由造纸黑液制取中孔活性炭的研究
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摘要
本研究以造纸黑液为原料，采用水蒸气活化法制取中孔活性炭。
研究中采用盐酸酸析法从造纸黑液中提取木质素。所提取的木质素在一定的温度炭化后，将炭化料粉碎至一定粒度后加入一定量的二茂铁作为催化剂。以水蒸气作为活化剂，在一定的温度下活化一定的时间，制取中孔活性炭，中孔率均大于55％。由于具有较多的中孔，对维生素B_(12)有良好的吸附性能。
本研究探讨了加酸沉淀回收碱法造纸黑液中木质素的工艺条件，研究了反应温度、pH值、反应时间等因素对木质素回收量的影响，得出了最佳反应条件分别为pH=2、反应温度为60℃、反应时间为60min，加酸速度以控制不产生大量泡沫为准，在该条件下，木质素的回收效果最佳，回收量达到了190.03g／L。还研究了水蒸气活化法制备中孔活性炭的工艺条件，讨论了炭化温度、炭化时间、炭化升温速度、活化温度、活化时间、催化剂用量等因素对维生素B_(12)吸附性能的影响，重点对炭化与活化条件进行考察，得到了最佳实验条件分别为：炭化时间为30min、炭化温度为550℃、活化温度为850℃，活化时间为3h。
水蒸汽活化开始以生成微孔为主，随着活化的深入，逐步向中孔、大孔发展，使平均孔径增大。
The mesoporous activated carbon was prepared from black liquor by water vapor.
In this experiment, the lignin was separated from black liquor of paper-aking by adding HC1, The recovered lignin was carbonized at the operational temperature, then some amount of ferrocene as catalysts was loaded into the carbonization material after it was comminuted to definite granularity. The mesoporous activated carbon was obtained after it is activated for some time in the steam atmosphere at the operational temperature. The mesopore ratio was more than 55% in the production. It is showed that the mesoporous activated carbon was suitable as a good adsorbent for VB12 because it has more mesopore.
Firstly, the process of recovering lignin from the alkaline paper-making black liquor by acidulation precipitation was studied. The effect of pH, reactivity temperature and reactivity time was discussed in detail ,while the optimum condition was obtained : pH=2, reactivity temperature=60 Cand reactivity time=60min. The acid flow rate was controlled not to form a lot of froth. Under the above condition, the lignin recovery impact was the best .The recovery amount was 190. 03g/L .The effect of carbonization temperature , carbonization time , carbonization calefactive velocity , activation temperature , activation time , the amount of catalysts on the ability of adsorption to VB12 was studied .The optimum condition was achieved by putting emphasis on studying the condition of carbonization and activation : carbonization time=30min, carbonization temperature =550 C , activation temperature =850 C , activation time=3h.
The activation with steam mainly generated microspore firstly, while the average pore size was increased due to the excess burn-off which made the microspore transfer into mesopore or macropore .
研究中采用盐酸酸析法从造纸黑液中提取木质素。所提取的木质素在一定的温度炭化后，将炭化料粉碎至一定粒度后加入一定量的二茂铁作为催化剂。以水蒸气作为活化剂，在一定的温度下活化一定的时间，制取中孔活性炭，中孔率均大于55％。由于具有较多的中孔，对维生素B_(12)有良好的吸附性能。
本研究探讨了加酸沉淀回收碱法造纸黑液中木质素的工艺条件，研究了反应温度、pH值、反应时间等因素对木质素回收量的影响，得出了最佳反应条件分别为pH=2、反应温度为60℃、反应时间为60min，加酸速度以控制不产生大量泡沫为准，在该条件下，木质素的回收效果最佳，回收量达到了190.03g／L。还研究了水蒸气活化法制备中孔活性炭的工艺条件，讨论了炭化温度、炭化时间、炭化升温速度、活化温度、活化时间、催化剂用量等因素对维生素B_(12)吸附性能的影响，重点对炭化与活化条件进行考察，得到了最佳实验条件分别为：炭化时间为30min、炭化温度为550℃、活化温度为850℃，活化时间为3h。
水蒸汽活化开始以生成微孔为主，随着活化的深入，逐步向中孔、大孔发展，使平均孔径增大。
The mesoporous activated carbon was prepared from black liquor by water vapor.
In this experiment, the lignin was separated from black liquor of paper-aking by adding HC1, The recovered lignin was carbonized at the operational temperature, then some amount of ferrocene as catalysts was loaded into the carbonization material after it was comminuted to definite granularity. The mesoporous activated carbon was obtained after it is activated for some time in the steam atmosphere at the operational temperature. The mesopore ratio was more than 55% in the production. It is showed that the mesoporous activated carbon was suitable as a good adsorbent for VB12 because it has more mesopore.
Firstly, the process of recovering lignin from the alkaline paper-making black liquor by acidulation precipitation was studied. The effect of pH, reactivity temperature and reactivity time was discussed in detail ,while the optimum condition was obtained : pH=2, reactivity temperature=60 Cand reactivity time=60min. The acid flow rate was controlled not to form a lot of froth. Under the above condition, the lignin recovery impact was the best .The recovery amount was 190. 03g/L .The effect of carbonization temperature , carbonization time , carbonization calefactive velocity , activation temperature , activation time , the amount of catalysts on the ability of adsorption to VB12 was studied .The optimum condition was achieved by putting emphasis on studying the condition of carbonization and activation : carbonization time=30min, carbonization temperature =550 C , activation temperature =850 C , activation time=3h.
The activation with steam mainly generated microspore firstly, while the average pore size was increased due to the excess burn-off which made the microspore transfer into mesopore or macropore .
引文
[1] 武书斌 造纸工业水污染控制与治理技术[M] 12—14 化学工业出版社 2001年
[2] 周书山 草浆造纸黑液综合利用工艺研究[J] 环境科学学报 1993，13(2)：250-254
[3] 王毓秀 韦彦斐 用燃煤烟道气处理造纸黑液的研究[J] 污染防治技术 1995，8(1)：41-44
[4] 白雪梅 王毓秀 烟道气处理草浆造纸黑液过程中CO2的行为研究 污染防治技术 1996 9(3)：141-144
[5] 宋云 二氧化硫处理草浆造纸黑液的新技术[J] 青海科技 1995年8月(3)：16-20
[6] 黄道战 从蔗渣碱法制纸浆黑液中提取木质素[J] 广西民族学院学报(自然科学版) 1998，4(2)：32-35
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[8] 秦毅红 王云燕 造纸黑液酸析法回收木质素[J] 环境污染与防治 1999年8月：5-7
[9] 杨卫民 石颐 酸析木素法处理造纸黑液的改进与应用[J] 环境工程 1997 15(2)：3-6
[10] 张小勇 张建安 碱法造纸黑液木质素生物酸析法 应用与环境生物学报[J] 1999，5(6)：618-622
[11] 贾增发 絮凝沉淀处理造纸黑液[J] 环境保护 1991：13-14
[12] 张琰 小型造纸厂处理研究[J] 环境污染和防治 1995
[13] 孔涛 何新胜 利用LB-1絮凝剂治理碱法造纸黑液并回收碱和木素[J] 环境保护 1998：37
[14] 李仲民 童张法 超滤法回收造纸黑液中木质素的研究[J] 化学工程 2003年第31卷第1期：49-52
[15] 白成志 造纸黑液中木质素的工业应用[J] 矿业科学技术 2000(3)：45-48
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[19] 胡淑宜 黄碧忠 硫酸盐草浆黑液制粉状活性炭的研究[J] 福建林业科技第20卷 30：33
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[23] 颜尚华 陈敏 竹浆黑液中木质素制取活性炭的研究[J] 广东造纸 1997年4月：20-23
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[25] Jun' ichi Hayashi Preparation of activated carbon from ligin by chemical activation[J] Carbon 38(2000):1873-1878
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[27] N.R. Khalilid J.D. Vyas Synthesis and characterization of activated carbon and bioactive adsorbent produced from paper mill sludge[J] Separation and Purification Technology 26(2002) :295-304
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[33] 陈长春 刘健 电渗析法处理造纸黑液回收碱的试验研究[J] 环境污染与防治 1997年4月：7—10
[34] Davy M.F. Uloth V.C Economic evalution of black liquor treatment processes for incremental kraft pulp production[J] .Pulp and Paper Canada 1998,99(2) 35-39
[35] Paleogou M., Cloutier J.N Membrane technologies for pulp and paper application [J].Pulp and Paper Canada 1994,95(10) :36-40
[36] Cloutier J.-N Azarniouch Eletrolysis of weak black liquor Part Ⅱ: Effect of process parameters on the energy efficiency of the electrolytic cell[J] Journal of Applied Electrochmisty 1995,25(5) :472-478
[37] Blanco M.A Negro C. Eletrochemical treatment of black liquor from straw pulping [J]Separation Science and Technology 1996,31(19) :2705-2712
[38] Andy Harrison Frovifors mill installs new recovery technology to be
de-bottle[J] Pulp and Paper 1993,67(13) :30-32
[39] Lars Stigsson Chemrec black liquor gasification[C]. International Chemical Recovery Conference 1998,2(1-4) :663-674
[40] Durai-Swamy K Warren D.W Pulse-assisted gasification of black liquor and organic waste medium-BTU gas Symposium-Energy from biomass and Wastes[J], 1990 publicized by Institute of Gas Technology :689-713
[41] 刘咏 龙炳清 碱法草浆造纸黑液资源化治理技术进展[J] 四川环境 2002，22(1)：42-44
[42] Sing K S W, Everett D H, Haul R A W, et at. Pure Appl Chem[J] 1985,57:603-619
[43] H. Tamon Improvement of mesoporsity of activated carbons from PET by novel pretreatment for steam activation[J]]Carbon 1999, (37):1643-1645
[44] Gadkaree, Fishor Method of making mesoporous carbon[P]W09939818,12 Avug ,1999:31pp.
[45] Hisashi Taimai Synthesis of Extremely Large Mesoporous Activated Carbon and its Unique Adsorption for Giant Molecules :1045—1065
[46] Zhichang Liu Licheng Ling Preparation of pitch-based spherical activated carbon with developed mesopore by the aid of ferrocene[J] Carbon 99:663-667
[47] D. Tateishi, K. Esumi and H. Honda Preparation of Organo-carbonaceous gel Carbon [J]1992:944
[48] Zhichang Liu, Licheng Ling Effects of various metals and their loading methods on the mesopore formation in pitch-based spherical activated carbon, Carbon [J]1999:1333-1335
[49] R. Leboda, J. Skubiszewska-Z Effect of calcium catalyst loading procedure onthe porous structure of active carbon from plum stones modified in the steam gasification process Carbon [J]1999:417-425
[50] Yih-Feng Chiu Coke reactivity of Fe2O3 and K2CO3 addition to the coal change before carbonization [J] Fuel 1985:1007-1010
[51] Kazutoshi Higashiyama. Action of nickel catalyst during steam gasification of bituminous and brown coals[J] Fuel 1985:1157-1162
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[2] 周书山 草浆造纸黑液综合利用工艺研究[J] 环境科学学报 1993，13(2)：250-254
[3] 王毓秀 韦彦斐 用燃煤烟道气处理造纸黑液的研究[J] 污染防治技术 1995，8(1)：41-44
[4] 白雪梅 王毓秀 烟道气处理草浆造纸黑液过程中CO2的行为研究 污染防治技术 1996 9(3)：141-144
[5] 宋云 二氧化硫处理草浆造纸黑液的新技术[J] 青海科技 1995年8月(3)：16-20
[6] 黄道战 从蔗渣碱法制纸浆黑液中提取木质素[J] 广西民族学院学报(自然科学版) 1998，4(2)：32-35
[7] 戴友芝 碱法草浆黑液酸析回收木质素[J] 环境科学与技术 1995(1)：5-7
[8] 秦毅红 王云燕 造纸黑液酸析法回收木质素[J] 环境污染与防治 1999年8月：5-7
[9] 杨卫民 石颐 酸析木素法处理造纸黑液的改进与应用[J] 环境工程 1997 15(2)：3-6
[10] 张小勇 张建安 碱法造纸黑液木质素生物酸析法 应用与环境生物学报[J] 1999，5(6)：618-622
[11] 贾增发 絮凝沉淀处理造纸黑液[J] 环境保护 1991：13-14
[12] 张琰 小型造纸厂处理研究[J] 环境污染和防治 1995
[13] 孔涛 何新胜 利用LB-1絮凝剂治理碱法造纸黑液并回收碱和木素[J] 环境保护 1998：37
[14] 李仲民 童张法 超滤法回收造纸黑液中木质素的研究[J] 化学工程 2003年第31卷第1期：49-52
[15] 白成志 造纸黑液中木质素的工业应用[J] 矿业科学技术 2000(3)：45-48
[16] 张宏伟 造纸黑液制备水煤浆添加剂的研究[J] 淮南工业学院学报 2002，22(2)：49-53
[17] 白成志 利用造纸黑液制备水煤浆添加剂[J] 化工环保 2002，22(1)：42-44
[18] 张晓杰 蒋佩雯 由制浆黑液提取木质素制备活性炭的可行性研究[J] 中国给水排水 1995年11月：15-20
[19] 胡淑宜 黄碧忠 硫酸盐草浆黑液制粉状活性炭的研究[J] 福建林业科技第20卷 30：33
[20] 徐志宏 漆辉 由纸浆黑液提取木质素制备活性炭[J] 四川农业大学学报 1999年9月：309—312
[21] 田永淑 草浆木质素制活性炭[J] 中国资源综合利用 2000年10月：8—9
[22] 汪永辉 蒋志贤 超滤法从造纸黑液中提取木质素制造活性炭[J] 上海环境科学 1994年2月：10—13
[23] 颜尚华 陈敏 竹浆黑液中木质素制取活性炭的研究[J] 广东造纸 1997年4月：20-23
[24] 杨润昌 周书天 由制浆造纸黑液提取木质素制取活性炭的研究[J] 轻工环保 1989年11月：9—13
[25] Jun' ichi Hayashi Preparation of activated carbon from ligin by chemical activation[J] Carbon 38(2000):1873-1878
[26] Jun' ichi Hayashi Katsuhiko Muroyama Vincent G..Gomes A. Paul Watkinson Fractal dimensions of activated carbon from ligin by chemical activation[J] Carbon40(2002):617-636
[27] N.R. Khalilid J.D. Vyas Synthesis and characterization of activated carbon and bioactive adsorbent produced from paper mill sludge[J] Separation and Purification Technology 26(2002) :295-304
[28] N.R. Khalilid Marta Campbell Production of micro- and mesoporous activated carbon from paper mill sludge I Effect of zinc chloride activation[J] Carbon 38(2000) :1905-1915
[29] 穆环珍 杨文波 造纸黑液木质素利用研究进展[J] 环境污染治理技术与设备 2001年6月：26—30
[30] 高新 造纸黑液中木质素的综合利用[J] 陕西化工 1998年12月：1—3
[31] 刘来红 刘健 造纸黑液的直接碱回收技术[J] 轻工环保 1997年19(2)：36-37
[32] 张建安 张小勇 碳铵法回收草浆黑液中的碱[J] 化工冶金 1999年10月：433-435
[33] 陈长春 刘健 电渗析法处理造纸黑液回收碱的试验研究[J] 环境污染与防治 1997年4月：7—10
[34] Davy M.F. Uloth V.C Economic evalution of black liquor treatment processes for incremental kraft pulp production[J] .Pulp and Paper Canada 1998,99(2) 35-39
[35] Paleogou M., Cloutier J.N Membrane technologies for pulp and paper application [J].Pulp and Paper Canada 1994,95(10) :36-40
[36] Cloutier J.-N Azarniouch Eletrolysis of weak black liquor Part Ⅱ: Effect of process parameters on the energy efficiency of the electrolytic cell[J] Journal of Applied Electrochmisty 1995,25(5) :472-478
[37] Blanco M.A Negro C. Eletrochemical treatment of black liquor from straw pulping [J]Separation Science and Technology 1996,31(19) :2705-2712
[38] Andy Harrison Frovifors mill installs new recovery technology to be
de-bottle[J] Pulp and Paper 1993,67(13) :30-32
[39] Lars Stigsson Chemrec black liquor gasification[C]. International Chemical Recovery Conference 1998,2(1-4) :663-674
[40] Durai-Swamy K Warren D.W Pulse-assisted gasification of black liquor and organic waste medium-BTU gas Symposium-Energy from biomass and Wastes[J], 1990 publicized by Institute of Gas Technology :689-713
[41] 刘咏 龙炳清 碱法草浆造纸黑液资源化治理技术进展[J] 四川环境 2002，22(1)：42-44
[42] Sing K S W, Everett D H, Haul R A W, et at. Pure Appl Chem[J] 1985,57:603-619
[43] H. Tamon Improvement of mesoporsity of activated carbons from PET by novel pretreatment for steam activation[J]]Carbon 1999, (37):1643-1645
[44] Gadkaree, Fishor Method of making mesoporous carbon[P]W09939818,12 Avug ,1999:31pp.
[45] Hisashi Taimai Synthesis of Extremely Large Mesoporous Activated Carbon and its Unique Adsorption for Giant Molecules :1045—1065
[46] Zhichang Liu Licheng Ling Preparation of pitch-based spherical activated carbon with developed mesopore by the aid of ferrocene[J] Carbon 99:663-667
[47] D. Tateishi, K. Esumi and H. Honda Preparation of Organo-carbonaceous gel Carbon [J]1992:944
[48] Zhichang Liu, Licheng Ling Effects of various metals and their loading methods on the mesopore formation in pitch-based spherical activated carbon, Carbon [J]1999:1333-1335
[49] R. Leboda, J. Skubiszewska-Z Effect of calcium catalyst loading procedure onthe porous structure of active carbon from plum stones modified in the steam gasification process Carbon [J]1999:417-425
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