【作者】 刘贤淼；

【导师】 江泽慧；

【作者基本信息】 中国林业科学研究院 ， 木材科学与技术， 2008， 博士

【摘要】 造纸术是我国古代四大发明之一,曾为人类文明进步做出了卓著贡献。目前,我国造纸工业的纸及纸板产量、总消费量均居世界第二位。然而,造纸工业的发展带来的造纸污泥的污染也越来越严重。本研究涉及利用造纸厂污泥制造纤维板技术,这种技术解决了造纸行业产生的大量污泥的处理问题,使废料得以再生利用,减少了环境污染,也为生产人造板开辟了广泛的原料来源,具有保护生态环境、节约使用木材的双重意义。通过研究了造纸污泥基础性质、脲醛树脂胶(UF)和酚醛树脂胶(PF)在造纸污泥纤维板上的应用、木纤维和玻璃纤维增强造纸污泥纤维板研究、造纸污泥及纤维板的除臭初步研究,得到以下研究结果:利用光学显微镜、电感耦合等离子直读光谱仪、元素分析仪、同步热分析仪、扫描电镜(SEM)、红外光谱分析、气相色谱-质谱联用(GC-MS)等手段和技术研究了造纸污泥基础性质有:(1)测得湿污泥含水率为72.70%;有机物含量为49.85%;pH值为6.6;干污泥纤维含量为34.09%;大部分(约77%)纤维的长度在0.20 mm以下;测试了污泥灰分中铜离子等重金属离子含量;湿污泥C、H、N、S元素分别为9.93%、1.44%、0.35%、0.39%。(2)研究了湿污泥、热干燥污泥、冷冻干燥污泥的同步热分析,发现造纸污泥的热解可以粗略分为水分析出、有机物析出、矿物质分解和残留灰分4个阶段,但这4个阶段也不是截然分开的。(3)扫描电镜湿观察污泥和干污泥中细菌及其形态,主要杆状菌和球状菌,烘干污泥中存有细菌尸体。红外光谱分析污泥中可能存在的基团,并推测可能存在的物质,主要存在-OH等基团,可能含有高岭土等物质。(4)气相色谱-质谱联用(GC-MS)分析,湿污泥与干污泥乙酸乙脂提取物的化学组成及含量,湿污泥中主要有正十六烷酸和十八烷酸,干污泥中主要有正十六烷酸、2-甲氧基-N-[2-[1-(4-溴苯)-5-四唑基]乙烯基]-苯胺。正交实验法研究脲醛树脂胶(UF)和酚醛树脂胶(PF)在纯污泥纤维板应用:(1)脲醛树脂胶应用于10～20目粉污泥纤维板,MOR、MOE、IB、IBb、TS的平均值分别为:6.53 MPa、1.40 GPa、2.21 MPa、1.10 MPa、5.61%。工艺参数对材料MOR和MOE影响顺序从大到小依次为:密度、施胶量、温度和时间;工艺参数对材料MOR和MOE均有非常显著影响,但时间对MOE仅在а=0.1水平下显著。工艺参数对材料IB影响顺序从大到小依次为:密度、施胶量、温度和时间。各个因素对材料IB影响均非常显著。工艺参数对材料IBb影响顺序从大到小依次为:密度、温度、施胶量和时间。除时间外,工艺参数对材料IBb影响均非常显著。工艺参数对材料TS影响顺序从大到小依次为:密度、温度、施胶量和时间。密度、温度、施胶量对材料TS影响均非常显著;时间材料TS影响显著。各指标的多元线性回归方程决定系数均大于0.80,说明拟合得非常好;显著性水平均为0.01说明因子水平取值合理。(2)脲醛树脂胶应用于不分级粉污泥纤维板,MOR、MOE、IB、IBb、TS的平均值分别为:8.21 MPa、1.57 GPa、2.25 MPa、1.14 MPa、5.54%。工艺参数对材料MOR、MOE和TS影响顺序从大到小依次为:密度、施胶量、温度和时间。工艺参数对材料IB和IBb影响顺序从大到小依次为:密度、温度、施胶量和时间。密度、施胶量和温度对材料各指标影响非常显著,但时间几乎没有影响。MOR、MOE、IBb的多元线性回归方程决定系数均大于0.80,说明拟和得很好;而IB和TS拟和效果不佳,但显著性水平均为0.01。(3)酚醛树脂胶应用于分级粉污泥纤维板,MOR、MOE、IBb、TS的平均值分别为:6.53 MPa、1.40 GPa、1.10 MPa、、5.61%。工艺参数对材料MOR、MOE和IBb影响顺序从大到小依次为:施胶量、粒度、温度和时间。施胶量、粒度对材料MOR影响非常显著,但温度和时间影响很小。施胶量、粒度和温度对材料MOE和IBb影响非常显著,但时间影响很小。对材料TS影响顺序从大到小依次为:施胶量、粒度、时间和温度。施胶量对材料TS影响非常显著,粒度影响显著,但时间和温度影响很小。MOR回归方程拟和得很好;其他的较差,但显著性水平均为0.01。(4)利用同步热分析(TG-DSC)研究发现,脲醛树脂胶与干污泥热反应不明显,酚醛树脂胶与干污泥热反应相对明显。使用木纤维、玻璃纤维布、玻璃纤维丝增强污泥纤维板研究:(1)使用木材纤维增强污泥纤维板研究,发现木材纤维置于污泥纤维板上下表面的效果好于木材纤维混和加入污泥纤维板。工艺参数对材料各项性能影响显著,回归方程拟和良好。木纤维量增加,材料的各项性能增加,在分层条件下木纤维达到50%及以上条件下,各项力学性能才达到国家标准。(2)使用玻璃纤维布增强污泥纤维板研究,发现随着偶联剂的加入各项性能均有所提高,但超过1.0%,增加不明显。偶联剂加入大于1.0%,各项力学性能才达到国家标准。工艺参数对材料各项性能影响显著,回归方程拟和不佳。(3)使用玻璃纤维丝增强污泥纤维板研究,发现随着偶联剂的加入量增加,玻璃纤维长度的增加,材料各项性能均有所提高。纤维长度达到4 cm,偶联剂施胶量达到1.0%及以上时候,材料各项力学性能才达到国家标准。所有工艺参数对材料性能影响均为非常显著,回归方程拟和良好。玻璃纤维增强污泥纤维板复合机理研究,红外光谱分析发现偶联剂改善玻璃纤维表面极性,使得玻璃纤维与酚醛树脂胶接近产生共价连接。扫描电镜观察发现偶联剂能增加玻璃纤维表面粗糙度,由于酚醛树脂对玻璃纤维表面是润湿的,因此进一步改善了玻璃纤维表面的润湿性,有利于胶合。造纸污泥及污泥纤维板脱臭初步研究:(1)使用《空气质量氨的测定次氯酸钠-水杨酸分光光度法》,研究污泥中氨气释放规律,处理剂影响。烘干后污泥比未烘干的释放氨气更多。处理剂效果从大到小依次为: NaClO、KMnO4、H2O2、CuSO4。(2)使用《水质硫化物的测定碘量法》,对本研究硫化氢释放量的测试效果不佳。使用《居住区大气中硫化氢卫生检验标准方法亚甲蓝分光光度法》研究污泥中硫化氢释放规律,处理剂影响。烘干后污泥比未烘干的释放硫化氢更多。处理剂效果从大到小依次为: CuSO4、NaClO、KMnO4、H2O2。(3)利用活性炭吸附法研究污泥纤维板的失重,在18周内是不断失重;失重速度前3周较为明显,后面的减少较为平稳,总的来说一直都在减少,但18周内一直没有到零。从放置的第3周开始,臭味明显减少,但有一种发酸的味道,从第5周开始,酸味也少,污泥纤维板的气味降低,保持到18周。更多还原

【Abstract】 Papermaking skill is one of the four great inventions in ancient China and has made a remarkable contribution. the progress of human civilization. At present, China’s paper and paperboard production, the total consumption ranked second in the world. However, papermaking sludge pollution has become increasingly serious with the development of the paper industry. This study involves the use of paper mill to manufacture sludge fiberboard technology which solve the problem of dealing with a lot of sludge, recycle the waste, reduce the environmental pollution, at the same time opene up a wide range of raw material sources for the production of wood-based panels, protect the ecological environment, use wood. economically. Through study the primary property of the paper sludge, urea-formaldehyde resin (UF) and phenolic resin (PF) applied to the paper sludge fiberboard, wood fibe r-reinforced and glassfiber-reinforced paper sludge fiberboard, the preliminary deodorization study on paper sludge and fiberboard. The main research findings are summarized as follows: Using Optical Microscope, Inductively Coupled Plasma Quantometer, Elemental Analysis, Synchronization Thermal Analyzer, Scanning Electron Microscope(SEM), Fourier Transform Infrared Spectrometer (FT-IR), Gas Chromatography-Mass spectrometry(GC-MS) to study the primary property of the paper sludge:(1) The moisture content of wet sludge is 72.70%; the organic material content is 49.85%;pH Value is 6.6;fiber content of dry sludge is 34.09%; the length of most fiber(about77%)is below 0.20 mm; testing the copper ion content and so on of sludge ash; C、H、N、S element of wet sludge is 9.93%、1.44%、0.35%、0.39%.(2) Study wet sludge, heat dry sludge; freeze dry sludge by Synchronization Thermal Analyzer. Paper sludge that pyrolysis can be roughly divided into four stages,water precipitation, organic matter precipitation, minerals and decomposition of residual ash, but four stages is not completely separate.(3) Study bacterial configuration of wet sludge and dry sludge, mainly including micrococcus and bacillus. Bacterial corpse is found in dry sludge. Analyze the groups which possibly exit in sludge, mainly is -OH and so on, possibly kaolin exit.(4) The compounds and content of Ethyl acetate extract of wet sludge and dry sludge by GC-MS. Mainly n-Hexadecanoic acid and octadecanoic acid in wet sludge; n-Hexadecanoic acid and Benzenamine, 2-methoxy-N-[2-[1-(4-Bromophenyl)-5-tetrazolyl]ethenyl] in dry sludgeThe study of urea-formaldehyde resin (UF) and phenolic resin (PF) applied to the paper sludge fiberboard by orthogonal design:(1) UF applied to the 10～20 mesh powder paper sludge fiberboard, the average of MOR、MOE、IB、IBb、TS is 6.53 MPa、1.40GPa、2.21MPa、1.10 MPa、5.61% respectively. The effect order of parameters on MOR and MOE is Density, Resin content, Temperature, Time. The effect of parameters on MOR and MOE is very significant, except effect of time is significant atа=0.1 level. The effect order of parameters on IB is Density, Resin content, Temperature, Time. The effect of parameters on IB is very significant. The effect order of parameters on IBb is Density, Temperature, Resin content, Time. The effect of parameters on IBb is very significant except time. The effect order of parameters on TS is Density, Temperature, Resin content, Time. The effect of Density, Temperature, Resin content on TS is very significant, except effect of time is significant. The coefficient of determinations of multiple linear regression equations are more than 0.80, mean fitting well and they are significant level at 0.01 level,mean the factors are reasonable value.(2) UF applied to unclassfied powder paper sludge fiberboard, the average of MOR、MOE、IB、IBb、TS is 8.21 MPa、1.57GPa、2.25MPa、1.14MPa、5.54% respectively. The effect order of parameters on MOR, MOE and TS is Density, Resin content, Temperature, Time. The effect order of parameters on IB and IBb is Density, Temperature, Resin content, Time. The effect of Density, Resin content, Temperature on performances is very significant, but few effect of time on performances. The coefficient of determinations of multiple linear regression equations of MOR, MOE, IBb are more than 0.80, mean fitting well, but IB and TS fitting bad. They are significant level at 0.01 level.(3) PF applied to unclassfied powder paper sludge fiberboard, the average of MOR、MOE、IBb、TS is 6.53 MPa、1.40GPa、1.10MPa、、5.61% respectively. The effect order of parameters on MOR, MOE and IBb is Resin content, Granularity, Temperature, Time. The effect of Resin content and Granularity on MOR is very significant, but few effect of Temperature and Time. The effect of Resin content, Granularity and Temperature on MOE and IBb is very significant but few effect of Time. The effect order of parameters on TS is Resin content, Granularity, Time, Temperature. The effect of Resin content on is very significant,the effect of Granularity is significant, but few effect of Time and Temperature. The equations of MOR is fitting well, others fitting bad, but they are significant level at 0.01 level.(4) Study by TG-DSC, we find Thermal reaction between UF and dry sludge is not significant, between PF and dry sludge is not significant comparatively.Wood fiber, fiberglass fabric and fiberglass thread reinforce paper sludge fiberboard:(1) Wood fiber reinforce paper sludge fiberboard. The effect of wood fiber putted on sludge fiberboard surface is better than that of wood fiber mixed to sludge fiberboard. The effect of parameters on performances is significant. The equations is fitting well. The performances increase with the wood fiber increase. The performances meet the national standard when wood fiber occupied 50% at dividing type.(2) Fiberglass fabric reinforce paper sludge fiberboard. The performances increase with the coupling agent increase, but not significant when excess 1.0%. The performances meet the national standard when coupling agent excess 1.0%. The effect of parameters on performances is significant, and the equations is fitting bad.(3) Fiberglass thread reinforce paper sludge fiberboard. The performances increase with the coupling agent and length of fiberglass thread increase. The performances meet the national standard when coupling agent excess 1.0% and the length of fiberglass thread excess 4 cm. The effect of parameters on performances is significant, and the equations is fitting well.(4) Study on composite mechanism for fiberglass reinforce paper sludge fiberboard. The coupling agent can improve fiberglass surface polarity by FT-IR, create covalent bond between fiberglass and PF. The coupling agent can improve coarseness of fiberglass surface, because fiberglass surface can be wetted by PF, and then improve the wettiability of fiberglass surface. It is good for bonding.The preliminary deodorization study on paper Sludge and fiberboard:(1) Study the ammonia release rule and effect of deodorizer by Air quality-Determination of ammonia - Sodium Salicylat-sodium hypochlorite spectrophotometric method. The ammonia of dry sludge release increase than that of wet sludge. The effect of deodorizer order is NaClO, KMnO4, H2O2, CuSO4.(2) It is not suitable for study sulfureted hydrogen release by Water quality -Determination of sulfides-Iodometric method. Study the sulfureted hydrogen release rule and effect of deodorizer by hydrogen sulfide in air of residential areas-Methylene blue spectrophotometric method. The sulfureted hydrogen of dry sludge release increase than that of wet sludge. The effect of deodorizer order is CuSO4, NaClO, KMnO4, H2O2.(3) Study weightlessness of sludge fiberboard by active carbon adsorption. The weight decrease in 18 weeks incessancy. The weight decrease rate is significant in the former 3 weeks, and the latter decrease on an even keel, but never become zero. From NO.3 week, odor decrease obviously, but release sourness. From NO.5 week, sourness decrease. Odor of sludge fiberboard decrease, retain to NO.18 week.更多还原