Hidaka Hisao, Saitou Aiko, Honjou Haruo, Hosoda Kazuo, Moriya Masafumi, Serpone Nick
Frontier Research Center for Global Environment Science, Meisei University, 2-1-1, Hodokubo, Hino, Tokyo 191-8506, Japan.
J Hazard Mater. 2007 Sep 5;148(1-2):22-8. doi: 10.1016/j.jhazmat.2007.01.143. Epub 2007 Feb 6.
Microwave-assisted dechlorination of chlorobenzene and the three dichlorobenzenes takes place in the presence of the hypophosphite (NaH(2)PO(2)) reductant and Pd-loaded activated carbon (Pd/C) in alkaline media at relatively low temperatures. The extent of loss/dechlorination at 90 degrees C followed the order: o-DCB approximately m-DCB>CB>p-DCB. Detected final products were mostly benzene and phenol. Dechlorination of pentachlorobenzene (PeCB) through reduction was slight even when both NaH(2)PO(2) and Pd/C were simultaneously employed in the absence of NaOH, nor when NaH(2)PO(2) alone was present in excess. The generated HCl proved to be an inhibitor, thus the need for the presence of NaOH to enhance dechlorination. Conventional heating of the reacting mixture above 90 degrees C to a reaction temperature of 180 degrees C led to no further dechlorination of the PeCB. Intermediate products of dechlorination of PeCP were the tetrachlorobenzenes with final products being benzene and phenol (GC-FID spectral analyses). Both salicylic acid (a constituent of humic acid) and l(+)-ascorbic acid used as possible promoters proved to be rather ineffective. The simultaneous presence of NaH(2)PO(2), Pd-loaded activated carbon and NaOH was crucial in the dechlorination of PeCB by microwave dielectric heating with maximal reduction of PeCB being ca. 75% under these conditions.
在碱性介质中,在次磷酸钠(NaH₂PO₂)还原剂和负载钯的活性炭(Pd/C)存在的情况下,氯苯和三种二氯苯在相对较低的温度下发生微波辅助脱氯反应。90℃时的损失/脱氯程度顺序为:邻二氯苯≈间二氯苯>氯苯>对二氯苯。检测到的最终产物主要是苯和苯酚。即使在没有NaOH的情况下同时使用NaH₂PO₂和Pd/C,或者单独过量存在NaH₂PO₂时,通过还原作用对五氯苯(PeCB)的脱氯作用也很轻微。生成的HCl被证明是一种抑制剂,因此需要NaOH的存在来增强脱氯作用。将反应混合物在90℃以上常规加热至180℃的反应温度,不会导致PeCB进一步脱氯。PeCP脱氯的中间产物是四氯苯,最终产物是苯和苯酚(气相色谱 - 火焰离子化检测器光谱分析)。用作可能促进剂的水杨酸(腐殖酸的一种成分)和L(+)-抗坏血酸都被证明效果不佳。在微波介电加热脱氯PeCB过程中,NaH₂PO₂、负载钯的活性炭和NaOH同时存在至关重要,在这些条件下,PeCB的最大还原率约为75%。