| 题名 | Pd/C 和Raney Ni 催化有机卤代物的液相高效加氢脱卤研究 |
| 作者 | 马宣宣 |
| 学位类别 | 博士 |
| 答辩日期 | 2015-05-19 |
| 授予单位 | 中国科学院大学 |
| 授予地点 | 北京 |
| 导师 | 夏传海 |
| 关键词 | 催化加氢脱卤 Pd/C Raney Ni 多氯联苯 氯代苯酚 催化剂表征 卤代芳烃 溶剂效应 |
| 中文摘要 | 持久性有机污染物（POPs）由于卤素原子的存在而具有环境持久性、生物蓄积性以及高毒性，其对人类和环境造成了巨大的危害而受到各国政府和广大研究人员的重视。多相催化加氢脱卤技术可以在温和条件下有效脱除卤素原子并降低其毒性，因此在消除POPs的环境污染方面受到广泛的关注。 本论文以Pd/C和Raney Ni作为催化剂，氢气作为氢源，对氯代苯酚、卤代苯酚、卤代苯、多氯联苯等在液相体系中的加氢脱卤进行了相关的研究。在液相体系中，详细考察了溶剂体系对催化剂活性和加氢脱卤反应的影响，并通过催化剂表征手段研究了催化剂在有机溶剂中失活的原因及其在含水体系中保持高活性和高稳定性的原因，发展了醇-水均相体系中PCBs等POPs的高效降解体系，实现了高浓度PCBs等POPs的高效加氢降解，同时实现了水中高浓度卤代苯酚在Raney Ni催化下的高效加氢降解，而且催化剂均能够保持高的活性和稳定性，这就为库存POPs的消减提供了一种有效的降解方法。针对DDT重污染场地土壤样品，发展了溶剂热萃取-催化加氢联合处理技术，可以有效消除DDT重污染场地土壤样品的毒性，并通过加氢处理达到降解萃取物毒性的目的。 研究了溶剂及碱对加氢脱卤反应活性及选择性的影响；对卤代芳烃在Pd/C和Raney Ni催化下的加氢脱卤进行了比较研究，并通过催化剂表征手段对卤代芳烃在两种催化剂催化下的表现出不同反应性的原因做了初步探讨。得出的主要结论如下： 在液相加氢脱氯反应中，溶剂效应对加氢脱氯反应有着非常重要的影响。与非质子溶剂相比，质子溶剂是更好的溶剂；对于质子溶剂中的加氢脱氯反应来说，加氢脱氯反应速率随着溶剂极性的增加而逐渐增大。 原位生成的无机盐，如NaCl，会沉积在Raney Ni催化剂表面，进而导致在有机溶剂中使用的催化剂失活。而有机溶剂中原位生成的NaCl等无机盐在催化剂表面的堆积导致的催化剂的失活是液相加氢脱氯反应过程中的共性规律，而不是一个特殊的现象。同时，醇-水混合溶剂作为反应介质能够避免原位生成的NaCl沉积在催化剂表面而使催化剂在加氢脱氯反应过程中保持较高的活性和稳定性。通过对溶剂体系对加氢脱氯反应的影响及其具体影响机制的研究，阐明了催化剂失活的具体原因，并基于此发展了一种条件温和、效率较高且环境友好的醇-水均相溶剂体系，可以用于高浓度库存POPs的多相催化加氢降解研究中。 基于溶剂效应的研究，将醇-水混合溶剂体系应用于库存电容器油的加氢处理并将其应用于商业Pd/C催化剂催化高浓度电容器油中多氯联苯的加氢脱氯处理，同时研究了温度、压力、溶剂及水的添加对电容器油中多氯联苯加氢脱氯的影响，并取得了比较好的降解效果。这就为高浓度多氯联苯的加氢脱氯处理提供了一种高效实用的溶剂体系。 针对土壤样品的处理，将溶剂热萃取与醇-水混合溶剂体系中液相加氢脱氯相结合用于DDTr重污染场地土壤样品的处理并为日后实际应用提供了一些指导，同时，同时研究了DDT、DDE和DDD液相加氢脱氯反应，取得了比较好的降解效果，并提出了这三种物质具体的脱氯反应路径。 研究并比较了醇-水混合溶剂体系中卤代芳烃在Pd/C和Raney Ni催化下的加氢脱卤。对于单一卤代芳烃的液相加氢脱卤，当Pd/C作为催化剂时，C-X键氢化裂解反应性顺序为：C-Br > C-Cl > C-I > C-F；而当Raney Ni作为催化剂时，C-X键氢化裂解反应性顺序为：C-I > C-Br > C-Cl > C-F。对于单一卤代芳烃的液相加氢脱卤来说，对于混合卤代芳烃的液相加氢脱卤，当Pd/C和Raney Ni作为催化剂时，C-X键氢化裂解反应性顺序均为：C-I > C-Br > C-Cl > C-F。基于对Pd/C催化单一和混合卤代芳烃加氢脱卤反应性的比较研究，我们认为单一卤代芳烃加氢脱卤反应中氯代芳烃和溴代芳烃加氢脱卤反应性要高于碘代芳烃加氢脱卤反应性主要是由于碘代芳烃在催化剂表面强烈的吸附作用导致的。 对于卤代芳烃的液相加氢脱卤，Pd/C催化剂对4-溴苯酚和4-氯苯酚的加氢脱卤表现出高的催化活性，而对4-碘苯酚和4-氟苯酚（尤其是4-氟苯酚）的加氢脱卤表现出低的催化活性。根据催化剂表征（SEM、EDSX和XRD）分析可知，原位生成的I-会吸附在催化剂表面，这是由于I-在催化剂表面具有强烈的吸附作用。在卤代芳烃液相加氢脱卤反应中，原位生成的I-的强烈吸附作用会导致催化剂活性降低，进而使卤代芳烃混合物的加氢脱卤反应性低于单一卤代芳烃加氢脱卤反应性。这可能是碘代芳烃或NaI存在时卤代芳烃加氢脱卤反应性低的主要原因。 对于温和条件下Raney Ni催化剂催化高浓度氯代苯酚类化合物的加氢脱氯来说，水是最有效的反应溶剂。在水中，一系列的氯代苯酚类化合物可以得到有效地降解，而且催化剂比在50%水-乙醇（50/50，v/v）中表现出更高的催化活性和稳定性。根据高倍扫描电镜分析，我们首次发现在液相加氢脱氯过程中溶剂能够影响Raney Ni催化剂的表面微观形貌。这可能是Raney Ni催化剂在水中比在50%水-乙醇（50/50，v/v）混合溶剂中表现出更高活性和稳定性得原因。 |
| 英文摘要 | Due to the existence of halogen atom, persistent organic pollutants (POPs) exhibit high toxicity, bioaccumulate in the food web, persist in the environment, and pose a risk of causing adverse effects to human health and the environment. Thus, it is urgent to develop an efficient and cost-effective method to detoxify and destroy them with the ever increasing concern about the environment protection. Catalytic hudrodehalogenation (HDH) represents a viable alternative and non-destructive treatment for transforming toxic hazardous material into less toxic products that can be more easily degraded or even possess commercial importance, and was received more and more attention. In this study, liquid-phase HDH of chlorophenols, halobenzenes, 4-halophenols, PCBs, and other HACs using Pd/C or Raney Ni catalyst under mild conditions were investigated. In liquid-phase system, the influence of solvent system on the activity of catalyst and HDH reactivity were studied in detail, and the reason for the deactivation of catalyst in organic solvent and the catalyst keep high activity and stability was elucidated by means of catalyst characterization. On the basis of these studies, alcohol-water homogeneous solvent system was developed for catalytic HDH of high concentrations PCBs and other POPs. And catalytic HDH of high concentration chlorophenols over Raney Ni was also achieved. Moreover, catalysts could keep high activity and stability in water containing solvent systems. This provided apractical strategy to establish solvent system which was suitablefor application in catalytic HDH of high concentration POPs. Meanwhile，we developed a combination technique of solvent extraction and catalytic HDH, and designed an experimental apparatus for the remediation of DDTr contaminated soil. DDTr contaminated soil could be efficiently detoxified by combination of solvent extraction and catalytic HDH. The combination method described in this manuscript is a good way for lab detection and removing of the contamination. Furthermore, effect of solvent and alkali on HDH reactivity and stability were also described. Meanwhile, comparative study on catalytic hydrodehalogenation of halogenated aromatic compounds over Pd/C and Raney Ni catalysts were carried out. To clarify the reason why hydrogenolytic scission reactivity of C-X bonds over Pd/C and Raney Ni catalysts exhibits different trends, liquid-phase HDH of mixed HACs over Pd/C and Raney Ni catalysts were studied, and catalysts were characterized by SEM, EDSX, and XRD techniques. The major results were summarized as follows: Solvent systems are considerably important factors to influence the liquid-phase HDC reaction. Compared with an aprotic solvent, protic solvents are much better solvents for liquid-phase HDH. Moreover, HDH rate increased with solvent polarity for the HDC carried out in protic solvents. Inorganic salts, such as NaCl, produced insitu, could deposit on the surface of Raney Ni catalyst, andthus caused deactivation of the catalyst in organic solvents. Moreover, the deactivation of the catalyst used in organicsolvents, which was caused by the accumulation of inorganic salts,such as NaCl, was a universal phenomenon in liquid-phase HDH. Meanwhile, alcohol-water mixed solvent as the reaction medium can prevent the inorganic salts from accumulating on the surface ofcatalyst and thereby enabled the catalyst to keep high activity andstability. On the basis of the mechanism above, alcohol-water solvent system was developed for catalytic HDH of high concentration POPs under mild conditions and the catalyst could be recovered and reused. This report provided apractical strategy to establish solvent system which was suitable for application in catalytic HDC of high concentration POPs. Based on the studies mentioned above, alcohol-water mixed solvent system applied to treatment of transformer oil-contained PCBs. Meanwhlie, the influences of temperature, pressure, solvents and water addition on HDH of transformer oil-contained PCBs were studied. This provides a practical and efficient solvent system for the HDH of high concentration transformer oil-contained PCBs. For the remediation of DDTr contaminated soil, we developed a combination technique of solvent extraction and catalytic HDC, and designed an experimental apparatus. DDTr could be completely extracted from the soil sample at ambient temperature and pressure. Then the extract from DDTr contaminated soil was effectively hydrodechlorinated over Pd/C with GC-MS analysis monitoring the HDC process of DDTr. The combination method described in this manuscript is a good way for lab detection and removing of the contamination. It provides a practical strategy and direction for rapid abatement of POPs contaminated soil under mild condition. However, for big scale application in industry or for a polluted soil field, this method might still need further investigation. Liquid-phase HDH of single and mixed halobenzenes/4-halophenols with H2 over 5% Pd/C and Raney Ni catalysts were investigated and compared. For liquid-phase HDH of single HACs, hydrogenolytic scission reactivity of C-X bonds decreases in order of C-Br > C-Cl > C-I > C-F over Pd/C catalyst, and in order of C-I > C-Br > C-Cl > C-F over Raney Ni catalyst. To clarify the reason why hydrogenolytic scission reactivity of C-X bonds over Pd/C and Raney Ni catalysts exhibits different trends, liquid-phase HDH of mixed HACs over Pd/C and Raney Ni catalysts were studied, and catalysts were characterized by SEM, EDX, and XRD techniques. It was found that the high adsorption of iodoarenes on Pd/C catalyst caused the HDH reactivity of iodoarenes to be lower than that of chloroarenes and bromoarenes in the HDH of single HACs. Moreover, the adsorption of in situ produced iodine ion (I-) to catalyst surface would result in the decline of catalytic activity, which might be the main reason why the HDH reactivity of HACs in the presence of NaI is rather low. For liquid-phase HDH of single HACs, Pd/C catalyst exhibits high catalytic activity for the HDH of bromoarenes and chloroarenes, but shows low catalytic activity for the HDH of iodoarenes and fluoroarenes. According to catalyst characterization (SEM, EDX, and XRD), I-, produced in situ, will adsorb on the catalyst surface. The high adsorption of in situ produced I- can lead to the decrease of the catalytic activity in liquid-phase HDH of HACs, and thereby the HDH reactivity of mixed HACs is lower than that of the HDH reactivity of single HACs. This may be the main reason why the HDH reactivity of HACs in the presence of NaI is rather low. According to the analysis of SEM under high magnification, itwas found, for the first time, that the surface micro-topographyof Raney Ni catalyst could be affected by solvent in liquid-phaseHDC. This presumably accounted for the higher activity and sta-bility of Raney Ni catalyst in water than that in water–alcoholmixed solvents.In summary, water was the most effective solvent for dispos-ing high-concentration chlorophenols over Raney Ni catalyst undermild conditions (30-40 ℃, 1 atm). In water, a variety of chlorophe-nols could be efficiently hydrodechlorinated, and high catalyticactivity and stability could be preserved. |
| 语种 | 中文 |
| 学科主题 | 有机化学 ; 物理化学 ; 化学其他学科 ; 环境科学技术基础学科 ; 环境科学技术其他学科 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.yic.ac.cn/handle/133337/7928]  |
| 专题 | 中科院烟台海岸带研究所知识产出_学位论文 |
| 作者单位 | 中国科学院烟台海岸带研究所 |
| 推荐引用方式 GB/T 7714 | 马宣宣. Pd/C 和Raney Ni 催化有机卤代物的液相高效加氢脱卤研究[D]. 北京. 中国科学院大学. 2015. |
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