草浆原料的湿法除氯和钾元素试验研究
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摘要
为了解决草浆黑液在流化床中燃烧时易烧结的问题,采用湿法预处理的方式来减少黑液中氯和钾元素的含量。分别选择25~100℃的去离子水以及25℃的0.25mol/L的氢氧化钠和柠檬酸溶液来对稻秆和麦秆进行浸泡试验,使用液-质联用色谱仪(LC-MS)以及原子发射光谱仪(ICP-OES)对浸泡液中氯和钾离子的浓度进行测量,并通过扫描电镜得到在不同条件下浸泡后的稻秆和麦秆的表面微观结构,得出了浸泡时间、浸泡温度以及酸和碱对生物质中氯和钾元素浸出的影响。结果表明:浸泡温度的增加能够破坏生物质细胞壁,从而促进稻秆和麦秆中氯和钾元素的浸出。0.25 mol/L的氢氧化钠溶液几乎不会影响稻秆和麦秆中氯和钾元素的浸出。0.25 mol/L的柠檬酸溶液会抑制麦秆中氯离子的浸出,对稻秆中氯离子的浸出则几乎没有影响。此外,0.25 mol/L的柠檬酸溶液还能有效地提高稻秆和麦秆中钾元素的浸出率。水浸法除氯和钾元素的效果很好,在100℃下浸泡3 h后,氯和钾元素的浸出率分别超过95.18%和85.12%。
To solve the problem that it is easy for the straw black liquor to agglomerate when burning in a circulating fluidized bed,the wet-method pretreatment procedure was used to reduce the chlorine and potassium content in the black liquor. The deionized water in a range of temperature from 25 ℃ to 100 ℃ and sodium hydroxide and citric acid solution at a temperature of 25 ℃ at a concentration of 0. 25 mol / L were chosen respectively to conduct a marination test of rice and wheat straw. In this connection,a liquid chromatograph mass spectrometer( LC-MS) and an inductively coupled plasma optical emission spectrometer( ICP-OES) were employed to measure the chlorine and potassium ion concentration in the marination solution and a scanning electronic microscope was applied to observe the microscopic structure of the rice and wheat straw on the surface having been marinated under various conditions. The influence of the marination time,temperature and acids and alkalis on the lixiviation rate of chlorine and potassium element in the biomass observed. It has been found that to raise the marination temperature can destroy the cell wall of the biomass,thus promoting the lixiviation of chlorine and potassium in the rice and wheat straw. The sodium hydroxide solution at a concentration of 0. 25 mol / L will have almost no influence on the lixiviation of chlorine and potassium in the rice and wheat straw. The citric acid solution at a concentration of 0. 25 mol / L will restrain the lixiviation of chlorine in the wheat straw,however,will have almost no influence on the lixiviation of chlorine in the rice straw. In addition,the citric acid solution at a concentration of 0. 25 mol / L will effectively enhance the lixiviation rate of potassium element in the rice and wheat straw. The water lixiviation method will have a very good result to remove chlorine and potassium element. After three hour lixiviation at 100 ℃,the lixiviation rate of chlorine and potassium element will exceed 95. 18% and 85. 12% respectively.
To solve the problem that it is easy for the straw black liquor to agglomerate when burning in a circulating fluidized bed,the wet-method pretreatment procedure was used to reduce the chlorine and potassium content in the black liquor. The deionized water in a range of temperature from 25 ℃ to 100 ℃ and sodium hydroxide and citric acid solution at a temperature of 25 ℃ at a concentration of 0. 25 mol / L were chosen respectively to conduct a marination test of rice and wheat straw. In this connection,a liquid chromatograph mass spectrometer( LC-MS) and an inductively coupled plasma optical emission spectrometer( ICP-OES) were employed to measure the chlorine and potassium ion concentration in the marination solution and a scanning electronic microscope was applied to observe the microscopic structure of the rice and wheat straw on the surface having been marinated under various conditions. The influence of the marination time,temperature and acids and alkalis on the lixiviation rate of chlorine and potassium element in the biomass observed. It has been found that to raise the marination temperature can destroy the cell wall of the biomass,thus promoting the lixiviation of chlorine and potassium in the rice and wheat straw. The sodium hydroxide solution at a concentration of 0. 25 mol / L will have almost no influence on the lixiviation of chlorine and potassium in the rice and wheat straw. The citric acid solution at a concentration of 0. 25 mol / L will restrain the lixiviation of chlorine in the wheat straw,however,will have almost no influence on the lixiviation of chlorine in the rice straw. In addition,the citric acid solution at a concentration of 0. 25 mol / L will effectively enhance the lixiviation rate of potassium element in the rice and wheat straw. The water lixiviation method will have a very good result to remove chlorine and potassium element. After three hour lixiviation at 100 ℃,the lixiviation rate of chlorine and potassium element will exceed 95. 18% and 85. 12% respectively.
引文
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[3]Gea G,Murillo MB,Arauzo J.Thermal degradation of alkaline black liquor from straw.thermogravimetric study[J].Industrial&Engineering Chemistry Research,2002,41(19):4714-4721.
[4]Roy,S.;Vashishtha,M.;Saroha,A.K.Catalytic wet air oxidationof oxalic acid using platinum catalysts in bubble column reactor:a review[J].Journal of Engineering Science and Technology Review,2010,3(1):95-107.
[5]刘长春.光催化氧化技术在造纸废水处理中的应用[J].安徽化工.2010,36(2):53-55.LIU Chang-chun.Applications of the photocatalytic oxidation technology in paper-making waste water treatment processes[J].Anhui Chemical Industry,2010,36(2):53-55.
[6]赵丽红,孙洪军.生物技术在造纸工业废水中的应用[J].辽宁工学院学报,2006,26(3):186~190.ZHAO Li-hong,SUN Hong-jun.Applications of the biological technologies in waste water from papermaking industry[J].Journal of Liaoning Institute of Technology,2006,26(3):186-190.
[7]兰泽全,曹欣玉,刘建忠,等.造纸黑液对水煤浆燃烧性能的影响及分析[J].中国造纸学报,2008,23(3):42-46.LAN Ze-quan,CAO Xin-yu,LIU Jian-zhong,et al.Effect of the black liquor in the paper making process on the combustion performance of water coal slurry and its analysis[J].Transactions of China Paper Making,2008,23(3):42-46.
[8]杨骥,刘开成,郭锐,等.黑液电渗析回收碱的研究[J].环境化学,2006,25(5):629-632.YANG Ji,LIU Kai-cheng,GUO Rui,et al.Study of the recovery of alkalies from black liquids by using the electro-dialysis method[J].Environmental Chemistry,2006,25(5):629-632.
[9]万金泉.当代制浆造纸废水深度处理技术与实践[J].中华纸业,2011,32(2):18-23.WAN Jin-quan.Contemporary pulp and paper making waste water in-depth treatment technology and practice[J].China Papermaking Industry,2011,32(2):18-23.
[10]胡杰,汪萍.麦草浆黑液碱回收现状及有关问题的探讨[J].中国造纸,1997,16:51-55.HU Jie,WANG Ping.Status quo of the alkali recovery from back liquids in wheat straw pulp and exploratory study of relevant problems[J].China Paper Making,1997,16:51-55.
[11]张志刚,张涛.麦草碱法制浆黑液提取的现状与思考[J].中国造纸,2000,16:65-68.ZHANG Zhi-gang,ZHANG Tao.Current status and thought of black liquids for making pulp extracted by using the wheat straw alkali method[J].China Paper Making,2000,19:65-68.
[12]别如山,赵莹,刘欢鹏,等.造纸黑液流化床碱回收装置及方法[P].中国:101210396,2008-07-02.BIE Ru-shan,ZHAO Ying,LIU Huan-peng,et al.Paper making black liquid fluidized bed alkali recovery device and method[P].China:101210396,2008-07-02.
[13]Li J J,Yang H R,Wu Y X,Lv J F,et al.Effects of the updated national emission regulation in China on circulating fluidized bed boilers and the solutions to meet them[J].Environ Sci Technol2013,47(12):6681-6687.
[14]Hupa M,Backman R,Skrifvar BJ.The Influence of chlorides on the fireside behavior in the recovery boiler[J].TAPPI J 1990,73(6):153-158.
[15]Bie R S,Zhao Y,Chen Z G,et al.Formation mechanism of agglomeration caused by burning NSSC black liquor in a fluidized bed incinerator[J].Energy Fuels,2009,23(2):683-689.
[16]吕宏俊,李晓东.化工有机废液流化床焚烧处理的结焦结渣问题研究[J].锅炉技术,2005,35(5):75-78.LU Hong-jun,LI Xiao-dong.Study of the problems relating to the coking and slagging in incineration processes in an organic waste liquid fluidized bed in chemical industry[J].Boiler Technology,2005,35(5):75-78.
[17]Liu H P,Zhang L Y,Han Z J,et al.The effects of leaching methods on the combustion characteristics of rice straw[J].Biomass and Bioenergy,2013(49):22-27.
[18]Keown D M,Favas G,Hayashi J,et al.Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass:differences between sugar cane bagasse and cane trash[J].Bioresour Technol,2005,96(14),1570-1577.
[19]P.Marschner,Marschner's mineral nutrition of higher plants[M].San Diego Third Edition.Academic Press,2012.