1、造 纸 湿 部 化 学 戴红旗,化学工程学院造纸与印刷工程系 Department of Paper &Print Science Nanjing Forestry University,湿部化学？,在造纸系统中相互作用的所有组成：表面/界面离子胶体,湿部化学研究的内容,一切你看不见，但你又确实看得到它们在影响着纸的质量及纸机的运行性能。,重要性,Achievement of Paper Properties 纸性 Structural formation 结构成形 Mechanical strength 机械强度 Appearance optical 外观光学 Barrier & Resis
2、tance sizing 抗液体渗透施胶 Permanence stability 形稳性 Enhancement of Runnability 运行性提高 Machine Efficiency 纸机效率 Drainage speed 滤水速度 Foaming 泡沫 Spots, Holes & Deposits 斑点、针眼、沉积,湿部化学,Materials 原材料 Types 类型 Characteristics 特性 Principles Surface Area 表面积 Conductivity 电导率 Electrostatic Charge 电荷密度 Coagulation & F
3、locculation 凝结和絮聚,纸料的组成?,Water 水 Dissolved Electrolytes 溶解性电介质 Suspended Fibers 纤维 Suspended Fiber Fines 细小纤维 Suspended Filler Particles 填料 Surface-active Molecules (alone or as aggregates, i.e. detergents, dispersants, wood extractives, defoamers) 表面活性剂 Dissolved Polyelectrolytes - i.e. PAM, cation
4、ic starch wet and dry strength resins 水溶性聚电介质 Aggregated Sizing Molecules 聚结的施胶剂分子,造纸组成的形状和尺寸,纤 维: 直径10-50 um ，长1-7 mm 细小纤维: 直径 1 um，长 76 um 填 料: 0.1-10 um ASA/AKD胶粒: 1 um 硅 溶 胶 颗 粒: 0.01 um,1.0 mm,0.1 mm,0.01 mm or 10 m,1.0 m,0.1 m,细小纤维和纤维的特性,Composition 构成 Surface Area 表面积 Charge/pH Effects 电荷/PH影
5、响 Ion Exchange离子交换,Fiber Structure 纤维结构,Fiber Bundle纤维束,Single Fiber单根纤维,Lumen细胞腔,Fiber Composition 纤维构成,Secondary Walls- Lower Lignin- Higher Cellulose,Middle Lamella & Primary Cell Wall- High Lignin- Low Cellulose,纤维与细小纤维的特性,Bleached Kraft Fibers:漂白硫酸盐浆纤维 Most Lignin is Removed 绝大多数木质素已脱除 Most “Pi
6、tch” is Removed 绝大多数树脂已脱除 Groundwood Fibers:磨石磨木浆纤维 Lignin Remains 保留木质素 “Pitch” Remains 保留树脂,纤维与细小纤维的特性,Pitch, Lignin & Cellulose contain Carboxyl Groups 树脂、木质素和纤维素带又羧基基团 Lignin also contains Phenolic OH Groups 木质素带有酚羟基基团 Sulfite Pulps also contain Sulfonic Acid Groups亚硫酸盐浆带有磺酸基团,羧基和磺酸基基团,Pulp（浆） C
7、OOH含 量 SO3H 含量(meq/100g) (meq/100g) 针叶木KP浆 2-4 0.5 阔叶木SP浆 2-8 1.5 桉木KP浆 2-3 0.5 CTMP 20-30 5-7 脱墨KP浆 7 - 办公废纸浆 9 - 废新闻纸浆 20 -,纤维与细小纤维的特性,All Groups Ionize and Become Anionic In Water 在水中，所有基团电离而成为阴离子 Ionization is pH Dependent 离子化取决于pH pH值从3升到7，纤维上的羧基、树脂和木素阴离子性更强。 pH8以上，酚羟基也开始呈阴电性。,100,50,0,磺酸基,-COO
8、H,2 4 6 8 10 12 14,酚- OH,% 离子化度,pH,Characteristics of Fiber & Fines 纤维与细小纤维的特性,The amount of anionic charge on fiber and fines has multiple effects: 纤维和细小纤维上的阴电荷量影响诸多方面 Retention of Additives 助剂的留着 Dewatering Rate 脱水速率 Formation 成形 Sizing 施胶 Effectiveness of Retention Aids 助留剂的助留效果,Characteristics o
9、f Fiber & Fines 纤维与细小纤维的特性,比表面积410 CSF 浆 2.1 m2/g 纤维部分 1.2 m2/g 细小纤维 (16.5%) 8.0 m2/g细料的表面积远比纤维大 大部分化学助剂优先吸附在细料上。,Characteristics of Fiber & Fines 纤维与细小纤维的特性,Additive（助剂）Fibers（纤维）Filler Clay（填料） Fines（细小纤维）Cationic Starch 1 4 5 （阳离子淀粉） Rosin Soap Size 1 4 16 （皂化松香胶） Dispersed Rosin 1 16 20 （分散松香胶）
10、Alum（硫酸铝） 1 2 3,Relative Adsorption Intensity相对吸附强度,Characteristics of Fiber & Fines 纤维与细小纤维的特性,Retention of the Fines Fraction of a Furnish is CRITICAL to the Effectiveness ofWet End Additives: 湿部助剂的效能关键是纸料中细小纤维的留着 Size 施胶剂 Dyes, FWA 染料、增白剂 Wet End Starch 湿部淀粉 Wet/Dry Strength Resins 干/湿强树脂,Non-Fib
11、er Materials 非纤维原料,来自浆、漂白工段和水源衍生的硫酸盐、氯化物、草酸盐和醋酸盐影响: Increased Scale Deposits（增加片状沉积） Increased Conductivity（电导率上升） Reduced Effectiveness of some Additives（削弱某些助剂的效果）,亲水和疏水性的造纸原材料,Hydrophilic - “water loving” Starch dissolved in water（淀粉） Hemicellulose dissolved in water（半纤维素） Surfactants, dispersant
12、s, wetting agents dissolved in water（表面活性剂、分散剂、润湿剂） Retention aids dissolved in water（助留剂） Hydrophobic - “water fearing” All pigments dispersed in water（各种颜料） Fines dispersed in water（细小纤维） Rosin size dispersed in water（施胶剂） Wood Pitch dispersed in water（树脂）,Colloidal Materials（胶体物质）,需要被保留下来的物质： 化学助
13、剂 干扰物质否则：在白水系统积累引起沉积、斑点、断纸,粒径对填料留着的影响,Clay fraction in microns（填料粒径分布）,% Retention,10,10080604020,电荷是什么？,造纸纸料中所有的物质与水接触的界面带有静电荷而且几乎都是阴电荷绝大部分胶体呈分散的特性,Charge 电荷,Zeta Potential（Z电位）the electrical potential at the point where the Stern & Diffuse layers meet Degree of Repulsion（排斥度） determined by the thi
14、ckness of the double layer or “cloud”,Must be overcome for coagulation to occur 必须克服排斥力达到凝结发生,DLVO 稳定理论,DLVO Theory of Stability,纸机,纸浆处理,湿部,干燥部,湿部的作用,Starch,WSR,Fiber,Size,Flocculant,Anionic Trash,Fixative,湿部控制,Good,有效,无效,speed,speed,Poor,Wet End Team WET,胶体溶解 电荷,纤维 表面电位,絮聚,助留助滤机理,凝聚：通过加入盐或聚电解质压缩双电层
15、而失稳。絮聚：通过加入高分子聚合物将胶体颗粒连接而失稳。,凝聚,_ _ _ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _ _ _ _,电解质,分散,凝聚,_ _ _ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _ _ _,+ _ + + _ + _ + _ + _+ + + + _ + + + + _ + + _ + + + _+ +_+ + + + + + +_+ + +_ + + + _ + + + _ + + _ + + + +_ +,+ + + + + + + + _ + + + + + + _ + + + + + _ + + _+ _ _ + _ _ +,_
16、,_,_,_,_,_,凝聚,凝聚物对剪切力敏感 多价阳离子的凝聚作用比单价阳离子更有效 Al+3 Ca+2 Na+1 聚电解质比简单电解质更有效 polyamine alum,絮聚,Patch Flocculation 补丁絮聚 Bridge Flocculation 桥联絮聚 “Un-Flocculation”缔合絮聚,Patch Flocculation补丁絮聚,_ _ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _ _,Anionic Particle,阴离子颗粒,低分子量、 高阳电荷密度聚合物,+ + + + + +,_ _ _ _ _ _ _ _ _,+ + + + +,
17、+ + + + +,Patch Flocculation补丁絮聚,通常采用低分子量阳电荷聚电解质对剪切力敏感剪切后的聚集为软絮聚,Bridging Flocculation桥联絮聚,高分子量 低电荷密度聚合物,吸附开始阶段,絮聚,_ _ _ _ _ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _ _ _ _ _,+ + + + + + + + + + + + + + + + + +,+ + + + + + + + + + + + + + + + + + + + + +,_ _ _ _ _ _ _ _ _ _ _,Bridging Flocculation桥联絮聚,Accomplis
18、hed with high molecularweight polymers 高分子量聚合物 Highly influenced by molecular weight and charge density of polymer 极大地受到聚合物分子量、电荷密度影响 Forms larger flocs 形成大絮聚 Aggregates tend to reform as patch (soft) flocs when sheared 当受剪切时，聚集倾向于重新形成补丁絮聚,Hard Floc Behavior硬絮聚行为,_ _ _ _ _ _ _ _ _Initial Adsorption,
19、+ + + + + + + + +,_ _ _ _ _ _ _ _ Initial Flocculation (Hard Floc),+ + + + + + + + +,_ _ _ _ _ _ _,SHEAR,+ + + + + + + + + +,_ _ _ _ _ _ _ _Reconfirmation,+ + + + + + + + + +,_ _ _ _ _ _ _ _ _ _Reflocculation (Soft Floc),_ _ _ _ _ _ _,The Two Can Be Combined 两者组合,Patching 补丁,Bridging 桥联,+,Dual Polym
20、erSystem 双组分系统,Dual Polymer System双组分系统,_ _ _ _ _ _ _ + +_ _ _ +,_ _ _ _ _ _ + + _ _ _+,_ _ _ _ _,Patch,Anionic Polymer,_ _ _ _ _ _ _ _ _,_ _ _ _ _ _ _ + +_ _ _ +,_ _ _ _ + + _ _ _ + + _ _,_ _ _ _ _ _ _,Bridge,Patch plus Anionic polymer,影响聚合物吸附的因素,Polymer Characteristics - charge density, molecular
21、weight, chain length, backbone conformation, flexibility 聚合物特性：电荷密度、分子量、链长、骨架构造、柔韧性 Particle Characteristics - available adsorption sites, surface area, surface charge 粒子特性：可吸附的位置、表面积、表面电荷 Physical Environment - shear and turbulence, furnish consistency, order of addition 物理环境：剪切力、浆浓、添加顺序 Chemical E
22、nvironment - pH, conductivity, “interfering substances”化学环境：pH、电导率、干扰物质,聚合物电荷密度,Weak Absorption, Weak FlocculationGood Absorption, Strong Bridge FormationStrong Adsorption, Good Patch Formation,_ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _,_ _ _ _ _ _ _ _,Low,Medium,High,+,+,+,+,+,+,+,+,+,+,+,Particle Charge Dens
23、ity 粒子电荷密度,Weak Absorption, Weak Flocculation 弱吸附、弱絮聚Good Absorption, Strong Bridge Formation 中等吸附、强的桥联 Strong Adsorption, Good Patch Formation 强吸附、中等补丁,_,_ _ _,_ _ _ _ _ _ _ _,Low低,Medium中,High高,+,+,+,+,+,+,+,+,+,+,+,Interfering Substances 干扰物质,Fresh Water（新鲜水） Calcium and Magnesium hardness（Ca、Mg硬
24、度） Organic Matter（有机物） Residual Chlorine（残余氯化物） Suspended solids（悬浮物） Pulping Residuals（制浆残余物） Sodium salts（钠盐） Rosin soaps（松香皂） Fatty acid soaps（脂肪酸皂） Lignin compounds（木素化合物）,Interfering Substances 干扰物质,Bleaching Residuals 漂白残留 Sodium salts 钠盐 Calcium salts from Calcium hypochlorite（钙盐基） Alkali-sol
25、uble cellulose and hemicellulose （碱溶性纤维素、半纤维素） Broke（损纸） Starch（淀粉） Adhesives（胶粘剂） Inks（油墨） Coating Components（涂料）,Interfering Substances 干扰物质,Conductivity 电导率 Measurement of dissolved ions 溶解离子的测量 Many “interfering substances” are soluble ionized materials许多干扰物质为水溶性的、离子化的物质 High levels = High Condu
26、ctivity 含量高=电导率高High Conductivity = Bad News 电导率高=坏消息,Conductivity of Interfering Substances 干扰物质的电导率,Reduces Charge on Particles 降低粒子表面的电荷 Reduces Affinity for Charged Polymers 降低带电聚合物表面的静电吸附力 Causes “Coiling” of Polymer Molecule 引起聚合物分子的卷曲 Reduces Efficiency of Polymer降低聚合物的效能,Interfering Substanc
27、es 干扰物质,Charge电荷 Most colloidal “interfering substances” are anionic（绝大部分“干扰物质”为阴离子） “Anionic Trash”（阴离子垃圾） High Amounts = Bad News高含量=坏消息,Charge of Interfering Substances 干扰物质的电荷,Increases Cationic Demand 增加阳离子需求量 Competes with desired materials for interaction with cationic polymers 争夺阳离子聚合物 Neutralizes cationic charge on polymers 在聚合物表面中和阳电荷 reduces efficiency 降低效能 Adsorbs onto bentonite 吸附到膨润土表面 Acts as a dispersant作为分散剂,Effect of pH on Paper Machine Slime PH对纸机结垢的影响,
