即ROPAC内的HO使铑 - 膦化学键发生氧化解离，导致Rh转化为Rh。随后，Rh形成氯水合铑（III）配合物进入水相，从而实现Rh的有效回收。
