铬渣污染控制及资源化利用试验研究
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摘要
本文在福建省铬渣产生与排放调查基础上，结合国内外铬渣污染控制与资源化利用研究成果，应用现代分析技术与测试手段（XRD、全化学分析、SEM等），对福州一化集团氯碱工业生产过程中产生的铬渣进行无害化和资源化利用的实验室模拟试验研究，探讨了铬渣水泥固化，高温解毒等无害化处理技术及工艺，分析了铬渣作为陶瓷、微晶玻璃配料的工艺技术条件与产品性能，所得的主要结论是：
1.福建省铬渣产生于氯碱工业、电镀和制革行业，虽然数量不大，但产生源分布较广，以闽东及闽南地区分布为主。这些铬渣基本上未经处理，随意堆存或混入垃圾中填埋，环境隐患大。
2.铬渣水泥常温固化试验研究结果表明，在铬渣30%的高掺量条件下，固化体性能符合无害化处理要求，固化体抗压强度大于10Mpa，Cr6+的浸出值为1.39mg/L，固化率为90%，增容比为4.2。
3.将铬渣作为陶瓷、微晶玻璃配料，经高温焙烧，试验表明，铬渣中的Cr6+可以通过化学还原、晶格化、吸附和包容作用而得到解毒和屏蔽，从而降低其的毒性和Cr6+的迁移性，Cr6+去除率均达到99%左右。
4.将15%的铬渣与其它陶瓷原料充分混合均匀并成型后，经1100℃高温焙烧所得到的陶瓷成品中的Cr6+浸出值为0.0046mg/L，低于国家饮用水0.05mg/L标准，其陶瓷成品的吸水率、外观特征和强度等均符合国家内墙砖产品质量标准，表明了铬渣作为陶瓷配料是可行的。
5.正交试验结果表明，在50%铬渣掺量条件下，微晶玻璃热处理的最佳工艺条件是：转化温度820℃，转化时间1小时 ，析晶温度1120℃，析晶时间1小时。所得到的微晶玻璃中Cr6+浸出率为0.005mg/L。外观、体密度，耐酸性等理化性能达到国家微晶玻璃产品质量标准，表明了铬渣作为微晶玻璃配料生产是可行。
The thesis is mainly about the production control and reclamation of the chromium slag in Fujian Province, P. R. china. The sources, distribution and properties of the chromium in Fujian Province have been reported in this paper. The processes and additives for the cement solidification of the chromium slag from the No.1 chemical factory in Fuzhou, which produce chlorate products mainly, and the mechanisms of detoxification by melting under a higher temperature (1100-1450) and reclamation as the raw material for ceramic tile and glass ceramics have been studied by controlled test in this paper. The results we have achieved in the study are following.
1.Chromium slags in Fujian Province are generated form electroplanting, leather tanning and chlorate industries. The amount of chromium slag generated per year is not very large (less than 26000 ton per year). But the sources of chromium slag ix abroad (the factories generated chromium slag are more than one 1000 points), mainly in the eastern and southern of Fujian Province.
2.The results of the controlled test for the cement solidification of chromium slag show that the strength of the solidified blocks with 30% chromium slag is more than 10Mpa and the content of Cr6+ in the blocks is 1.39mg/L (fixation rate of Cr6+ reaches 90%), volume factor is 4.2.
3.The results of the melting test of higher temperature (1100-1450) show that the hexavalent chromium can be reduced to its trivalent form chemically, and also be absorbed to, crystal and contained in the products of ceramic tile or glass ceramics during the melting process, when the chromium slag is as the raw material of ceramic tile and glass ceramic. The removable rate of Cr6+ in the products of ceramic tile or glass ceramics is about 99%, meeting the regulations for the Cr6+ pollution control.
4.The content of Cr6+ in the products of ceramic tile is 0.0046mg/L when 15%chromium slag is contributed to the raw material of ceramic, meeting the regulations for hexavalent chromium pollution in drinking water sanitary standards. The main parameters of the ceramic tile performance reach the national standards. That means that chromium slag can be used as the raw material of ceramic tile.
5.The results of the cross-test for the glass ceramics show that the optimizing process conditions for the glass ceramics production is : nucleation temperature,820, nucleation time,1h, crystallization temperature, 1120, crystallization time, 1h.
And the content of Cr6+ in the products of glass ceramics is 0.005mg/L, meeting the regulations for the Cr6+ pollution control in drinking water sanitary standards. The main parameters of the glass ceramics performance reach the national standards. That means that chromium slag can be used as the raw material of glass ceramic.
1.福建省铬渣产生于氯碱工业、电镀和制革行业，虽然数量不大，但产生源分布较广，以闽东及闽南地区分布为主。这些铬渣基本上未经处理，随意堆存或混入垃圾中填埋，环境隐患大。
2.铬渣水泥常温固化试验研究结果表明，在铬渣30%的高掺量条件下，固化体性能符合无害化处理要求，固化体抗压强度大于10Mpa，Cr6+的浸出值为1.39mg/L，固化率为90%，增容比为4.2。
3.将铬渣作为陶瓷、微晶玻璃配料，经高温焙烧，试验表明，铬渣中的Cr6+可以通过化学还原、晶格化、吸附和包容作用而得到解毒和屏蔽，从而降低其的毒性和Cr6+的迁移性，Cr6+去除率均达到99%左右。
4.将15%的铬渣与其它陶瓷原料充分混合均匀并成型后，经1100℃高温焙烧所得到的陶瓷成品中的Cr6+浸出值为0.0046mg/L，低于国家饮用水0.05mg/L标准，其陶瓷成品的吸水率、外观特征和强度等均符合国家内墙砖产品质量标准，表明了铬渣作为陶瓷配料是可行的。
5.正交试验结果表明，在50%铬渣掺量条件下，微晶玻璃热处理的最佳工艺条件是：转化温度820℃，转化时间1小时 ，析晶温度1120℃，析晶时间1小时。所得到的微晶玻璃中Cr6+浸出率为0.005mg/L。外观、体密度，耐酸性等理化性能达到国家微晶玻璃产品质量标准，表明了铬渣作为微晶玻璃配料生产是可行。
The thesis is mainly about the production control and reclamation of the chromium slag in Fujian Province, P. R. china. The sources, distribution and properties of the chromium in Fujian Province have been reported in this paper. The processes and additives for the cement solidification of the chromium slag from the No.1 chemical factory in Fuzhou, which produce chlorate products mainly, and the mechanisms of detoxification by melting under a higher temperature (1100-1450) and reclamation as the raw material for ceramic tile and glass ceramics have been studied by controlled test in this paper. The results we have achieved in the study are following.
1.Chromium slags in Fujian Province are generated form electroplanting, leather tanning and chlorate industries. The amount of chromium slag generated per year is not very large (less than 26000 ton per year). But the sources of chromium slag ix abroad (the factories generated chromium slag are more than one 1000 points), mainly in the eastern and southern of Fujian Province.
2.The results of the controlled test for the cement solidification of chromium slag show that the strength of the solidified blocks with 30% chromium slag is more than 10Mpa and the content of Cr6+ in the blocks is 1.39mg/L (fixation rate of Cr6+ reaches 90%), volume factor is 4.2.
3.The results of the melting test of higher temperature (1100-1450) show that the hexavalent chromium can be reduced to its trivalent form chemically, and also be absorbed to, crystal and contained in the products of ceramic tile or glass ceramics during the melting process, when the chromium slag is as the raw material of ceramic tile and glass ceramic. The removable rate of Cr6+ in the products of ceramic tile or glass ceramics is about 99%, meeting the regulations for the Cr6+ pollution control.
4.The content of Cr6+ in the products of ceramic tile is 0.0046mg/L when 15%chromium slag is contributed to the raw material of ceramic, meeting the regulations for hexavalent chromium pollution in drinking water sanitary standards. The main parameters of the ceramic tile performance reach the national standards. That means that chromium slag can be used as the raw material of ceramic tile.
5.The results of the cross-test for the glass ceramics show that the optimizing process conditions for the glass ceramics production is : nucleation temperature,820, nucleation time,1h, crystallization temperature, 1120, crystallization time, 1h.
And the content of Cr6+ in the products of glass ceramics is 0.005mg/L, meeting the regulations for the Cr6+ pollution control in drinking water sanitary standards. The main parameters of the glass ceramics performance reach the national standards. That means that chromium slag can be used as the raw material of glass ceramic.
引文
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[25]张敖荣.铬渣烧制早强普通硅酸盐水泥［J］.水泥工程.1998.（5）,37-38.
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[2]成思危,铬盐生产工艺［M］,化学工业出版社,1988.1.128-250.
[3]陈荔英,福建省危险废物现状分析及防治对策［J］,福建环境,1998,15（4）,18-18,35.
[4]李在明,福建省环境状况公报1999,2000,6.3
[5](美)索斯坦森著,万克武译,实用制革学[M],轻工业出版社,1984.9.55-86.
[6]田庆芳.制革厂铬鞣废水铬回收利用与处理［J］.环境污染与防治,1996,(3),13～16.
[7]李莉.高温熔融法治理铬渣--铬的分布及六价铬解毒机理的探讨[M].太原工业大学. 1988.7.30-33
[8]赵万有,郑玉兰,关连,铬渣对地下水、土壤、蔬菜污染机制的研究［J］,环境保护科学,1994.20(1),15-19.
[9]李有光,龚七一,秦德酬等.利用铬渣制造微晶玻璃建筑装饰板［J］,环境科学,1994.15（6）,41-42.
[10]陈建平.用页岩、煤矸石制砖法治理铬渣的实验研究[M].重庆大学.1991.4
[11]王永增,杨国武,赵敏等.利用铬渣烧制彩釉玻化砖试验研究［J］.环境科学.1995.16（5）,41-44.
[12] 邢磊.工业固体废弃物的矿物学研究及其资源化途径探讨--以德阳磷石膏、钢渣,锦阳铬渣为例[M].成都理工学院.2002.5
[13]任庆玉.铬渣的治理与综合利用［J］.环境工程.1989.7（3）,50-55.
[14]孟庆英,渠荣遴.铬渣低氧焙烧水淬急冷无毒化治理反应机理［J］.环境工程.1989.7（4）,9-18
[15]唐秋泉.选择铬渣治理方法的探讨［J］.无机盐工业.1988.（3）,19-22.
[16]丁翼.铬渣治理工作回顾及经验教训［J］.化工环保.1994.14（4）,210-215
[17]兰嗣国,殷惠民,狄一安等.浅谈铬渣解毒技术［J］.环境科学研究.1998.11（3）,53-56.
[18]马书文.铬渣治理与资源化综述［J］.无机盐工业.1997.（2）,19-22.
[19]丁翼.我国铬盐生产状况及发展建议［J］.无机盐工业.2000.32（4）,28-44.
[20]陈娴文.铬渣资源化技术[M]. 277-281.
[21]丁翼.我国铬盐生产环境保护工作的现状、展望及建议[M].436-440.
[22]方荣利,卢忠远,李维国等.利用工业废渣生产新型贝利特水泥的研究［J］.水泥.1993.(3),1-5.
[23]王玉才.用铬渣生产水泥熟料的试验［J］.水泥工程.2000.（2）,57-58.
[24]张敖荣.铬渣综合利用制水泥［J］.无机盐工业.1998.30（4）,34-35.
[25]张敖荣.铬渣烧制早强普通硅酸盐水泥［J］.水泥工程.1998.（5）,37-38.
[26]席耀忠.水泥研究和开发的新成果、新动向（第九届国际水泥化学会议关于水泥论文的索引（上））［J］.水泥.1993.9,40-42.
[27]席耀忠.水泥研究和开发的新成果、新动向（第九届国际水泥化学会议关于水泥论文的索引（下））［J］.水泥.1993.10.40-42
[28]张懿,李佐虎,王志宽等.绿色化学与铬盐工业的新一代产业革命［J］.化学进展.1998.10（2）,172-178.
[29]齐涛,张懿,郭跃华等.铬渣零排放绿色化工新过程［J］.化工冶金.1999.20（1）,92-97.
[30]苏威译.用铬渣制成无毒的新型复合材料.化学工业日报（日）,1985.5.13（1）
[31]丁翼.铬盐生产过程中含铬副产物的综合利用［J］.无机盐工业.1999.31（4）,37-39.
[32]兰嗣国,狄一安,王家贞等.解毒铬渣安全性研究［J］.环境科学研究.1998.11（1）,53-56.
[33]方玉萍.陶瓷砖的现状及今后发展目标和措施［J］.新型建筑材料.1996,3,29-34.
[34]方玉萍.陶瓷砖的现状及今后发展目标和措施（续）［J］.新型建筑材料.1996,4.11-15.
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