纸浆漂白废水的毒性研究及其关键毒性物质的鉴别
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摘要
纸浆漂白废水，特别是含氯漂白废水具有COD、BOD负荷较大，含有毒性较强的物质，主要是氯代有机物等污染特点，特别是对水生生物具有急性毒性，已引起了业内人士的普遍关注。根据我国制浆工业的特点及现状，选择了蔗渣浆、苇浆、木浆具有代表性的纸浆为研究对象，分别针对传统的CEH漂白工艺和华南理工大学造纸与污染控制国家工程中心研究开发的少污染漂白工艺-OHMP漂白技术，利用快速、准确的发光细菌急性毒性测试技术以及化学分析技术，系统地研究了各种纸浆不同漂白工艺漂白废水的毒性、COD负荷以及关键毒物的鉴别，获得如下研究成果。
蔗渣浆CEH漂白废水总COD负荷为94.43kg COD／吨浆，总毒性排放因子(TEF)为423.92TU m~3／吨浆，相当于42.93gHgCl_2／吨浆，其中C段毒性负荷最大，约占67.5％，其次是E段废水，约占25.7％，H段废水的毒性排放负荷最小，约占6.8％。废水有机成份分析结果表明，2，6—二氯苯酚、4，5二氯愈创木酚、3，4，6—三氯愈创木酚和四氯愈创木酚是蔗渣浆CEH漂白工艺C段漂白废水中的关键毒性物质。3，4，6-三氯愈创木酚、四氯愈创木酚、2，5-二氯-4-甲氧基苯酚、4，5-二氯愈创木酚、3，5，6-三氯愈创木酚、2，4-二氯苯酚是蔗渣浆E段废水中的关键毒物。H段废水中检测出的氯代有机物的毒性占全废水毒性的22.23％，在一定程度上可以说明这些氯代有机物是蔗渣浆CEH漂白工艺H段漂白废水毒性的主要来源。
蔗渣浆OHMP漂白工艺过程中O段和H段漂白废水外排，总COD负荷为55.738kgCOD／吨浆，毒性因子(TEF)为54.776TUm~3／吨浆，其中O段废水TEF为18.786 TUm~3／吨浆，占总量的34.3％，H段占总量的65.7％。蔗渣浆OHMP漂白工艺毒性排放当量相当于5.477gHgCl_2／吨浆，毒性当量较小。H段废水污染成分分析结果表明，有机酸类占有量最多，约33.63％，烷烃类占有11.14％，还有少量酯类和酮类。氯代有机物占检测总量的25.12％，是H段废水毒性的主要组成部分。
苇浆CEH漂白废水的COD负荷为81.043kg COD／吨浆，总毒性负荷(TEF)为472.016TUm~3／吨浆，其中C段最大，TEF为393.88 TUm~3／吨浆，占83.45％，其次是E段废水，占10.03％，H段最小，约6.52％。苇浆CEH漂白工艺所排放出的废水的毒性总量相当于47.20g HgCl_2／吨浆，毒性排放负荷比较严重。1，3，3-三氯-4-甲基-2-戊酮、3，4，5-三氯愈创木酚、3，4，6-三氯愈创木酚、2，4，5-三氯苯酚、2-氯萘、2，4，6-三氯苯酚、2，6-二氯苯酚和2，5-二氯苯酚是苇浆CEH漂白工艺C段
There are environmental concerns over pulp bleaching effluents, especially chlorine bleaching effluents because of its high COD, BOD load and its formation of toxic chlorinated organic compounds. Based on the characteristic and actuality of our country's pulp industry, bagasse pulp> weed pulp and wood(masson pine) pulp were selected as studied objects. The traditional bleaching process(CEH) and small pollution bleaching process(OHMP) which is researched by National engineering research center of paper making & pollution control, South China University of Technology, were used. With the quickly and exact photobacteria acute toxicity method and chemical analytical method, the toxicity、COD load and key toxicants of pulp bleaching effluents were studied in this paper.
The COD load of bagasse pulp CEH bleaching effluent was 94.43kgCOD/ton, its toxicity emission factor(TEF) was 423.92TUm~3/ton, be equivalent to 42.93gHgCl2/ton. In bagasse pulp CEH bleaching effluents, the TEF of C bleaching effluent was the largest, which was 67.5% of total TEF, the less one was E bleaching effluent, which was 25.7%, and the TEF of H bleaching effluent was the smallest, with its percentage of 6.8%. The organic compounds analysis results showed that 2,6-dichlorophenol 、4,5-dichloroguaiacol、3,4,6-trichloroguaiacol and tetrachloroguaiacol were key toxicants of C bleaching effluent.
3,4,6-trichloroguaiacol 、 tetrachloroguaiacol 、 2,5-dichloro-4-methoxyphenol 、 4,5-dichloroguaiacol 、 3,5,6-trichloroguaiacol and 2,4-dichlorophenol were key toxicants of E bleaching effluent. Chlorinated organic compounds' toxicity in H bleaching effluent was 22.23% of total toxicity, which were key toxicants of H bleaching effluent of bagasse pulp CEH bleaching process.
There were only O bleaching effluent and H bleaching effluent in the OHMP bleaching process of bagasse pulp. The total COD load was 55.738kgCOD/ton, and the total TEF was 54.776 TU ? m~3/ton. The TEF of O bleaching effluent was 18.786 TU ? m~3/ton, shared 34.3% of total TEF, and the TEF of H bleaching effluent shared 65.7% of the total TEF. The total TEF of bagasse pulp OHMP bleaching effluents was equivalent to 5.477 gHgCl_2/ton, so its toxicity was small. The organic compounds analysis showed that there are 33.63% organic acid、11.14% hydrocarbon of methane series and a small quantity of ester and ketone. Chlorinated organic
蔗渣浆CEH漂白废水总COD负荷为94.43kg COD／吨浆，总毒性排放因子(TEF)为423.92TU m~3／吨浆，相当于42.93gHgCl_2／吨浆，其中C段毒性负荷最大，约占67.5％，其次是E段废水，约占25.7％，H段废水的毒性排放负荷最小，约占6.8％。废水有机成份分析结果表明，2，6—二氯苯酚、4，5二氯愈创木酚、3，4，6—三氯愈创木酚和四氯愈创木酚是蔗渣浆CEH漂白工艺C段漂白废水中的关键毒性物质。3，4，6-三氯愈创木酚、四氯愈创木酚、2，5-二氯-4-甲氧基苯酚、4，5-二氯愈创木酚、3，5，6-三氯愈创木酚、2，4-二氯苯酚是蔗渣浆E段废水中的关键毒物。H段废水中检测出的氯代有机物的毒性占全废水毒性的22.23％，在一定程度上可以说明这些氯代有机物是蔗渣浆CEH漂白工艺H段漂白废水毒性的主要来源。
蔗渣浆OHMP漂白工艺过程中O段和H段漂白废水外排，总COD负荷为55.738kgCOD／吨浆，毒性因子(TEF)为54.776TUm~3／吨浆，其中O段废水TEF为18.786 TUm~3／吨浆，占总量的34.3％，H段占总量的65.7％。蔗渣浆OHMP漂白工艺毒性排放当量相当于5.477gHgCl_2／吨浆，毒性当量较小。H段废水污染成分分析结果表明，有机酸类占有量最多，约33.63％，烷烃类占有11.14％，还有少量酯类和酮类。氯代有机物占检测总量的25.12％，是H段废水毒性的主要组成部分。
苇浆CEH漂白废水的COD负荷为81.043kg COD／吨浆，总毒性负荷(TEF)为472.016TUm~3／吨浆，其中C段最大，TEF为393.88 TUm~3／吨浆，占83.45％，其次是E段废水，占10.03％，H段最小，约6.52％。苇浆CEH漂白工艺所排放出的废水的毒性总量相当于47.20g HgCl_2／吨浆，毒性排放负荷比较严重。1，3，3-三氯-4-甲基-2-戊酮、3，4，5-三氯愈创木酚、3，4，6-三氯愈创木酚、2，4，5-三氯苯酚、2-氯萘、2，4，6-三氯苯酚、2，6-二氯苯酚和2，5-二氯苯酚是苇浆CEH漂白工艺C段
There are environmental concerns over pulp bleaching effluents, especially chlorine bleaching effluents because of its high COD, BOD load and its formation of toxic chlorinated organic compounds. Based on the characteristic and actuality of our country's pulp industry, bagasse pulp> weed pulp and wood(masson pine) pulp were selected as studied objects. The traditional bleaching process(CEH) and small pollution bleaching process(OHMP) which is researched by National engineering research center of paper making & pollution control, South China University of Technology, were used. With the quickly and exact photobacteria acute toxicity method and chemical analytical method, the toxicity、COD load and key toxicants of pulp bleaching effluents were studied in this paper.
The COD load of bagasse pulp CEH bleaching effluent was 94.43kgCOD/ton, its toxicity emission factor(TEF) was 423.92TUm~3/ton, be equivalent to 42.93gHgCl2/ton. In bagasse pulp CEH bleaching effluents, the TEF of C bleaching effluent was the largest, which was 67.5% of total TEF, the less one was E bleaching effluent, which was 25.7%, and the TEF of H bleaching effluent was the smallest, with its percentage of 6.8%. The organic compounds analysis results showed that 2,6-dichlorophenol 、4,5-dichloroguaiacol、3,4,6-trichloroguaiacol and tetrachloroguaiacol were key toxicants of C bleaching effluent.
3,4,6-trichloroguaiacol 、 tetrachloroguaiacol 、 2,5-dichloro-4-methoxyphenol 、 4,5-dichloroguaiacol 、 3,5,6-trichloroguaiacol and 2,4-dichlorophenol were key toxicants of E bleaching effluent. Chlorinated organic compounds' toxicity in H bleaching effluent was 22.23% of total toxicity, which were key toxicants of H bleaching effluent of bagasse pulp CEH bleaching process.
There were only O bleaching effluent and H bleaching effluent in the OHMP bleaching process of bagasse pulp. The total COD load was 55.738kgCOD/ton, and the total TEF was 54.776 TU ? m~3/ton. The TEF of O bleaching effluent was 18.786 TU ? m~3/ton, shared 34.3% of total TEF, and the TEF of H bleaching effluent shared 65.7% of the total TEF. The total TEF of bagasse pulp OHMP bleaching effluents was equivalent to 5.477 gHgCl_2/ton, so its toxicity was small. The organic compounds analysis showed that there are 33.63% organic acid、11.14% hydrocarbon of methane series and a small quantity of ester and ketone. Chlorinated organic
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