塑料污染控制已成为全球最值得关注的环境问题之一。作为典型的含卤塑料，聚氯 乙烯(PVC)及多溴联苯醚树脂分别广泛应用于建筑设施管道、生活消费塑料制品及电子 工业中。随着各种塑料产品更新换代加快，待处理的废旧含卤塑料数量急剧增加。传统 的处置方式容易引发土壤和地下水的污染，甚至产生氯代或溴代二噁英等高毒性物质。 废旧含卤塑料实现其无害化脱毒及资源化回收的关键是安全高效脱卤，本文以含多溴联 苯醚的废旧印刷线路板(WPCBs)及含氯废旧 PVC 塑料为研究对象，分别构建了亚临界 甲醇(SubCM)和亚临界水(SubCW)脱卤体系，实现了 WPCBs 及废旧 PVC 的低温高效脱 卤，为含卤塑料废弃物的脱卤脱毒提供了新的方案。主要结论如下： （1）WPCBs 中多溴联苯醚在亚临界甲醇中的脱溴。亚临界甲醇温度升高、停留时 间增加和固液比的降低有利于提高多溴联苯醚的去除效率,最佳参数条件为:200 o C, 60 分钟, 1:20 g/mL。最佳条件下对多溴联苯醚总量的去除率可达 91.3%。NaOH 的引入可 进一步强化多溴联苯醚的去除，亚临界甲醇+NaOH (4 g/L)体系对多溴联苯醚总量的去除 率可达 98.8%。经过亚临界甲醇处理后，高溴化的多溴联苯醚在低于 200 o C 时降解为 2,3',4',6-四溴二苯醚和 2,4,4'-三溴二苯醚。温度超过 200 o C 时，2,3',4',6-四溴二苯醚和 2,4,4'-三溴二苯醚可进一步脱溴生成 4-溴二苯醚和二苯醚。亚临界甲醇+NaOH 体系可 显著降低多溴联苯醚的脱溴温度。亚临界甲醇和亚临界甲醇+NaOH体系可分别在300 o C 和 250 o C 下实现 WPCBs 中多溴联苯醚的完全脱溴。根据降解产物的表征分析，亚临界 甲醇和亚临界甲醇+NaOH 体系对多溴联苯醚的脱溴降解路径没有显著差异。 （2）废旧 PVC 在亚临界水-粉煤灰/煤矸石(SubCW-CFA/CG)体系中的脱氯。采用 粉煤灰及煤矸石作为 PVC 脱氯强化剂，引入亚临界水体系，构建了废旧 PVC 的亚临界 水-粉煤灰/煤矸石脱氯体系。升高温度、增加粉煤灰/煤矸石添加量和降低固液比有利 于脱氯。停留时间过长导致废旧 PVC 基体碳化，形成多孔结构，导致脱除的氯被重新 固定。最佳脱氯参数条件为:220 o C，60 分钟，粉煤灰/煤矸石:0.4 g，1:30 g/mL。在最 佳参数条件下，亚临界水-粉煤灰/煤矸石体系对废旧 PVC 的脱氯效率分别达到 96%和 97.34%。傅里叶红外光谱和元素分析表明废旧 PVC 的脱氯包括两种路径:直接脱氯化氢 和羟基取代。直接脱氯化氢导致多烯结构的生成，C-Cl 键的羟基取代导致了 C=O 稳定 结构的形成，C=O 稳定结构的形成进一步促进了脱氯过程。 （3）废旧 PVC 在亚临界水-零价铁粉(SubCW-Fe)体系中的脱氯。将零价铁粉引入 亚临界水中，利用亚临界水独特的物化性质和零价铁的强还原性，构建了废旧 PVC 的 亚临界水-零价铁脱氯体系。升高温度、降低固液比、适当的铁粉添加量和适宜的停留 时间，能有效促进脱氯。最佳脱氯参数条件:200 ℃, 60 分钟,1:30 g/mL,Fe:0.4 g (PVC:Fe=4:1)，脱氯效率可达 96.02%。脱除的氯全部以无机氯的形式转移至水相，消除 了氯的环境风险。采用 XRD 分析和傅里叶红外分析研究了废旧 PVC 在亚临界水-零价 铁粉体系中的脱氯机制。脱氯过程包含两个路径：直接脱氯化氢和羟基取代。直接脱氯 化氢导致生成多烯结构，羟基取代形成更稳定的碳氧双键(C=O)结构，并进一步促进了 脱氯过程。 （4） PVC 和废旧 LCD 面板的亚临界水共处理体系。将另一类固体废物 LCD 面板 引入 PVC 的亚临界水脱氯体系，同时实现了 PVC 低温高效脱氯和废旧 LCD 面板中有 机物的高效剥离去除。废旧 LCD 面板中大量的金属氧化物可以显著提高 PVC 的脱氯效 率，同时脱除的氯化氢对 LCD 面板中金属氧化物的浸出具有一定的促进作用。升高共 处理温度、增加停留时间、适当的 PVC-LCD 质量比和较低的固液比能有效提高脱氯效 率。最佳工艺参数:220 ℃, 90 分钟, PVC-LCD 质量比 4:1，固液比 1:30 g/mL。最佳条件 下 PVC 的脱氯效率可达 100%，且氯全部转移至水相。当共处理温度超过 200 ℃时，废 旧 LCD 中所含有机物的剥离去除率达 100%。在亚临界水共处理中 PVC 残渣形成稳定 的烯烃-羰基结构(=C-C=O)，进一步促进了 PVC 的脱氯反应。

Plastic pollution control has become one of the most worthy of attention environmental issues in the world. As a typical halogen-containing plastics, polyvinyl chloride (PVC) and polybrominated diphenyl ethers resins are widely used in the construction pipelines, consumer plastic products and electronics industry, respectively. With the accelerated upgrading of various plastic products, the number of waste halogen-containing plastics to be treated has increased sharply. Traditional disposal methods can easily cause soil and groundwater pollution, and even produce highly toxic substances such as chlorinated or brominated dioxins. The key to the harmless detoxification and resource recycling of waste halogen-containing plastics is safe and efficient dehalogenation, this article uses polybrominated diphenyl ethers-containing waste printed circuit boards (WPCBs) and chlorine-containing waste PVC plastics as the research objects, respectively construction subcritical methanol (SubCM) and subcritical water (SubCW) dehalogenation system to realizes the low-temperature and high-efficiency dehalogenation of WPCBs and waste PVC, and provides a new solution for the dehalogenation and detoxification of halogen-containing plastic waste. The primary conclusions as follows:

The debromination of polybrominated diphenyl ethers in WPCBs in subcritical methanol (SubCM). The increase of subcritical methanol temperature, the increase of residence time and the decrease of solid-liquid ratio were beneficial to improve the removal efficiency of polybrominated diphenyl ethers, the optimal parameter conditions were as follows: 200 ^oC, 60 min, 1:20 g/mL. Under the optimal parameter conditions, the removal efficiency of polybrominated diphenyl ethers can reach 91.3%. The introduction of NaOH can further strengthen the removal of polybrominated diphenyl ethers, and the removal rate of polybrominated diphenyl ethers (Σ₈PBDEs) by the subcritical methanol+NaOH (4 g/L) system can reach 98.8%. When the temperature is below 200℃, highly brominated polybrominated diphenyl ethers congeners were degraded into 2,3',4',6-Tetrabromodiphenyl ether and 2,4,4' -Tribromodiphenyl ether after SubCM treatment. When the temperature exceeds 200 ^oC, 4-Bromophenyl ether and diphenyl ether were generated by the further debromination of 2,3',4',6-Tetrabromodiphenyl ether and 2,4,4' -Tribromodiphenyl ether. The debromination temperature of polybrominated diphenyl ethers congeners in SubCM+NaOH system could be markedly lowered. So the complete debromination of polybrominated diphenyl ethers congeners in WPCBs could be achieved at 300 ^oC and 250 ^oC for the developed system of SubCM and SubCM+NaOH, respectively. According to the characterization analysis of degradation products, there is no significant difference in the debromination degradation pathways of polybrominated diphenyl ethers by subcritical methanol and subcritical methanol+NaOH systems. 

Dechlorination of waste PVC in subcritical water-coal fly ash/coal gangue (SubCW-CFA/CG) system. Use of coal fly ash and coal gangue as PVC dechlorination enhancers, the introduction of subcritical water system, the construction of subcritical water-coal fly ash/gangue dechlorination system of waste PVC. Increasing the temperature, increasing the amount of coal fly ash/coal gangue added, and decreasing the solid-liquid ratio are favorable for dechlorination. Excessive residence time causes the carbonization of the waste PVC matrix, forming a porous structure, and causes the removed chlorine to be re-fixed. The optimal dechlorination parameters were as follows: 220 ^oC, 60 min, 0.4 g, 1:30 g/mL. Under the optimal parameters, the chlorine removal efficiency of PVC reached 96% and 97.34% in the subcritical water-coal fly ash/coal gangue system. Fourier transform infrared and elemental analysis were used to analyze the dechlorination mechanism of PVC contains two pathways: direct dehydrochlorination and hydroxyl substitution. The direct dehydrochlorination resulted in the generation of polyene structure, and the hydroxyl substitution of C-Cl induced the formation of the stable structure of C=O, the formation of C=O stable structure further promotes the dechlorination process.

Dechlorination of waste PVC in subcritical water-zero valent iron powder (SubCW-Fe) system. The zero valent iron powder is introduced into subcritical water, and the unique physical and chemical properties of subcritical water and the strong reducibility of zero valent iron are used to construct a subcritical water-zero valent iron dechlorination system for waste PVC. Increasing the temperature, decreasing the solid-to-liquid ratio, adding appropriate amount of zero valent iron and appropriate residence time can effectively promote dechlorination. The optimal dechlorination parameter conditions  were as follows : 200 ^oC, 60 min, 1:30 g/mL, Fe:0.4 g (PVC:Fe=4:1), and the dechlorination efficiency reached 96.02%. All of the removed chlorine was transferred to the aqueous phase in the form of inorganic chlorine, and eliminated the environmental risk of chlorine. The dechlorination mechanism of waste PVC in subcritical water-zero valent iron powder system was studied by XRD analysis and Fourier transform infrared analysis. The dechlorination mechanism contains two pathways: direct dehydrochlorination and hydroxyl substitution. The direct dehydrochlorination resulted in the generation of polyene structure, and the hydroxyl substitution of C-Cl induced the formation of the stable structure of C=O, and further promotes the dechlorination process.

Subcritical water co-treatment system for PVC and waste LCD panels. Will the other solid waste LCD panel was introduced into the subcritical water dechlorination system of PVC, and at the same time it realizes the low-temperature and high-efficiency dechlorination of PVC and the efficient stripping and removal of organic matter in the waste LCD panel. A large amount of metal oxides in waste LCD panels can significantly improve the dechlorination efficiency of PVC, and the removed hydrogen chloride has a certain promoting effect on the leaching of metal oxides in LCD panels. Increasing the co-treatment temperature, increasing the residence time, proper PVC-LCD mass ratio and lower solid-to-liquid ratio can effectively improve the efficiency of dechlorination. The optimum parameter conditions: 220 ^oC, 90 min, PVC-LCD mass ratio 4:1, solid-liquid ratio 1:30 g/mL. Under the optimal parameter conditions, the dechlorination efficiency of PVC can reach 100%, and all the chlorine is transferred to the aqueous phase. When the co-processing temperature exceeds 200 ^oC, the stripping and removal rate of organic matter contained in the waste LCD reaches 100%. The stable alkene-carbonyl structure (=C-C=O) formed in the subcritical water co-treatment of PVC residue further promoted the dechlorination reaction of PVC.

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