液相脱色用颗粒活性炭的吸附行为及再生机理研究
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摘要
活性炭具有发达的孔隙结构，巨大的比表面积和良好的化学稳定性。活性炭的吸附性能优良，是使用最广泛，也是较为经济的吸附剂，在工业应用中已有多年的历史。活性炭应用初期主要是粉状活性炭(PAC)在糖液精制中逐步代替了原来的骨炭；第一次世界大战中出现的颗粒活性炭(GAC)首先应用在防毒面具中；如今活性炭在水处理、环境保护、食品工业、化学工业和军事国防工业等领域中发挥着巨大的作用。
液相吸附精制中，以前完全使用PAC，现在使用也很多，但现在大规模的精制及新建的精制工艺中，GAC的用量正在增加。GAC应用于液相脱色精制，脱色效果好，操作简便，整个生产过程易于实现连续化、自动化。GAC可再生，能够反复使用，节省资源，减少二次污染，在工业应用及环保方面有良好的发展前景。本论文选用本所自制的GAC作为吸附剂，以B法焦糖和某企业的柠檬酸发酵液中的色素作为吸附质，作静态吸附试验，摸索最佳吸附工艺条件；将GAC装柱作动态吸附试验，绘制穿透曲线，计算理论塔板数(n)和理论塔板高度(HETP)；对吸附精制柠檬酸发酵液达饱和的GAC进行再生试验，初步研究化学法再生的机理。对传统应用的化学再生法进行了工艺方法和操作条件的改进，获得的结果可为工业应用提供参考。本论文的主要研究内容与结果归纳如下：
1．摸索活性炭用量、吸附时间、吸附温度和溶液初始浓度等参数对静态吸附效果的影响，并比较所选GAC对B法焦糖溶液和柠檬酸发酵液的吸附情况。得出结论，在实验室静态吸附试验中可用B法焦糖溶液代替柠檬酸发酵液作模拟试验，实验室中得到的最佳工艺条件可以作为工业应用的参考。
2．绘制所选GAC对B法焦糖液的吸附等温线，绘制活性炭对柠檬酸发酵液的吸附等温线，并作比较。证明了所选GAC对B法焦糖和柠檬酸发酵液中的色素都是容易吸附的，也证明可以用B法焦糖溶液代替柠檬酸发酵液在实验室中做模拟试验。举例说明由吸附等温线可计算处理一定量发酵液所需活性炭的量。
3．将所选GAC装柱作动态吸附试验，并绘制穿透曲线。采用HAMDIA．MOSTAFA提出的经验公式计算该活性炭柱的理论塔板数(n)和理论塔板高度(HETP)，获得的结果可为设计实用装置提供必要的理论依据。计算出的理论塔板数n=342块，理论塔板高度为HETP=0.35mm。
4．以吸附柠檬酸发酵液达饱和的GAC为原料，用酸碱化学法进行再生。讨论NaOH溶液质量分数、再生时间和再生温度对再生效果的影响。GAC再生过程中，增加水洗及添加氧化剂、表面活性剂的操作，能有效提高活性炭的再生效率。不
Activated carbon has huge porosity , specific surface and excellent stability. It is one of the most popular and economical adsorbents and has been widely used for many decades. In the early days of activated carbon application, the powdered activated carbon (PAC) has replaced original bone charcoal in the process of sugar refinement gradually. During the world war I, the granular activated carbon (GAC) was firstly produced and applied in the gas mask; nowadays, GAC has played an important role in water treatment and environmental protection.
It is effectually to decolor, easily and simply to handle and the whole production process is apt to realize continuous and automatic operation if we apply GAC in the liquid decoloration and refining.
It will achieve excellent results to apply GAC in the process of liquid decoloration and refining. GAC is simple to handle and be apt to realize continuous and automatic processing.
GAC is renewable, which will save resources and cut down secondary pollution, we can fully believe the GAC has good prospects in the industrial application. Having selected our institute self-made GAC which has high caramel decoloration as adsorbent, self-made B-caramel liquid and one corporation's citric acid liquor as adsorbate in this static adsorption experiment, the author tried to find out the best process conditions. Installing GAC into column, performing the dynamic adsorption experiment, plotting breakthrough curve, counting n (theoretical plate) and HETP (height of a theoretical plate), Recycling exhausted GAC, the author made the further study on different technics and conditions for acid and alkali regeneration of traditional way, which can
液相吸附精制中，以前完全使用PAC，现在使用也很多，但现在大规模的精制及新建的精制工艺中，GAC的用量正在增加。GAC应用于液相脱色精制，脱色效果好，操作简便，整个生产过程易于实现连续化、自动化。GAC可再生，能够反复使用，节省资源，减少二次污染，在工业应用及环保方面有良好的发展前景。本论文选用本所自制的GAC作为吸附剂，以B法焦糖和某企业的柠檬酸发酵液中的色素作为吸附质，作静态吸附试验，摸索最佳吸附工艺条件；将GAC装柱作动态吸附试验，绘制穿透曲线，计算理论塔板数(n)和理论塔板高度(HETP)；对吸附精制柠檬酸发酵液达饱和的GAC进行再生试验，初步研究化学法再生的机理。对传统应用的化学再生法进行了工艺方法和操作条件的改进，获得的结果可为工业应用提供参考。本论文的主要研究内容与结果归纳如下：
1．摸索活性炭用量、吸附时间、吸附温度和溶液初始浓度等参数对静态吸附效果的影响，并比较所选GAC对B法焦糖溶液和柠檬酸发酵液的吸附情况。得出结论，在实验室静态吸附试验中可用B法焦糖溶液代替柠檬酸发酵液作模拟试验，实验室中得到的最佳工艺条件可以作为工业应用的参考。
2．绘制所选GAC对B法焦糖液的吸附等温线，绘制活性炭对柠檬酸发酵液的吸附等温线，并作比较。证明了所选GAC对B法焦糖和柠檬酸发酵液中的色素都是容易吸附的，也证明可以用B法焦糖溶液代替柠檬酸发酵液在实验室中做模拟试验。举例说明由吸附等温线可计算处理一定量发酵液所需活性炭的量。
3．将所选GAC装柱作动态吸附试验，并绘制穿透曲线。采用HAMDIA．MOSTAFA提出的经验公式计算该活性炭柱的理论塔板数(n)和理论塔板高度(HETP)，获得的结果可为设计实用装置提供必要的理论依据。计算出的理论塔板数n=342块，理论塔板高度为HETP=0.35mm。
4．以吸附柠檬酸发酵液达饱和的GAC为原料，用酸碱化学法进行再生。讨论NaOH溶液质量分数、再生时间和再生温度对再生效果的影响。GAC再生过程中，增加水洗及添加氧化剂、表面活性剂的操作，能有效提高活性炭的再生效率。不
Activated carbon has huge porosity , specific surface and excellent stability. It is one of the most popular and economical adsorbents and has been widely used for many decades. In the early days of activated carbon application, the powdered activated carbon (PAC) has replaced original bone charcoal in the process of sugar refinement gradually. During the world war I, the granular activated carbon (GAC) was firstly produced and applied in the gas mask; nowadays, GAC has played an important role in water treatment and environmental protection.
It is effectually to decolor, easily and simply to handle and the whole production process is apt to realize continuous and automatic operation if we apply GAC in the liquid decoloration and refining.
It will achieve excellent results to apply GAC in the process of liquid decoloration and refining. GAC is simple to handle and be apt to realize continuous and automatic processing.
GAC is renewable, which will save resources and cut down secondary pollution, we can fully believe the GAC has good prospects in the industrial application. Having selected our institute self-made GAC which has high caramel decoloration as adsorbent, self-made B-caramel liquid and one corporation's citric acid liquor as adsorbate in this static adsorption experiment, the author tried to find out the best process conditions. Installing GAC into column, performing the dynamic adsorption experiment, plotting breakthrough curve, counting n (theoretical plate) and HETP (height of a theoretical plate), Recycling exhausted GAC, the author made the further study on different technics and conditions for acid and alkali regeneration of traditional way, which can
引文
[1]．M．Smisek编著(1981)．活性炭．国营新华化工厂设计研究所。
[2]．哈斯勒著<美>，林秋华译(1980)．活性炭．中国建筑工业出版社。
[3]. Jenkins S.H.(1979). Activated carbon manufacture and regeneration.. 13(4). 403-404.
[4]. Conchi O Ania, Teresa J Bandos (2005), Importance of structural and chemical heterogeneity of activated carbon surface for adsorption of dibenzothiophene.. 21 (17). 7752-7759.
[5] Kirti V Dubey, Asha A Juwarkar(2005). Adsorption-desorption process using wood-based activated carbon for recovery of biosurfactant from fermented distillery wastewater.. 21 (3). 860-867.
[6]郏其庚等(2003)．活性炭的应用．华东理工大学出版社。
[7]蒋剑春，顾瑞生(2004)．我国木质活性炭工业概况和发展前景．2004年全国活性炭学术研讨会论文集．415-419．
[8]立本英机，安部郁夫主编，高尚愚译编(2002)．活性炭的应用技术．东南大学出版社。
[9]Ania C.O., Parra J.B., Perida C (2005). Pyrolysis of activated carbons exhausted with organic compounds.. 518-524.
[10]张会平，肖新颜(2004)．活性炭再生技术研究进展．2004年全国活性炭学术研讨会论文集．463-469．
[11]Kharoune M, Pauss A, Lebeault J M (2001),. Aerobic biodegration of an oxgenates mixture: ETBE, MTBE and TAME in an upflow fixed-bed reator.. 35(7). 1665-74.
[12]Tamon H., Okazaki M. (1996).. 179-181.
[13]刘勇第，高勇，袁渭康(1999)．超临界流体活性炭再生技术．<化工进展>．11．457-459．
[14]张会平，叶李艺，傅志鸿等(2001)．活性炭的电化学再生技术研究．<化工进展>．20(10)．17-20．
[15]陈岳松，陈玲，赵建夫(1998)．湿式氧化再生活性炭研究进展．<上海环境科学>．17(9)．5-7．
[16]C.M.Gastilla, J.R.Utrilla, J.P. Joly (1995).. 33.1417.
[17]Roberto.M.Narbaitz, Joanqi.Cen(1994).. 28(8). 1771.
[18]Zhang H.P., Zhong H, Ye L.Y. (2001).. Vol. 77(10). 1246-1250.
[19]Huling S.G., Jones P.K. (2005). Fenton-driven chemical regeneration of MTBE-spent??GAC.. 39(10). 2145-2153.
[20]Zhang H.P. (2002). Regeneration of exhausted activated carbon by electrochemical method..
[21]Arslanoglu F.N., Kar F., Ar slan N.(2005). Adsorption of dark colored compounds from peach pulp by using powdered-activated carbon.. 71(2). 156-163.
[22]Conchi O Ania, Feresa J Bandosz (2005). Importane of structural and chemical heterogeneity of activated carbon surface for adsorption of dibenzothiophene.. 21(11). 7752-7759.
[23]叶振华(1988)．吸着分离过程基础．化学工业出版社．
[24]D S Chaudhary, S Vigneswaran (2003). Granular activated carbon(GAC) adsorption in tertiary wastewater treatment: experiments and models.. 47(1). 113-120.
[25]M．A．安德森[美]，A．J．鲁宾，刘蓬生，张正斌译(1989)．水溶液吸附化学．北京科学出版社。
[26]王乃忠，滕兰珍(1988)．水处理理论基础．西南交通大学出版社。
[27]蒋剑春，孙康(2004)．活性炭吸附性能对水处理的影响．2004年全国活性炭学术研讨会论文集．363-367．
[28]HAMD A., MOSTAFA, A.S.SAID. Theoretical--Plate concept for Fixed--Bed Adsorption and Ion--Exchange.
[29]蒋剑春等(2001)．针剂活性炭对VB6溶液的脱色实验研究．第六次全国活性炭学术讨论会论文集．75-76．
[30]北川浩，铃木谦一郎，鹿政理译(1988)．<吸附的基础与设计>．化学工业出版社。
[31]井出哲夫等著，张自杰等译(1978)．<水处理工程理论与应用>．中国建筑工业出版社。
[32]Sotelo J.L., Uguina M.A., Delgado J.A. (2004). Adsorption of methyl ethyl ketone and trichloroethene from aqueous solution onto activated carbon fixed-bed adsorbers.. 37(2). 149-160.
[33]同32
[34]同28
[35]许乃鑫，庞乾椿(1986)．血液灌流用FQ活性树脂的制备及其体外吸附行为．上海市生物医学工程学会第二届学术年会论文(摘要)集。
[36]同28[38]秦玉春，王海涛等(2001)．活性炭的再生方法，<炭素技术>．6．29-31．
[39]刘守新等(2001)．活性炭再生技术研究进展．<东北林业大学学报>．29(3)．61-63．
[40]刘守新，王岩等(2001)．活性炭光催化再生技术的研究．第六次全国活性炭学术讨论会论文集．92-97．
[41]Chi-Cheng Leng, Neville G. Pinto (1996). Investigation of the mechanisms of chemical regeneration of activated carbon.. 35.2004-2031.
[42]Milsom P E, Meer J L (1985). Citric Acid. Comprehensive biotechnology. New York:Persimmon Press Ltd.
[43]Sabio E., Gonzalez-Martin M.L. (2001). Influence of the regeneration of temperature on the phenols adsorption on activated carbon.. 342(1). 31-35.
[44]同41．
[45]韦朝海，孙寿家(1995)．活性炭处理含氰废水作用机理分析与研究．<环境科学与技术>．2．1-5．
[46]同2．
[2]．哈斯勒著<美>，林秋华译(1980)．活性炭．中国建筑工业出版社。
[3]. Jenkins S.H.(1979). Activated carbon manufacture and regeneration.
[4]. Conchi O Ania, Teresa J Bandos (2005), Importance of structural and chemical heterogeneity of activated carbon surface for adsorption of dibenzothiophene.
[5] Kirti V Dubey, Asha A Juwarkar(2005). Adsorption-desorption process using wood-based activated carbon for recovery of biosurfactant from fermented distillery wastewater.
[6]郏其庚等(2003)．活性炭的应用．华东理工大学出版社。
[7]蒋剑春，顾瑞生(2004)．我国木质活性炭工业概况和发展前景．2004年全国活性炭学术研讨会论文集．415-419．
[8]立本英机，安部郁夫主编，高尚愚译编(2002)．活性炭的应用技术．东南大学出版社。
[9]Ania C.O., Parra J.B., Perida C (2005). Pyrolysis of activated carbons exhausted with organic compounds.
[10]张会平，肖新颜(2004)．活性炭再生技术研究进展．2004年全国活性炭学术研讨会论文集．463-469．
[11]Kharoune M, Pauss A, Lebeault J M (2001),. Aerobic biodegration of an oxgenates mixture: ETBE, MTBE and TAME in an upflow fixed-bed reator.
[12]Tamon H., Okazaki M. (1996).
[13]刘勇第，高勇，袁渭康(1999)．超临界流体活性炭再生技术．<化工进展>．11．457-459．
[14]张会平，叶李艺，傅志鸿等(2001)．活性炭的电化学再生技术研究．<化工进展>．20(10)．17-20．
[15]陈岳松，陈玲，赵建夫(1998)．湿式氧化再生活性炭研究进展．<上海环境科学>．17(9)．5-7．
[16]C.M.Gastilla, J.R.Utrilla, J.P. Joly (1995).
[17]Roberto.M.Narbaitz, Joanqi.Cen(1994).
[18]Zhang H.P., Zhong H, Ye L.Y. (2001).
[19]Huling S.G., Jones P.K. (2005). Fenton-driven chemical regeneration of MTBE-spent??GAC.
[20]Zhang H.P. (2002). Regeneration of exhausted activated carbon by electrochemical method.
[21]Arslanoglu F.N., Kar F., Ar slan N.(2005). Adsorption of dark colored compounds from peach pulp by using powdered-activated carbon.
[22]Conchi O Ania, Feresa J Bandosz (2005). Importane of structural and chemical heterogeneity of activated carbon surface for adsorption of dibenzothiophene.
[23]叶振华(1988)．吸着分离过程基础．化学工业出版社．
[24]D S Chaudhary, S Vigneswaran (2003). Granular activated carbon(GAC) adsorption in tertiary wastewater treatment: experiments and models.
[25]M．A．安德森[美]，A．J．鲁宾，刘蓬生，张正斌译(1989)．水溶液吸附化学．北京科学出版社。
[26]王乃忠，滕兰珍(1988)．水处理理论基础．西南交通大学出版社。
[27]蒋剑春，孙康(2004)．活性炭吸附性能对水处理的影响．2004年全国活性炭学术研讨会论文集．363-367．
[28]HAMD A., MOSTAFA, A.S.SAID. Theoretical--Plate concept for Fixed--Bed Adsorption and Ion--Exchange.
[29]蒋剑春等(2001)．针剂活性炭对VB6溶液的脱色实验研究．第六次全国活性炭学术讨论会论文集．75-76．
[30]北川浩，铃木谦一郎，鹿政理译(1988)．<吸附的基础与设计>．化学工业出版社。
[31]井出哲夫等著，张自杰等译(1978)．<水处理工程理论与应用>．中国建筑工业出版社。
[32]Sotelo J.L., Uguina M.A., Delgado J.A. (2004). Adsorption of methyl ethyl ketone and trichloroethene from aqueous solution onto activated carbon fixed-bed adsorbers.
[33]同32
[34]同28
[35]许乃鑫，庞乾椿(1986)．血液灌流用FQ活性树脂的制备及其体外吸附行为．上海市生物医学工程学会第二届学术年会论文(摘要)集。
[36]同28[38]秦玉春，王海涛等(2001)．活性炭的再生方法，<炭素技术>．6．29-31．
[39]刘守新等(2001)．活性炭再生技术研究进展．<东北林业大学学报>．29(3)．61-63．
[40]刘守新，王岩等(2001)．活性炭光催化再生技术的研究．第六次全国活性炭学术讨论会论文集．92-97．
[41]Chi-Cheng Leng, Neville G. Pinto (1996). Investigation of the mechanisms of chemical regeneration of activated carbon.
[42]Milsom P E, Meer J L (1985). Citric Acid. Comprehensive biotechnology. New York:Persimmon Press Ltd.
[43]Sabio E., Gonzalez-Martin M.L. (2001). Influence of the regeneration of temperature on the phenols adsorption on activated carbon.
[44]同41．
[45]韦朝海，孙寿家(1995)．活性炭处理含氰废水作用机理分析与研究．<环境科学与技术>．2．1-5．
[46]同2．