造纸污泥中木质素的提取及其改性研究.pdf

造纸污泥中木质素的提取及其改性研究 ＊ 李淑勉 蒋 玲 李占才 王晓杰 张华林 郑州轻工业学院材料与化工学院, 河南 450002 摘要 针对木质素的特性, 从造纸污泥中用酸析法提取, 提取产物进行磺化改性, 探讨了反应温度、时间、pH 值等因素 对磺化产物的影响。 研究表明, 磺化反应的适宜条件为 木质素∶ 亚硫酸钠4∶ 3、pH10. 5, 80～ 90 ℃下加热4 h, FeCl3 可作为木质素磺化反应的催化剂。 改性产品经测定, 表面活性有明显提高, 各项指标基本符合国家标准。 关键词 造纸污泥 木质素 磺化 减水率 ＊河南省科技厅资助项目 项目编号 0424440042 0 前言 造纸工业的迅速发展造成了严重的环境污染 ,其 主要表现为黑液的大量排放和污泥的大量堆放。国 内外对造纸黑液的污染治理技术研究得较多 [ 1] ,主要 概括为碱回收技术 ,物化加生化技术和资源化技术, 其资源化技术是将黑液中的有用物质作原料 ,生产可 利用的产品, 既消除了污染又能获得很好的经济效 益,若处理得当 ,甚至能实现黑液的零排放。 而造纸中产生的大量污泥 [ 2] , 由于含水率高 60以上 , 呈淤泥状态 , 成分复杂 , 处理利用难度 大。目前我国对制浆造纸污泥大部分只采取简单的 堆放 、 填埋或焚烧。填埋法虽简便易行 ,投资少,但该 法不仅占用大量土地资源, 而且若填埋后处理不当, 其渗液将会对地下水造成严重的污染; 目前发达国家 多采用脱水后先焚烧 ,烧余再填埋的方法处理造纸污 泥。污泥经焚烧后体积大大减少, 因而能节约大量填 埋场地 ; 烧余中有害成分的含量极低, 且可利用产生 的热量使资源得到充分利用, 但焚烧法设备投资大, 适用于大型造纸厂 ,我国中小型造纸厂较多 ,该法不 适合我国国情。由于造纸污泥酸碱度较大,所以也不 适用于农业利用 。因为环境压力或费用太高 ,前几种 方式的应用受到一定限制 。如何根据污泥的特征有 效地利用污泥中的有效成分生产高附加值产品,经济 而有效地治理污泥的二次污染问题具有非常重要的 意义 。造纸污泥含大量的木质素、糖类和盐 [ 3] , 而木 质素具有良好的表面活性、分散性和粘合性 ,其基本 结构单元为苯丙烷基 ,碱法制浆过程中易发生反应, 若对其进行改性 ,产品将有很广阔的用途。 以河南某造纸厂的造纸污泥为主要研究对象 ,对 造纸污泥的资源化进行探讨。利用木质素在酸性条 件下易析出的特性, 用酸析法从造纸污泥中进行提 取; 由于木质素易与亚硫酸 、 亚硫酸盐等磺化剂起反 应,又对提取后的木质素进行磺化改性研究 ; 磺化产 品用作水泥减水剂 ,并对其减水性进行性能测试, 各 项指标基本符合国家标准 。 1 试验部分 1. 1 木质素提取 试验所用污泥采自河南省某造纸厂造纸污泥 。 称取20 g污泥于烧杯中, 先加热水将可溶物初步 溶解 ,再加一定量10NaOH 溶液使污泥中的木质素 溶解, 过滤 ,将滤液分别用适量浓硫酸和 10H2SO4 调节 pH 值使沉淀完全, 再于 80 ～ 90 ℃下加热保温 50 min, 溶液变为黄褐色, 抽滤, 并用水洗涤沉淀至中 性,将沉淀烘干 ,称重 ,得粗品木质素 。 1. 2 木质素磺化 称取提取后的木质素10 g于适量水中, 加入7 mL 10NaOH 使之溶解 , 再加入 Na2SO3和0. 1 g FeCl3, 用10NaOH 或 10H2SO4调节 pH 值至 10. 5, 控制 反应液体积 5 时,木质素提取量很少; pH 4. 5～ 3 时, 随 pH 变小, 提取量增加 ; pH 7. 5 g时 ,产品质量增加缓慢。这是 因为木质素磺化可能是 FeCl3引发的自由基反应 [ 4] , 随Na2SO3用量增多,亚硫酸根自由基增多 ,磺化的速 度比较快 ,因此产品质量增加较快 ; 随着反应的进行, 当Na2SO3用量过高时 ,体系中木质素的磺化基本完 成,进入链终止阶段, 产品质量增加较缓慢 。故本实 验Na2SO3用量为 7. 5 g 。 2. 2. 2 反应温度的影响 结果表明 60～ 80 ℃产品质量随体系温度升高 而增加较快, 高于85 ℃后增加缓慢 。故反应温度控 制在 80～ 90 ℃。 2. 2. 3 反应时间的影响 结果表明,反应开始阶段, 磺化产品质量随反应 时间明显增加, 当反应时间达到4 h后 ,磺化产品质量 增幅减小。故反应时间为4 h。 2. 2. 4 pH 值的影响 结果表明, 当 pH 值较小时 , 对磺化产品质量影 响不大; 当 pH8～ 10. 5 时 ,随 pH 值增加 ,产品质量 逐渐升高; 但 pH 10. 5,产品质量又下降。故将反应 液酸度控制在 pH 10. 5。 2. 2. 5 磺化反应优选条件 由上述各因素的影响可知 ,磺化时间和反应温度 是影响木质素磺化产品质量的主要因素 。反应适宜 条件为 木质素与亚硫酸钠用量比为 4∶ 3 w w , pH 10. 5,于 80～ 90 ℃下反应4 h。 在反应体系中加入适量 的FeCl3作催化剂, 能有效地提高木质素磺化反应的 效果 。 2. 2. 6 磺化产品的表征 木质素磺酸盐结构特别复杂 , 又是高分子化合 物,其分析鉴定手段可用的不多, 红外光谱是常用的 研究手段 。其 IR 图谱表征为 1 610 ～ 1 600 cm -1 , 1 520 ～ 1 500 cm - 1 为 芳 香 环 骨 架 振 动, 1 470 ～ 1 460 cm -1为 CH 3-、-CH2-、C -H 的弯曲振动, 1 140 cm -1为磺酸基 、1 043 cm- 1 为磺酸基和烷基醚 键振动的混合峰 。 3 正交试验 由单因素试验可知 ,Na2SO3的用量 、磺化时间和 反应温度是影响木质素磺化反应的主要因素。为揭 示3 种因素对磺化产品质量和性能的影响程度 ,设计 了 L9 3 4 正交实验,其因素和水平如表1 所示。试验 结果由产品质量和减水率来检测, 并按照 GB8076- 87 标准对水泥净浆减水率进行测试试验。 表 1 正交试验的因素水平表 水平 因素A 反应温度 ℃B 反应时间 hC 磺化剂用量 g 1 水平7035. 0 2 水平8047. 5 3 水平90510. 0 试验结果为 C ※B ※ A ,即磺化剂的用量是影响 水泥减水率的主要因素, 反应时间是次要因素, 反应 温度对减水率的影响最小。由此确定磺化反应的较 优工艺为 控制磺化剂用量为7. 5 g , 于80 ℃ 反应4 h, 此条件下所得磺化产品的减水性能最好 。 下转第 55 页 63 环 境 工 程 2006年 4 月第24 卷第2 期 慢,系统散热超过生物反应放热, 温度开始下降到 45～ 50 ℃ 之间, 这时风机启动时间50 min d 。 图9 OTM 在线检测数据 由于系统一方面保证了供氧, 另一方面又避免了 过量的通风,所以全过程无需再加水。物料的原始含 水率为65,30 d后为 50。 4. 3 比较 通过前面的举例与分析, 归纳和比较见表 2。 表 2 OTM 控制在堆肥应用中的初步比较 项目传统堆肥OTM 控制 气味排放 350～ 11 000 OU m3经生物过滤器 处理后 350 ～ 750 OU m3 Jager et al. , 1996 140～ 300 OU m3 通风耗能20～ 35 kWh t 或更高 Kern,20054～ 5 kWh t 停留时间 腐 熟度德国标准 Ⅴ级 12 周 通风, 每周翻堆 1 ～ 2 次 20 周或更长 只翻堆 Bilitewski et al. 1993 8 周 翻堆耗能OTM 控制仅需翻堆1 次 参考文献 [ 1] 我国城市生活垃圾处理行业 2004 年发展报告. 中国环境产业 发展报告. 中国城市环境保护产业协会,2005, 5. [ 2] 李玉春, 李彦富, 李国学. 北京市生活垃圾堆肥化现状及存在问 题分析, 2004. 10. [ 3] 苏凡. 垃圾好氧生化处理. 中国环保产业, 1999. [ 4] 李国学, 张福锁. 固体废物堆肥化与有机复混肥生产. 北京 化 学工业出版社, 2000. [ 5] Jager, J. Muellhandbuch,1991. [ 6] 万若 北京 环境工程技术有限公司. 垃圾生化好氧处理装置及 其控制方法, 专利申请号 20051020032794 . [ 7] Kern, M . Die Behandlung und Beseitigung fester Abfaelle durch biologische Verfahren inMuellhandbuch, Band 5, Erich Schmidt Verlag, Berlin, 2004. [ 8] Jager, J. ; Kuchta , K. ; Reinhardt, T . , Technische Moeglichkeit und Konzepte zur weitergehenden Abluftreinigung fuer MBA, in VDI - Seminar“ Planungvonbiologisch -mechanischenRestabfall - behandlungsanlagen, Betriebserfahrungen, Risiken” , Duesseldorf , Juni 1996. [ 9] Biletewski,B. , Haedtle, G. , Marek, K. , Abfallwirtschaft, Springer Verlag, 1993. 作者通讯处 张健 100037 万若 北京 环境工程技术有限公司 电话 010 68513149 E -mail j. zhang envi8. com 2005- 09-02 收稿 上接第 63页 4 磺化产品性能测试 磺化产品经河南省建材研究院对其性能进行测 试,结果见表 2。 表 2 木质素磺酸钠减水率测试 检验项目 国标要求 合格品一等品 检验结果 减水率≥5≥816. 7 3 d≥ 110≥115142 抗压强度比7 d≥ 110≥115109 28 d≥ 115≥110101 对钢筋的锈蚀作用对钢筋无锈蚀作用对钢筋无锈蚀作用 由表 2 可知, 参照国家标准, 减水性能基本达到 国家标准 ,抗压强度有待进一步提高。 参考文献 [ 1] 潘婵, 方继敏, 杨红刚. 草浆造纸黑液用于粘结剂生产的研究. 安全与环境工程, 2004, 11 2 24 -26. [ 2] 周肇秋, 赵增立, 杨雪莲. 造纸废渣污泥基础特性研究. 造纸科 学与技术, 2001, 20 6 14-17. [ 3] 蒋挺大. 木质素. 北京 化学工业出版社,2001, 3. [ 4] 穆环珍, 黄衍初, 杨问波. 碱法蔗渣制浆黑液木质素磺化反应研 究. 环境科学, 2003, 22 4 377 -379. 作者通讯处 李淑勉 450002 郑州市东风路 5 号 郑州轻工业学院 材料与化工学院 E -mail lsm22eyou. com 2005- 09-12 收稿 55 环 境 工 程 2006年 4 月第24 卷第2 期 AN EXPERIMENTAL STUDY ON SPRAY PERANCES OF TWIN FLUID NOZZLE FOR FLUE -GAS DECONTAMINATIONZhang Li Li Wushen Pu Ge 40 Abstract Experiment has been done on a twin fluid nozzle in spray drying chamber of flue -gas decontamination. Factors affecting spray angle anddistribution of liquid -drop diameter etc have been analyzed. It is found that air liquid ratio and slurry concentration are crucial to spraying character. A suitable liquid -drop diameter and spraying angle can be obtained by changing parameter of running. The nozzle can be used for decontaminating acid gas of drying flue gas to obtain better decontaminating efficiency. Keywords spray drying, twin fluid nozzle, spray angle and spray particle size TECHNICAL RE OF DEDUSTING SYSTEM OF DRY COAL SEPARATION Li Duosong Sun Jianming 44 Abstract Through on -the -spot test, analysis of the existing questions, theoretical calculation, etc, the control project s optimization of coal dust is realized, connected with dust removal system s reation of Baijiazhuang dry coal separation. On this basis, it is also put forward the control technique of special dust source that has multiple -point, large quantity , extensive area and so on according to the project s actualization, debugging and the running situation. Keywords dry coal separation and dust removal technolgy CLEANING OF FLUE GAS IN PRODUCTION OF AUTO -LINER MADE OF REGENERATIVE FIBER USING PLASMASun Chunbao Xing Yi Huang Liming 47 Abstract Plasma air cleaning technology was used to control the flue gas by the production of auto -linerwith regenerative fiber asmaterial. Its structure and operation parameters were optimized, and its cleaning principle was also studied. it is shown that plasma air cleaning technology can treat superfine particles and can also refine inhalant particulate andgas pollutant. Structure of the equipment is simple and the operation cost is low. It can be used in any industry field where the same kind of flue gas is produced. Keywords cleaning of flue gas, plasma, auto -liner and regenerative fiber material DISCUSSION ON THE FUNCTION AND PROCESS OPTIMIZATION OF MSW COMPOSTING COMPREHENSIVE CONTROL OF OXYGEN CONTENT, TEMPERATURE AND MOISTURE IN COMPOSTING PROCESSXu Wenlong Zhang Jing Ullus Leidel et al 50 Abstract Taking into account the current situation in China, the function and application of the MSW composting are discussed. In addition to the traditional application of the compost as fertilizer for farming, forest or greening , the composting can be understood as an important pretreatment ofMSW prior to the landfilling or biological drying before the incineration, in order to increase the heating value of the MSW. From the point of decreasing investment and operational costs, the analysis is made that the priority should be given to the main reaction conditions of biological systems and ventilation optimization instead of simply emphasizing on mechanization. The main factors of process such as the oxygen content, temprature and moisture are discussed, and a new engineering technology aswell as the control are introduced accordingly . Keywords municipal solid waste MSW, composting, biological treatment, oxygen content, temperature, moisture and control THE RESEARCH ON TREATING THE WASTE ACID OF CRUDE BENZOL REFINING Li Meixiang Su Guangwu Cheng Xiaodong 56 Abstract Waste acid of crude benzol refining was processedwith roasting . It is studied the technical process of waste acid of crude benzol refining by employing roasting ; the best operating parameters are discussed and the technical process is also optimized. Experimental results have shown that this can treat waste acid effectively, and has the advantages of easy operation, no secondary pollution and good economic benefit. Keywords roasting , crude benzol refining, waste acid and research EXPLORATION AND PRACTICE OF DEVELOPING BUILDING MATERIALS FROM FLUOR - GYPSUM DEBRISLi Ruyi Li Li Cao Zuogang 58 Abstract Fluor -gypsum debris from chemical production is used to make building materials, such as cement retarder, gypsum block and gypsum brick etc, whose technical properties can meet the requirements. It can solve not only environmental pollution, but also realize resource reuse of industrial debris. Keywords fluor -gypsum, environment protection and resource reuse RESEARCH ON EXTRACTION AND MODIFICATION OF LIGNIN INTHE PAPER MILL SLUDGE Li Shumian Jiang Ling Li Zhancai et al 62 Abstract The of extracting lignin from paper mill sludge and its sulfonated condition for modification have been studied. Some influencing factors such as the reaction temperature, reaction time, pH value etc. have been researched in detail. The experiment results indicate 4 ENVIRONMENTAL ENGINEERING Vol. 24, No. 2,Apr. ,2006 the optimal condition of extracting ligninis in pH3～ 4, extracting for 50 min at 80～ 90 ℃; the optimal condition for ligninsulfonated reaction is lignin Na2SO34∶ 3 w w, pH10. 5, reacting for 4 h at 80～ 90 ℃. The detection of the products shows that the surface activity of lignin has been improved obviously. Keywords paper mill sludge, lignin, sulfonation and water -reducing rate DETERMINATION OF COD IN HIGH SALINITY ORGANIC LIQUID WASTES BY HIGH -SPEED CATALYTIC Ma Jingying Ma Zengyi Yan Jianhua et al 64 Abstract Incineration is an ideal for high salinity organic liquid wastes. Determination of COD in these organic waste liquids is dominant for design of burmer and estimation of incineration efficiency. It is presented high-speed catalytic for oganic liquid with high concentration of chloride ion and organic compounds. Relative error is 0. 15～ 5. 8 when the concentration of Cl-is 20 000～ 60 000 mg L. Accuracy of the is good, the relative error of six measured results is less than 2 and the recovery is 98～ 102. There is no “ prominent difference” between standard and high-speed catalytic . Keywords COD, Cl-, high -speed catalytic, organic liquid wastes and incineration TESTING OF TOTAL PHOSPHORUS USING MODIFIED DISSOLVING PROCESS Zhang Fengru 66 Abstract It is studied that determination of total phosphorus in a water sample by hydrogen peroxide -boiling water bath dissolving process. The results show that the new process features simple operation, complete dissolution, which can be well compared with the traditional , whose precision and accuracy are satisfactory. Keywords total phosphorus, hydrogen peroxide -boiling water bath dissolving process, precision and accuracy ASSESSMENT ON TRAFFIC ATMOSPHERE ENVIRONMENTAL QUALITY BY EQUIVALENT NUMERICAL Qin Zhibin Bian Yaozhang Li Yuzhi 68 Abstract The model of equivalent numerical is established for atmosphere quality grade according to state standard for atmosphere quality, its use shows that it is a scientific and a new for uating traffic environmental atmosphere quality . Keywords quality standard, atmosphere quality assessment and equivalent numerical GREY PREDICTION OF AIR QUALITY IN THE YEAR OF 2008 IN BEIJING Liu Xuexin Xue An 69 Abstract A result is obtained that PM10, TSP and SO2are the main factors of the atmospheric pollutant in Beijing by grey relational analysis. Based on the result, a forecasting modelof main pollution factor is established by using grey systems. The forecasting result is thatTSP and PM10will exceed the national standard Ⅱ in the year of 2008 in Beijing. In the next years, the most important tasks of air pollution control in Beijing are to reduce the particulate pollution. Keywords air quality , prediction, grey systems and model ENGINEERING DESIGN OF WASTEWATER TREATMENT IN A SMALL PHARMACEUTICAL FACTORYLiu Wei Chen Minghui Shang Jincheng 72 Abstract The wastewater from a small pharmaceutical factory features large flucluation in its quality and quantity. Using popular technology is hardly fit for the great change. The technology of hydrolytic acidificationbiocontact oxidization has higher resistance to shock load. The results of engineering examples show that the equipment with the procedure can be operated stably for a long time; the effluent can reach standard of discharging. Keywords hydrolytic acidification, bio -contact oxidization, small scale and wastewater of pharmacy THE INFLUENCE OFREACTOR TEMPERATURE ON AUTOTHERMALTHERMOPHILIC AEROBIC DIGESTIONCheng Jiehong Feng Lei Yin Binkui et al 74 Abstract Biosolidswas produced by sewage plant in the course of treatment urban sewage. A pilot scale facility of atuothermal thermophilic aerobic digestion ATADwas designed for stabilization of the biosolid. The affect of reactor temperature on stabilization of the biosolid and main factors affecting reactor temperature increasing were studied by the way of batch operation. The results showed a. the remarkable effects of reactor temperature on the removal of volatile suspended solid VSSwere obtained. And a higher reactor temperature produces a higher removal of VSS. b. Factors of reactor temperature were Influencedby influenttotal suspended solid, digestion time and aeration rate. Biosolidwasstabilizedwhen the highest reactor temperature and the removal of VSS were 49 ℃ and 41. 7 respectively under the conditions of 37. 2 g L of influent VSS and 14 ～ 17 d of digestion time. Keywords biosolids stabilization, ATAD, reactor temperature and removal of VSS 5 ENVIRONMENTAL ENGINEERING Vol. 24, No. 2,Apr. ,2006