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邻苯二甲酸二乙酯富聚氯乙烯和废铜催化剂的亚临界水(水热处理)低温共处理:脱氯、回收邻苯二甲酸二乙酯和铜。

A low-temperature co-treatment of diethylhexyl phthalate-rich polyvinyl chloride and waste copper catalyst by subcritical water (hydrothermal treatment): Dechlorination, recovery of diethylhexyl phthalate and copper.

机构信息

College of Geology and Environment, Xi'an University of Science and Technology, Xi'an 710054, China.

College of Geology and Environment, Xi'an University of Science and Technology, Xi'an 710054, China.

出版信息

Waste Manag. 2024 Dec 1;189:276-289. doi: 10.1016/j.wasman.2024.08.032. Epub 2024 Aug 31.

Abstract

As one of the most widespread plastics in the world, the recycling of diethylhexyl phthalate-rich polyvinyl chloride (DEHP-rich PVC) faces great challenges because of the high levels of Cl and plasticizers. On the other hand, waste copper catalyst (WCC) discharged from various industrial processes is not effectively recycled. In this study, a significant synergistic effect between the DEHP-rich PVC and WCC was found in a subcritical water (SubCW) medium, and a co-treatment of the DEHP-rich PVC and WCC was developed by the SubCW process. The introduction of WCC significantly improved the dechlorination efficiency of the DEHP-rich PVC to 96.03 % at a low temperature of 250 °C. Under the optimal conditions, the leaching of copper from WCC reached a maximum of 81.08 %. Oil products included DEHP (55.7 %, GC peak area%), 3-methyl-3-heptene (37.3 %, GC peak area%), and 2-ethyl-1-hexanol (7.0 %, GC peak area%). The dechlorination pathways of the DEHP-rich PVC included hydroxyl substitution and direct dechlorination. HCl released from the DEHP-rich PVC led to a decrease in the pH of the system and significant copper leaching from the WCC. DEHP was decomposed by hydrolysis, dehydration, and rearrangement reaction by the SubCW co-treatment process. The enhancement mechanism of the WCC for the dechlorination of the DEHP-rich PVC was based on that the conversion of copper species in the SubCW promoted the formation of hydroxyl radicals and the hydroxyl substitution for chlorine in PVC molecular chain. The proposed SubCW low-temperature co-treatment could be a prospective strategy for the low-energy and synchronous recovery of the two different wastes of the DEHP-rich PVC and WCC.

摘要

作为世界上应用最广泛的塑料之一,由于氯和增塑剂含量高,富含邻苯二甲酸二乙酯的聚氯乙烯 (DEHP 富 PVC) 的回收面临巨大挑战。另一方面,各种工业过程中排放的废铜催化剂 (WCC) 尚未得到有效回收。在本研究中,在亚临界水中 (SubCW) 介质中发现富含邻苯二甲酸二乙酯的 PVC 和 WCC 之间存在显著的协同效应,并通过 SubCW 工艺开发了富含邻苯二甲酸二乙酯的 PVC 和 WCC 的共处理。WCC 的引入显著提高了 DEHP 富 PVC 在 250°C 的低温下的脱氯效率,达到 96.03%。在最佳条件下,WCC 中铜的浸出率达到最大值 81.08%。油产品包括邻苯二甲酸二乙酯 (55.7%,GC 峰面积%)、3-甲基-3-庚烯 (37.3%,GC 峰面积%)和 2-乙基-1-己醇 (7.0%,GC 峰面积%)。DEHP 富 PVC 的脱氯途径包括羟基取代和直接脱氯。来自 DEHP 富 PVC 的 HCl 导致系统 pH 值降低,并且 WCC 中铜的浸出量显著增加。DEHP 通过水解、脱水和重排反应被 SubCW 共处理过程分解。WCC 增强 DEHP 富 PVC 脱氯的机制基于 SubCW 中铜物种的转化促进了羟基自由基的形成以及 PVC 分子链中氯的羟基取代。提出的 SubCW 低温共处理可以作为一种有前景的策略,用于两种不同废物(富含邻苯二甲酸二乙酯的 PVC 和 WCC)的低能耗和同步回收。

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