造纸废水处理及工业回用研究
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摘要
本课题在总结前人厌氧水处理技术和造纸废水回用技术的基础上，将厌氧处理工艺中的UASB技术应用于造纸废水处理中，并将其作为废水回用系统的中心处理单元，辅以粉煤灰后处理，使废水中有机物、硫酸根、碱土金属离子、重金属离子、总硬度等多类物质得到有效去除，废水能够回用于造纸生产。此类方法在国内外文献中还未见报道。
根据实际情况需要，实验在对华光集团等造纸企业实地调研的基础上，对二次纤维制浆造纸废水进行了实验室模拟。实验配制的模拟废水COD达到1100mg／L，接近多数二次浆造纸废水特征，UASB水力停留时间达到4.43小时，与正常工业化运行的反应器一致，并由此得到UASB容积负荷约6.0kgCOD／(m~3·d)，这些参数可以满足华光集团等二次纤维制浆造纸企业的实际情况。
实验重点观察了UASB系统启动和处理模拟造纸废水的运行情况，通过对水温、出水VFA浓度、出水碱度等指标的监测，及时调整UASB反应器的运行负荷，补充N、P及微量元素，使系统保持了较高的处理效率，UASB稳定运行时可去除90％以上的COD，50％以上的总硬度以及80％以上的硫酸根离子。
影响UASB处理效果的主要因素有温度、营养物质和污泥与基质的接触程度。特别是温度，与UASB产气速率关系密切，分析发现二者符合Arrhenius方程，并可以表达为：
v为T温度(K)下的产甲烷速率，单位L_(CH4)／(L·d)。
由于UASB反应器对难降解物质和Na~+、K~+、Ca~(2+)等离子的去除效率不高，故考虑对UASB出水进行后处理。
经过对活性污泥法和粉煤灰吸附处理的比较，实验确定了用粉煤灰吸附作为UASB的后处理工艺。经粉煤灰处理后，金属离子，包括Na~+、K~+、Ca~(2+)等，浓度普遍降低，说明用粉煤灰处理UASB出水不但不存在金属溶出问题，反而能够控制体系的金属离子和盐份。粉煤灰对难降解物质也有良好的吸附效果，灰水比达到1.33g／L就可使UASB出水色度降至15度，即可达到饮用水卫生标准(GB549-85)。粉煤灰对色度的去除效果满足Freundlich等温方程：
lnq=0.674lnC+2.821
According to the summary of the techniques of the anaerobic water treatment and the reuse of the wastewater from papermaking, the Up-flow Anaerobic Sludge Bed (UASB) was used to treat the wastewater from pulp and paper making with recycled fiber in this research. The UASB was used as the central unit of the system, and the coal fly ash was settled to treat the effluent from the UASB. In addition to organic substance, many species of contaminants were removed by this system, such as group S042-, ions of alkaline earth metal and heavy metal, and total hardness et al. After the treatment, the wastewater could be recycled into the production of papermaking.
Because the treatment system was operated in laboratory, simulated wastewater was confected according to the investigation of papermaking process in several companies. The COD of simulated wastewater was about 1100 mg/L, which was close the property of the wastewater of most paper mills using recycled fiber. The HRT of UASB reactor was about 4.43h, which was accord with most UASB plants.
During the research, the starting up and operating process of the UASB reactor were observed. The temperature of the water, the VFA and alkalinity concentration of the UASB effluent was surveyed particularly. The UASB reactor was found can keep high treatment efficiency by adjusting the load of the UASB and supplying N, P elements and some other microelements. The process on average removed about 90% of COD, 50% of total hardness, and 80% of sulfate.
The main factors affecting the treatment efficiency were temperature, nutriments and the sludge exposure level to substrate. Especially, the temperature had a close relationship with the methane yield rate. The relation could be given with the equation:
V is the methane yield rate at the temperature T (K).
According to the comparison between activated sludge process (AS) and absorption with coal fly ash, the coal fly ash absorption was decided as the reprocessing technique of the UASB effluent. After the process, the concentration of metal ions reduced obviously. The process of coal fly ash absorption wouldn't bring the dissolving of metal ions, and, withal, the concentration of metal ions could be controlled effectively. The removal of chromaticity meets the Freundlich isothermal equation:
In q = 0.674 In C + 2.821
根据实际情况需要，实验在对华光集团等造纸企业实地调研的基础上，对二次纤维制浆造纸废水进行了实验室模拟。实验配制的模拟废水COD达到1100mg／L，接近多数二次浆造纸废水特征，UASB水力停留时间达到4.43小时，与正常工业化运行的反应器一致，并由此得到UASB容积负荷约6.0kgCOD／(m~3·d)，这些参数可以满足华光集团等二次纤维制浆造纸企业的实际情况。
实验重点观察了UASB系统启动和处理模拟造纸废水的运行情况，通过对水温、出水VFA浓度、出水碱度等指标的监测，及时调整UASB反应器的运行负荷，补充N、P及微量元素，使系统保持了较高的处理效率，UASB稳定运行时可去除90％以上的COD，50％以上的总硬度以及80％以上的硫酸根离子。
影响UASB处理效果的主要因素有温度、营养物质和污泥与基质的接触程度。特别是温度，与UASB产气速率关系密切，分析发现二者符合Arrhenius方程，并可以表达为：
v为T温度(K)下的产甲烷速率，单位L_(CH4)／(L·d)。
由于UASB反应器对难降解物质和Na~+、K~+、Ca~(2+)等离子的去除效率不高，故考虑对UASB出水进行后处理。
经过对活性污泥法和粉煤灰吸附处理的比较，实验确定了用粉煤灰吸附作为UASB的后处理工艺。经粉煤灰处理后，金属离子，包括Na~+、K~+、Ca~(2+)等，浓度普遍降低，说明用粉煤灰处理UASB出水不但不存在金属溶出问题，反而能够控制体系的金属离子和盐份。粉煤灰对难降解物质也有良好的吸附效果，灰水比达到1.33g／L就可使UASB出水色度降至15度，即可达到饮用水卫生标准(GB549-85)。粉煤灰对色度的去除效果满足Freundlich等温方程：
lnq=0.674lnC+2.821
According to the summary of the techniques of the anaerobic water treatment and the reuse of the wastewater from papermaking, the Up-flow Anaerobic Sludge Bed (UASB) was used to treat the wastewater from pulp and paper making with recycled fiber in this research. The UASB was used as the central unit of the system, and the coal fly ash was settled to treat the effluent from the UASB. In addition to organic substance, many species of contaminants were removed by this system, such as group S042-, ions of alkaline earth metal and heavy metal, and total hardness et al. After the treatment, the wastewater could be recycled into the production of papermaking.
Because the treatment system was operated in laboratory, simulated wastewater was confected according to the investigation of papermaking process in several companies. The COD of simulated wastewater was about 1100 mg/L, which was close the property of the wastewater of most paper mills using recycled fiber. The HRT of UASB reactor was about 4.43h, which was accord with most UASB plants.
During the research, the starting up and operating process of the UASB reactor were observed. The temperature of the water, the VFA and alkalinity concentration of the UASB effluent was surveyed particularly. The UASB reactor was found can keep high treatment efficiency by adjusting the load of the UASB and supplying N, P elements and some other microelements. The process on average removed about 90% of COD, 50% of total hardness, and 80% of sulfate.
The main factors affecting the treatment efficiency were temperature, nutriments and the sludge exposure level to substrate. Especially, the temperature had a close relationship with the methane yield rate. The relation could be given with the equation:
V is the methane yield rate at the temperature T (K).
According to the comparison between activated sludge process (AS) and absorption with coal fly ash, the coal fly ash absorption was decided as the reprocessing technique of the UASB effluent. After the process, the concentration of metal ions reduced obviously. The process of coal fly ash absorption wouldn't bring the dissolving of metal ions, and, withal, the concentration of metal ions could be controlled effectively. The removal of chromaticity meets the Freundlich isothermal equation:
In q = 0.674 In C + 2.821
引文
[1] 张珂，中国造纸工业节约用水迫在眉睫，纸和造纸，Vol．2001，No．3，No．2，5-7
[2] 赵振东，谈山东造纸十佳企业，中华纸业，2001年4月，Vol．22，No．4，35
[3] 李相然等，山东半岛水资源开发和利用中的环境效应研究，地质灾害与环境保护，Vol．11，No．3，263-267
[4] 刘洪滨，解决山东水资源短缺问题的对策，国土与自然资源研究，Vol．1996，No．4，39-42
[5] 朱平盛等，山东水资源分析及趋势预测，气象，Vol．24，No．3，3-8
[6] 李素菊，山东冲积平原地下水的合理开发与保护，山东建筑工程学院学报，Vol．15，No．1，44-47
[7] 贺延龄，废纸制浆造纸废水的封闭循环和零排放，中华纸业，Vol．22，No．2，13-16
[8] M. N. De Pinho, et al., Integration of flotation/ultrafiltration for treatment of bleached pulp effluent, Pulp & Paper Canada, 101:4(2000), 50-54
[9] Subhash Chandra, Effluent minimization — a little water goes a long way, TAPPI, 1997, Vol.80, No.12, 37-42
[10] S. Bédard, et al., Application of process integration in water re-use projects, Pulp & Paper Canada, 102:3(2001), 53-56
[11] Douglas A. Barton, et al., Experience with water system closure at recycled paperboard mills, TAPPI, 1996, Vol.79, No.3, 191-197
[12] 蔡悦胜，造纸废水循环回用过程中出现的问题及解决方法，广东造纸，2000，No．6，53-55．
[13] X. Zhang, et al., Accumulation of Specific Dissolved and Colloidal Substances During White Water Recycling Affects Paper Properties, JPPS, 1999, Vol.25, No.9, 206-210
[14] Linda R. Robertson, A Clean Machine with Minimal Fresh Water, PIMA, 1995, 4, 42-43
[15] 何北海等，造纸清洁生产与系统水封闭回用，中国造纸，2000，No．5，43-48
[16] Christine Foster, et al., How Recycling, Water Reuse Impact Chemistry, PIMA, 1997, 79(1), 48-53
[17] N. Jemaa, et al., Non-process elements in the kraft recovery cycle, Part Ⅱ :control and removal options, Pulp & Paper Canada, 101:2(2001), 41-46
[18] M. Montanhese, et al., Green liquor filtration at Aracruz Celulose Mill: Causticizing and Effluent close-up, pilot plant and practical results, Pulp & Paper Canada, 102:1(2001), 39-41
[19] 刘秉钺等，制浆造纸节能技术，中国轻工业出版社，1999，第五章，第一节
[20] H. Park, et al., Precipitation conditions of aluminosilicate scales in the recovery cycle of kraft pulp mills, Pulp & Paper Canada, 102:2(2001), 20-24
[21] Bertel Myreen, Straw's new horizons-A novel desilication technology could prove a valuable
boost for straw pulp mills. Pulp & Paper Asia. October(2000)
[22]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．2，16-18
[23]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．3，7-9
[24]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．2，9-11，22
[25]贺延龄，废水的厌氧生物处理，中国轻工业出版社，1998年第一版
[26]贺延龄，废水厌氧技术的新进展，纸和造纸，2001，No．6，45-48
[27]R．E．Speece著，李亚新译，工业废水的厌氧生物技术，中国建筑工业出版社，2001年第一版
[28]Guiot,et al.,A Structured Model of the Anaerobic Granule Consortium,Water Sci.Tech.,1992,Vol.25,1-10
[29]Benjamin,et al.,Wat.Res.,1984(18),601-607
[30]李亚峰等，粉煤灰处理废水的理论与实践，工业用水与废水，1999，Vol．30，No．3，1-3
[31]李亚峰等，粉煤灰处理废水研究与应用的现状及发展，沈阳建筑工程学院学报，Vol．15， No．4，348-351
[32]卢素焕等，粉煤灰在废水处理中的应用，电力情报，Vol．1998，No．2，27-30
[33]付尔登，粉煤灰吸附处理麻黄素废水的实验研究，新疆环境保护，Vol．18，No．4，54-57
[34]王福元、吴正严，粉煤灰利用手册，中国电力出版社，1997年7月第一版
[35]张建平等，粉煤灰处理废水的机理及应用，粉煤灰综合利用，Vol．1996，No．4，33-35
[36]张警声等，粉煤灰吸附生活污水中磷的研究，东北电力学院学报，1999，Vol．19，No．3， 50-53
[37]阎存仙，粉煤灰对亚甲基兰溶液的吸附脱色研究，电镀与环保，Vol．16，No．5，27-29
[38]邵颖等，活化粉煤灰对弱酸性艳绿GS吸附性能的研究，工业水处理，1997，Vol．17， No．1，21-23、27
[39]刘国光等，粉煤灰吸附性能的研究，环境科学研究，Vol．7，No．5，62-64
[40]夏畅斌等，粉煤灰及改性粉煤灰对邻甲酚吸附性能的研究，环境污染治理技术与设备，2000，Vol．1，No．2，82-85
[41]于衍真等，粉煤灰在废水处理工程中应用，硅酸盐通报，Vol．1998，No．3，42-45
[42]王晓钧等，粉煤灰基质多孔吸附材料的研制，粉煤灰综合利用，Vol．1994，No．4，33-36
[43]王晓钧等，粉煤灰基质多孔吸附材料显微结构及性能研究，分析测试技术与仪器，1995， Vol．1，No．2，38-41
[44]制浆造质手册，第12分册，轻工出版社，1990年12月版
[2] 赵振东，谈山东造纸十佳企业，中华纸业，2001年4月，Vol．22，No．4，35
[3] 李相然等，山东半岛水资源开发和利用中的环境效应研究，地质灾害与环境保护，Vol．11，No．3，263-267
[4] 刘洪滨，解决山东水资源短缺问题的对策，国土与自然资源研究，Vol．1996，No．4，39-42
[5] 朱平盛等，山东水资源分析及趋势预测，气象，Vol．24，No．3，3-8
[6] 李素菊，山东冲积平原地下水的合理开发与保护，山东建筑工程学院学报，Vol．15，No．1，44-47
[7] 贺延龄，废纸制浆造纸废水的封闭循环和零排放，中华纸业，Vol．22，No．2，13-16
[8] M. N. De Pinho, et al., Integration of flotation/ultrafiltration for treatment of bleached pulp effluent, Pulp & Paper Canada, 101:4(2000), 50-54
[9] Subhash Chandra, Effluent minimization — a little water goes a long way, TAPPI, 1997, Vol.80, No.12, 37-42
[10] S. Bédard, et al., Application of process integration in water re-use projects, Pulp & Paper Canada, 102:3(2001), 53-56
[11] Douglas A. Barton, et al., Experience with water system closure at recycled paperboard mills, TAPPI, 1996, Vol.79, No.3, 191-197
[12] 蔡悦胜，造纸废水循环回用过程中出现的问题及解决方法，广东造纸，2000，No．6，53-55．
[13] X. Zhang, et al., Accumulation of Specific Dissolved and Colloidal Substances During White Water Recycling Affects Paper Properties, JPPS, 1999, Vol.25, No.9, 206-210
[14] Linda R. Robertson, A Clean Machine with Minimal Fresh Water, PIMA, 1995, 4, 42-43
[15] 何北海等，造纸清洁生产与系统水封闭回用，中国造纸，2000，No．5，43-48
[16] Christine Foster, et al., How Recycling, Water Reuse Impact Chemistry, PIMA, 1997, 79(1), 48-53
[17] N. Jemaa, et al., Non-process elements in the kraft recovery cycle, Part Ⅱ :control and removal options, Pulp & Paper Canada, 101:2(2001), 41-46
[18] M. Montanhese, et al., Green liquor filtration at Aracruz Celulose Mill: Causticizing and Effluent close-up, pilot plant and practical results, Pulp & Paper Canada, 102:1(2001), 39-41
[19] 刘秉钺等，制浆造纸节能技术，中国轻工业出版社，1999，第五章，第一节
[20] H. Park, et al., Precipitation conditions of aluminosilicate scales in the recovery cycle of kraft pulp mills, Pulp & Paper Canada, 102:2(2001), 20-24
[21] Bertel Myreen, Straw's new horizons-A novel desilication technology could prove a valuable
boost for straw pulp mills. Pulp & Paper Asia. October(2000)
[22]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．2，16-18
[23]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．3，7-9
[24]皇甫浩，贺延龄，造纸工业废水的厌氧处理技术，西南造纸，1999，No．2，9-11，22
[25]贺延龄，废水的厌氧生物处理，中国轻工业出版社，1998年第一版
[26]贺延龄，废水厌氧技术的新进展，纸和造纸，2001，No．6，45-48
[27]R．E．Speece著，李亚新译，工业废水的厌氧生物技术，中国建筑工业出版社，2001年第一版
[28]Guiot,et al.,A Structured Model of the Anaerobic Granule Consortium,Water Sci.Tech.,1992,Vol.25,1-10
[29]Benjamin,et al.,Wat.Res.,1984(18),601-607
[30]李亚峰等，粉煤灰处理废水的理论与实践，工业用水与废水，1999，Vol．30，No．3，1-3
[31]李亚峰等，粉煤灰处理废水研究与应用的现状及发展，沈阳建筑工程学院学报，Vol．15， No．4，348-351
[32]卢素焕等，粉煤灰在废水处理中的应用，电力情报，Vol．1998，No．2，27-30
[33]付尔登，粉煤灰吸附处理麻黄素废水的实验研究，新疆环境保护，Vol．18，No．4，54-57
[34]王福元、吴正严，粉煤灰利用手册，中国电力出版社，1997年7月第一版
[35]张建平等，粉煤灰处理废水的机理及应用，粉煤灰综合利用，Vol．1996，No．4，33-35
[36]张警声等，粉煤灰吸附生活污水中磷的研究，东北电力学院学报，1999，Vol．19，No．3， 50-53
[37]阎存仙，粉煤灰对亚甲基兰溶液的吸附脱色研究，电镀与环保，Vol．16，No．5，27-29
[38]邵颖等，活化粉煤灰对弱酸性艳绿GS吸附性能的研究，工业水处理，1997，Vol．17， No．1，21-23、27
[39]刘国光等，粉煤灰吸附性能的研究，环境科学研究，Vol．7，No．5，62-64
[40]夏畅斌等，粉煤灰及改性粉煤灰对邻甲酚吸附性能的研究，环境污染治理技术与设备，2000，Vol．1，No．2，82-85
[41]于衍真等，粉煤灰在废水处理工程中应用，硅酸盐通报，Vol．1998，No．3，42-45
[42]王晓钧等，粉煤灰基质多孔吸附材料的研制，粉煤灰综合利用，Vol．1994，No．4，33-36
[43]王晓钧等，粉煤灰基质多孔吸附材料显微结构及性能研究，分析测试技术与仪器，1995， Vol．1，No．2，38-41
[44]制浆造质手册，第12分册，轻工出版社，1990年12月版