用化成箔废水制取红矾钠的工艺研究
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摘要
含铬废水处理研究的意义不仅在于处理后水质达到排放标准,更在于资源的回收利用。本文在充分阅读了国内外含铬废水处理文献的基础上,提出了化成箔生产企业的含Cr废水资源化和无害化处理新工艺。工艺包括还原—沉淀—氧化—酸化—浓缩制取红矾钠等工序,并分别对前三个阶段的工艺条件进行了较系统地研究。试验结果表明,在合适的条件下,铬的回收利用率达到79%以上,制得红矾钠晶体。进行了初步的技术经济分析。
有机物蔗糖作为还原剂,将Cr(Ⅵ)(浓度27 g/L)还原为Cr(Ⅲ),通过试验获得了较理想的工艺参数:对100 mL水样,蔗糖的用量为2.6 g,反应温度为97℃,反应时间8 min。还原率98.9%。
沉淀Cr(Ⅲ)(包括由Cr(Ⅵ)还原产生的Cr(Ⅲ)及水样中原来已有的Cr(Ⅲ)(浓度20 g/L))。试验得到较理想的工艺参数:反应温度维持在60～70℃左右,100 mL水样消耗NH_4HCO_324克,NaOH消耗量15 g,得到Cr(OH)_3沉淀8.69 g;Cr(Ⅲ)去除率93.9%。
在强碱性条件下用H_2O_2将Cr(OH)_3中的Cr(Ⅲ)氧化成CrO_4~(2-)。较理想的工艺参数为:对8.69 g Cr(OH)_3,当pH维持在13.5,反应时间为40分钟时,消耗29 mL H_2O_2、14.6 g NaOH,氧化率达92.1%。
用H_2SO_4将pH值调到2,91.5%的CrO_4~(2-)转化成Cr_2O_7~(2-)。
The research significance of Cr-contained wastewater treatment not only lies in making the concentration of pollutants in the discharged water below the discharge standard limit but also in recycling the resource. Based on reviewing internal and external relative literature, this paper presents a new recycling and innocuous process to reclaim Cr(VI) and Cr (III) from the industrial wastewater generated by a chemosynthesis aluminum-foil plant in Guangdong province, then produce Na_2Cr_2O_7 with it. The whole process involves five major steps: reducing, chromium-precipitation, oxidation, acidizing and concentration. Series experiments were performed to grope the optimum process parameters for the first three steps. The results indicate that under certain process parameters the total recovery rate could be more than 79% while the final production is Na_2Cr_2O_7. Later, a primary economical analysis was made.Adopting sugar as reducer to reduce the Cr (VI) in sample (which concentration is 27 g/L) to Cr (III). For 100 mL wastewater sample the optimum dosage of reducer was 2. 6 g, the optimum reaction temperature was 97℃, the optimum reaction duration was 8 minutes while the reducing rate was
98. 9%.In order to precipitate the reduced Cr(III) and the original existed Cr (III) ( which concentration is 20 g/L) in water sample, MH_4CO_3 and NaOH were put in. The optimum process parameters are as follows: for 100 mL reduced sample, 24 g NH_4HCO_3 and 15 g NaOH were consumed and produced Cr(OH)_3 8.69 g, while the reaction temperature fluctuated between 60 and 70℃. Totally, 93.9% Cr (III) was got rid of from the sample.Transforming the Cr(III) in Cr(OH)_3 sediment into CrO_4~2-with H_2O_2 under the condition of high pH value. The optimum process parameters are as follows: for 8.69g Cr(OH)_3 maintaining the pH value at 13. 5, 29 mL H_2O_2 and 14. 6 g NaOH were consumed. 40 minutes later, the oxidation rate was 92. 1%.Adopting H_2SO_4 to regulate the pH value, when pH = 2, 91. 5% CrO_4~2- transformed to Cr_2O_7~2-Treating 1000 kg wastewater could produce 93 kg Na_2Cr_2O_7 crystal, the gross profit is about 726 Yuan RMB per ton production. Hence, considerable economic benefits could be achieved.
有机物蔗糖作为还原剂,将Cr(Ⅵ)(浓度27 g/L)还原为Cr(Ⅲ),通过试验获得了较理想的工艺参数:对100 mL水样,蔗糖的用量为2.6 g,反应温度为97℃,反应时间8 min。还原率98.9%。
沉淀Cr(Ⅲ)(包括由Cr(Ⅵ)还原产生的Cr(Ⅲ)及水样中原来已有的Cr(Ⅲ)(浓度20 g/L))。试验得到较理想的工艺参数:反应温度维持在60～70℃左右,100 mL水样消耗NH_4HCO_324克,NaOH消耗量15 g,得到Cr(OH)_3沉淀8.69 g;Cr(Ⅲ)去除率93.9%。
在强碱性条件下用H_2O_2将Cr(OH)_3中的Cr(Ⅲ)氧化成CrO_4~(2-)。较理想的工艺参数为:对8.69 g Cr(OH)_3,当pH维持在13.5,反应时间为40分钟时,消耗29 mL H_2O_2、14.6 g NaOH,氧化率达92.1%。
用H_2SO_4将pH值调到2,91.5%的CrO_4~(2-)转化成Cr_2O_7~(2-)。
The research significance of Cr-contained wastewater treatment not only lies in making the concentration of pollutants in the discharged water below the discharge standard limit but also in recycling the resource. Based on reviewing internal and external relative literature, this paper presents a new recycling and innocuous process to reclaim Cr(VI) and Cr (III) from the industrial wastewater generated by a chemosynthesis aluminum-foil plant in Guangdong province, then produce Na_2Cr_2O_7 with it. The whole process involves five major steps: reducing, chromium-precipitation, oxidation, acidizing and concentration. Series experiments were performed to grope the optimum process parameters for the first three steps. The results indicate that under certain process parameters the total recovery rate could be more than 79% while the final production is Na_2Cr_2O_7. Later, a primary economical analysis was made.Adopting sugar as reducer to reduce the Cr (VI) in sample (which concentration is 27 g/L) to Cr (III). For 100 mL wastewater sample the optimum dosage of reducer was 2. 6 g, the optimum reaction temperature was 97℃, the optimum reaction duration was 8 minutes while the reducing rate was
98. 9%.In order to precipitate the reduced Cr(III) and the original existed Cr (III) ( which concentration is 20 g/L) in water sample, MH_4CO_3 and NaOH were put in. The optimum process parameters are as follows: for 100 mL reduced sample, 24 g NH_4HCO_3 and 15 g NaOH were consumed and produced Cr(OH)_3 8.69 g, while the reaction temperature fluctuated between 60 and 70℃. Totally, 93.9% Cr (III) was got rid of from the sample.Transforming the Cr(III) in Cr(OH)_3 sediment into CrO_4~2-with H_2O_2 under the condition of high pH value. The optimum process parameters are as follows: for 8.69g Cr(OH)_3 maintaining the pH value at 13. 5, 29 mL H_2O_2 and 14. 6 g NaOH were consumed. 40 minutes later, the oxidation rate was 92. 1%.Adopting H_2SO_4 to regulate the pH value, when pH = 2, 91. 5% CrO_4~2- transformed to Cr_2O_7~2-Treating 1000 kg wastewater could produce 93 kg Na_2Cr_2O_7 crystal, the gross profit is about 726 Yuan RMB per ton production. Hence, considerable economic benefits could be achieved.
引文
[1] 北京师范大学,华中师范大学,南京师范大学无机化学教研室.无机化学(第二版)[M].北京:高等教育出版社,1986,772～773.
[2] 王岑生.工业环保员手册[M].南宁:广西人民出版社,1995,630.
[3] 张希衡等.废水治理工程(第二版)[M].北京:冶金工业出版社,1996,167.
[4] 石华等.一种新型还原剂处理含铬废水[J].湘潭大学自然科学学报,2003,15(3):79～81.
[5] 安成强,崔化兴,郝建军.电镀三废治理技术[M].国际工业出版社,2002.
[6] 廖自基.环境中微量重金属的污染危害与迁移转化.北京:科学出版社,1989.
[7] 王小文.水污染控制工程[M] 北京:煤炭工业出版社,2002,100～101,114,117～118.
[8] 陈天虎,冯有亮等.层状双氢氧化物即时合成处理含Cr(Ⅵ)废水[J].环境科学,2004,25(2):89～94.
[9] Li Yang chang. Alternative Chromium Reduction and Heavy Metal Precipitation Methods for Industrial Wastewater[J] . Environmental Progress, 2003, 22(3): 174～182.
[10] 孙德智.环境工程中的高级氧化技术[M].北京:化学工业出版社,2002,183～184.
[11] 冯玉杰等.电化学技术在环境工程中的应用[M].北京:化学工业出版社,2002,128～130.
[12] M.西丁.金属与无机废物回收百科全书[M].北京:冶金工业出版社,1989,35～37.
[13] 郑宝华,李峥嵘,马奇,孙宏斌,乔军平.含铬废水处理方法综 述[J].化工设备与防腐蚀,1996,22(6):76～79.
[14] 贾金平,谢少艾,陈红锦.电镀废水处理技术及工程实例[M].北京:化学工业出版社,2001.
[15] 孟祥和,胡国飞.重金属废水处理[M].北京:化学工业出版社,环境科学与工程出版中心,2000.
[16] 刘满红,王如阳.凤鸣村腐植酸和活性褐煤对Cr(Ⅵ)离子的吸附等温式[J].云南化工,2002,29(2):6～7.
[17] 曹明礼,彭先佳等.羟基铝柱撑蒙脱石对水溶液中Cr~(6+)吸附作用的研究[J].中国矿业,2003,12(11):44～45.
[18] 黄彪,吴新华,黄碧忠.粉煤灰活性炭吸附水中Cr(Ⅵ)试验[J].化工环保,1997(17):346～349.
[19] 刘俊良,杨金利,刘明德.含铬废水处理技术综述[J].河北科技图苑,1997,37(3):7～9.
[20] 廖亮.含铬废水治理技术的应用[J].环境技术,2002.
[21] 戴遐明,陈永华等.半导体氧化物超细粉末对Cr(Ⅵ)的光催化还原作用研究[J].环境科学,1996,17(6):34～36.
[22] 龙腾发等.生物法解毒Cr(Ⅵ)技术的应用现状与进展[J].安全与环境工程,2004,11(3):22～26.
[23] E.M.N. Chirwa and Y.T. Wang, Hexavalent chromium Reduction by Bacillus sp. in a Packed Bed Bioreactor[J] . Environ. Sci. Technol.,1997, (31): 1446～1451.
[24] 陈坚等.环境生物技术应用与发展[M].北京,中国轻工业出版社,2001,227～233.
[25] M. N. Evans, Heaavalent chromirm Reduetion by baeollussp in a Packed-bed, bioreacter[J] .Environmental Secience& Wech-nology, 1997,31(5) 153～159.
[26] 陶颖,王竞等.新型生物吸附剂去除水中Cr(Ⅵ)的研究[J].上海环境科学,2000,19(12)572～573.
[27] Chai Liyuan, He De-wen, Yu Xia, et al. Technological. progress on detoxification and comprehensive utilization of chromium containing slag[J] .rruns. Nonferrous Met. Soc. China, 2002,12(3):514～518.
[28] 郑宝华,李峥嵘,马奇,孙宏斌,乔军平.含铬废水处理方法综述[J].化工设备与防腐蚀.1996,16(3).
[29] 张胜涛等.电镀工程[M].化学工业出版社,2002.
[30] 施耀,张清宇,吴祖成,沈铎(美).21世纪的环保理念—污染综合预防[M].北京:化学工业出版社,2002.
[31] 钱易,郝吉明,吴天宝.工业性环境污染的防治[M].北京:中国科学技术出版社,1989.
[32] 奚旦立,孙裕生,刘秀英.环境监测[M].北京:高等教育出版社,2001.
[33] 国家环境环保总局,《水和废水监测分析方法》编委会.水和废水监测分析方法[M].北京:中国环境科学出版社,2002.
[34] 北京师范大学等.无机化学(下册)(第二版)[M].北京:高等教育出版社,1986.
[35] 武汉大学,吉林大学等.无机化学(第三版)[M].北京:高等教育出版社,1994.
[36] 杭州大学化学系分析化学教研室,分析化学手册(第一分册)[M].北京:化学工业出版社,1997.
[37] 张胜涛等.电镀工程[M].化学工业出版社,2002.
[38] 颜家宝.还原沉淀法处理含铬废水的工艺研究[J].武汉科技大学学报,2002,25(1):43～46.
[39] 刘天齐.石油化工环境保护手册[M].烃加工出版社,1990.
[40] Seaman, J.C., P.M. Bertsch, and L. Schwallie, In Situ Cr (Ⅵ) Reduction Within Coarse-Textured. Oxide-Coated Soil and Aquifer Systems Using Fe(Ⅱ) Solutions. Environ. Sci. Technol.,1999,33(3):938～944.
[41] 华东化工学院,成都科技大学.分析化学(第三版)[M].北京:高等教育出版社,1989.
[42] 中国科学院数学研究所统计组.常用数理统计方法[M].北京:科学出版社,1979.
[43] 正交试验设计法编写组.正交试验设计法[M].上海:上海科学技术出版社,1979.
[44] 田学达.English on Environmental and Engineering[M].北京化学工业出版社,2002.
[45] 张自杰.废水处理理论与设计[M].北京:中国建筑工业出版社,2003.
[46] 熊文强,郭孝菊,洪卫.绿色环保与清洁生产概论[M].北京:化学工业出版社,2002.
[47] 成思危.铬盐生产工艺[M].北京:化学工业出版社,1988.
[48] 王绍文,梁富智,王纪曾.固体废弃物资源化技术与应用[M].北京:冶金工业出版社,2003.
[49] 邓南圣,吴峰.工业生态学——理论与应用[M].北京:化学工业出版社,2002.
[2] 王岑生.工业环保员手册[M].南宁:广西人民出版社,1995,630.
[3] 张希衡等.废水治理工程(第二版)[M].北京:冶金工业出版社,1996,167.
[4] 石华等.一种新型还原剂处理含铬废水[J].湘潭大学自然科学学报,2003,15(3):79～81.
[5] 安成强,崔化兴,郝建军.电镀三废治理技术[M].国际工业出版社,2002.
[6] 廖自基.环境中微量重金属的污染危害与迁移转化.北京:科学出版社,1989.
[7] 王小文.水污染控制工程[M] 北京:煤炭工业出版社,2002,100～101,114,117～118.
[8] 陈天虎,冯有亮等.层状双氢氧化物即时合成处理含Cr(Ⅵ)废水[J].环境科学,2004,25(2):89～94.
[9] Li Yang chang. Alternative Chromium Reduction and Heavy Metal Precipitation Methods for Industrial Wastewater[J] . Environmental Progress, 2003, 22(3): 174～182.
[10] 孙德智.环境工程中的高级氧化技术[M].北京:化学工业出版社,2002,183～184.
[11] 冯玉杰等.电化学技术在环境工程中的应用[M].北京:化学工业出版社,2002,128～130.
[12] M.西丁.金属与无机废物回收百科全书[M].北京:冶金工业出版社,1989,35～37.
[13] 郑宝华,李峥嵘,马奇,孙宏斌,乔军平.含铬废水处理方法综 述[J].化工设备与防腐蚀,1996,22(6):76～79.
[14] 贾金平,谢少艾,陈红锦.电镀废水处理技术及工程实例[M].北京:化学工业出版社,2001.
[15] 孟祥和,胡国飞.重金属废水处理[M].北京:化学工业出版社,环境科学与工程出版中心,2000.
[16] 刘满红,王如阳.凤鸣村腐植酸和活性褐煤对Cr(Ⅵ)离子的吸附等温式[J].云南化工,2002,29(2):6～7.
[17] 曹明礼,彭先佳等.羟基铝柱撑蒙脱石对水溶液中Cr~(6+)吸附作用的研究[J].中国矿业,2003,12(11):44～45.
[18] 黄彪,吴新华,黄碧忠.粉煤灰活性炭吸附水中Cr(Ⅵ)试验[J].化工环保,1997(17):346～349.
[19] 刘俊良,杨金利,刘明德.含铬废水处理技术综述[J].河北科技图苑,1997,37(3):7～9.
[20] 廖亮.含铬废水治理技术的应用[J].环境技术,2002.
[21] 戴遐明,陈永华等.半导体氧化物超细粉末对Cr(Ⅵ)的光催化还原作用研究[J].环境科学,1996,17(6):34～36.
[22] 龙腾发等.生物法解毒Cr(Ⅵ)技术的应用现状与进展[J].安全与环境工程,2004,11(3):22～26.
[23] E.M.N. Chirwa and Y.T. Wang, Hexavalent chromium Reduction by Bacillus sp. in a Packed Bed Bioreactor[J] . Environ. Sci. Technol.,1997, (31): 1446～1451.
[24] 陈坚等.环境生物技术应用与发展[M].北京,中国轻工业出版社,2001,227～233.
[25] M. N. Evans, Heaavalent chromirm Reduetion by baeollussp in a Packed-bed, bioreacter[J] .Environmental Secience& Wech-nology, 1997,31(5) 153～159.
[26] 陶颖,王竞等.新型生物吸附剂去除水中Cr(Ⅵ)的研究[J].上海环境科学,2000,19(12)572～573.
[27] Chai Liyuan, He De-wen, Yu Xia, et al. Technological. progress on detoxification and comprehensive utilization of chromium containing slag[J] .rruns. Nonferrous Met. Soc. China, 2002,12(3):514～518.
[28] 郑宝华,李峥嵘,马奇,孙宏斌,乔军平.含铬废水处理方法综述[J].化工设备与防腐蚀.1996,16(3).
[29] 张胜涛等.电镀工程[M].化学工业出版社,2002.
[30] 施耀,张清宇,吴祖成,沈铎(美).21世纪的环保理念—污染综合预防[M].北京:化学工业出版社,2002.
[31] 钱易,郝吉明,吴天宝.工业性环境污染的防治[M].北京:中国科学技术出版社,1989.
[32] 奚旦立,孙裕生,刘秀英.环境监测[M].北京:高等教育出版社,2001.
[33] 国家环境环保总局,《水和废水监测分析方法》编委会.水和废水监测分析方法[M].北京:中国环境科学出版社,2002.
[34] 北京师范大学等.无机化学(下册)(第二版)[M].北京:高等教育出版社,1986.
[35] 武汉大学,吉林大学等.无机化学(第三版)[M].北京:高等教育出版社,1994.
[36] 杭州大学化学系分析化学教研室,分析化学手册(第一分册)[M].北京:化学工业出版社,1997.
[37] 张胜涛等.电镀工程[M].化学工业出版社,2002.
[38] 颜家宝.还原沉淀法处理含铬废水的工艺研究[J].武汉科技大学学报,2002,25(1):43～46.
[39] 刘天齐.石油化工环境保护手册[M].烃加工出版社,1990.
[40] Seaman, J.C., P.M. Bertsch, and L. Schwallie, In Situ Cr (Ⅵ) Reduction Within Coarse-Textured. Oxide-Coated Soil and Aquifer Systems Using Fe(Ⅱ) Solutions. Environ. Sci. Technol.,1999,33(3):938～944.
[41] 华东化工学院,成都科技大学.分析化学(第三版)[M].北京:高等教育出版社,1989.
[42] 中国科学院数学研究所统计组.常用数理统计方法[M].北京:科学出版社,1979.
[43] 正交试验设计法编写组.正交试验设计法[M].上海:上海科学技术出版社,1979.
[44] 田学达.English on Environmental and Engineering[M].北京化学工业出版社,2002.
[45] 张自杰.废水处理理论与设计[M].北京:中国建筑工业出版社,2003.
[46] 熊文强,郭孝菊,洪卫.绿色环保与清洁生产概论[M].北京:化学工业出版社,2002.
[47] 成思危.铬盐生产工艺[M].北京:化学工业出版社,1988.
[48] 王绍文,梁富智,王纪曾.固体废弃物资源化技术与应用[M].北京:冶金工业出版社,2003.
[49] 邓南圣,吴峰.工业生态学——理论与应用[M].北京:化学工业出版社,2002.