不同树龄杂交构树的纤维特性及制浆性能研究
何连芳 白淑云 刘秉钺*
（大连工业大学，辽宁大连，116034）
摘 要：对不同树龄杂交构树的产量、化学成分、纤维形态、制浆性能进行了研究。结果表明，2年生的杂交构树，其经济性要高于1年生和3年生。不同树龄杂交构树木质部纤维形态差别较小，纤维粗短，长宽比小，细小组分含量较多。而杂交构树韧皮部纤维平均长度均大于7 mm，纤维细长，是优质的纤维原料。从化学组成上看杂交构树木质部化学组成相当于一般的阔叶木原料。杂交构树全皮中1%NaOH和苯-醇抽出物含量较高，主要集中在黑皮中。杂交构树白皮的木素含量较低，全皮的木素含量相对较高，且主要集中在黑皮中，同时黑皮中灰分含量高达10.68%，所以黑皮的存在对韧皮纤维原料制浆是不利的，应尽量除去。不同树龄杂交构树的APMP浆物理性能差别较小。杂交构树APMP与适量的针叶木化学浆配抄，可以制得优等轻型纸和新闻纸。
关键词：杂交构树；纤维形态；化学组成；APMP
中图分类号：TS721+.1
文献标识码：A
文章编号：1000-6842（2009）01-0001-05
Study on the Fiber Characteristics and Pulping Properties of Hybrid Paper Mulberry at Different Ages
HE Lian-fang BAI Shu-yun LIU Bing-yue*
(Dalian polytechnic university, Dalian, Liaoning Province, 116034)
（*E-mail: liubingyue1948@yahoo.com.cn）
Abstract：The production, fiber morphology and pulping properties of hybrid paper mulberry were investigated. The results showed that the economic efficiency of 2 years rotation of hybrid paper mulberry was higher than 1 year and 3 years. The fiber of xylem has the characteristics of shortness, small length-width ratio, and plenty of fine components, and there was little difference of fiber morphology with age. The phloem fiber was quality with the average length longer than 7mm. The chemical composition of xylem was equal to the hard wood. The extraction content of benzene-alcohol and 1%NaOH of the whole bark were higher, and mainly concentrated in black bark. The content of lignin of the whole bark was lower, but the content of lignin in white bark was higher and mainly in black bark. The content of ash in the black bark was 10.68%. Therefore black bark was disadvantages for pulping and should be removed as far as possibly. The APMP of xylem at different ages has small difference in physical properties. The excellent light paper and newspaper could be made with the mixed pulp of APMP and soft wood chemical pulp.
Key words:hybrid paper mulberry;fiber morphology;chemical composition;APMP
（责任编辑：常 青）
Bio-CMP制浆过程中的纤维分离机制（Ι）
雷晓春1,3 赵 宇2 林 鹿3
（1.杭州电子科技大学新闻出版学院，浙江杭州，310018；
2.浙江理工大学材料与纺织工程学院，浙江杭州，310018；
3.华南理工大学制浆造纸工程国家重点实验室，广东广州，510640）
摘 要：在传统化学机械法制浆之前，用木聚糖酶预处理木片获得生物化学机械浆（Bio-CMP）。在预处理阶段，木聚糖酶能水解纤维细胞壁上的部分木聚糖，从而引起木片中部分木聚糖的溶出，疏松了木片结构。由于阔叶木纤维细胞壁的初生壁和次生壁S1层具有较高浓度的半纤维素，阔叶木半纤维素的主要组分是木聚糖，因此在后续的盘磨磨浆过程中，纤维之间的分离更多地发生在结构疏松的初生壁P层和次生壁的S1层，而不是传统CMP磨浆过程中的胞间层（ML），使得更多的微细纤维能够暴露在纤维的表面。
关键词：木聚糖酶；Bio-CMP；纤维分离
中图分类号：TS743+.3
文献标识码：A
文章编号：1000-6842（2009）01-0006-05
Fiber Separation Mechanism of Bio-chemi-mechanical Pulping (Part Ι)
LEI Xiao-chun1,3,* ZHAO Yu2 LIN Lu3
(1. Hangzhou Dianzi University, Hangzhou, Zhejiang Province, 310018;
2. Zhejiang Sci-Tech University, Hangzhou, Zhejiang Province, 310018;
3. South China University of Technology, Guangzhou, Guangdong Province, 510640)
(*E-mail: paperlxc@gmail.com)
Abstract：The fiber separation in traditional chemi-mechanical pulping (CMP) occurs in the middle lamella (ML) layer due to the reaction between the chemicals and lignin in the chemical pretreatment stage. Thus, the fiber surfaces are covered with quite a lot of lignin and extractives, and those hydrophobic materials will prevent the bonding between the fibers. It was confirmed in this paper that when the wood chips were pretreated with xylanase prior to the CMP process, some xylan in the primary and secondary walls of the fiber cells was removed, which led the fiber structure to loosing. In the subsequent refining process of Bio-CMP, the fiber separation occurred mainly in the primary wall and secondary wall rather than the middle lamella because much xylan dissolved in the primary wall and secondary wall for hardwood, it created more microfibrills on the fiber surfaces after refining. Therefore, those fibers with much carbohydrate and less lignin and extractives on the surface could benefit to the interfiber bonding.
Key words:xylanase;Bio-CMP;fiber separation
（责任编辑：刘振华）
漆酶/丁香酸甲酯改善未漂硫酸盐浆纤维特性的EPR研究
刘 娜1 石淑兰2 秦梦华1
（1.山东轻工业学院制浆造纸工程省级重点学科，山东济南，250353；
2.天津科技大学天津市制浆造纸重点实验室，天津，300457）
摘 要：采用电子顺磁共振（EPR）研究了漆酶/丁香酸甲酯（L/MS）对未漂硫酸盐浆纤维特性的改善。结果显示，与单独漆酶处理相比，纤维经L/MS处理后自由基浓度提高的幅度更大。L/MS处理纸浆的反应液中出现的自由基的精细结构与漆酶处理MS反应液中的自由基精细结构相同，g值与纤维上的自由基g值相同。L/MS处理纸浆的过程中，纤维中自由基的增长速度远远高于单独漆酶处理；反应后期，纤维的自由基浓度和反应液中的自由基浓度均衰减。可以推测，MS的参与使得漆酶对纤维的改性延伸至纤维内部，且MS“嫁接”在了纤维上，促进了纤维的活化。来自MS和纤维木素的酚氧自由基的交联反应致使纤维间胶合作用增强。
关键词：漆酶；丁香酸甲酯；未漂硫酸盐木浆；自由基；EPR
中图分类号：Q55；TS743+.14
文献标识码：A
文章编号：1000-6842（2009）01-0011-05
EPR Study on Modification of Unbleached Kraft Pulp Fiber with Laccase and Methyl Syringate
LIU Na1,* SHI Shu-lan2 QIN Meng-hua1
(1. Shandong Key Lab of Pulp and Paper Engineering, Shandong Institute of Light Industry, Ji’nan, Shandong Province, 250353;
2. Tianjin Key Lab of Pulp & Paper, Tianjin University of Science & Technology, Tianjin, 300457)
(*E-mail: liuna_cn@yahoo.cn)
Abstract：The modification of unbleached kraft pulp with laccase in presence of methyl syringate (L/MS) was studied by electron paramagnetic resonance. The results showed that L/MS treatment caused a much higher increase of phenoxy radical concentration in fibers than laccase alone treatment. The radical in L/MS solution with pulp had the same hyperfine structure with the radical in reaction suspension for L/MS-treated pulp and the g-value was the same with that of the radicals of the fibers. The increase rate of radical concentration in fibers was much higher in L/MS treatment than that in laccase-treatment and the decay of free radicals was observed in fibers or in suspension in the later stage of the reaction. It was suggested that MS extended the enzymatic oxidation into cell wall and the MS was grafted onto the fibers, which accelerated the activation of the fibers. The cross-linking reaction of the phenoxy radicals of MS and lignin in fibers contributed to the enhancement of adhesion between the fibers.
Key words:laccase;methyl syringate;unbleached kraft pulp;radical;EPR
（责任编辑：梁 川）
玉米秸皮生物化机浆与改性秸穰联合抄纸的研究
陈洪雷1 杨桂花1 陈嘉川1 许志鸿1 黄 峰2
（1.山东轻工业学院制浆造纸工程省级重点学科，山东济南，250353；
2.山东大学微生物技术国家重点实验室，山东济南，250100）
摘 要：将玉米秸皮经过生物预处理后磨制化学机械浆，并与秸穰混合抄制瓦楞原纸。制得的秸皮化机浆粗浆得率为85.7%、白度为27.1%，经漂白后浆料得率为82.1%、白度为71.2%，打浆后各项强度性能指标都较为优良。改性秸穰的加入进一步改善秸皮浆性能，漂白浆返黄值有所下降，当秸穰含量为20%时，漂白浆的抗张指数和耐破指数达到最大值，分别增加了27.8%和17.4%；秸穰含量为30%时，未漂浆的抗张指数和耐破指数分别增加了96.8%和83.3%。同时，两种浆的耐折度也有显著改善。
关键词：玉米秸秆；改性秸穰；生物预处理；化学机械浆
中图分类号：TS749
文献标识码：A
文章编号：1000-6842（2009）01-0016-04
Preliminary Study on Bio Chemi-mechanical Pulp of Leaf-free Corn Stalks
CHEN Hong-lei1,* YANG Gui-hua1 CHEN Jia-chuan1 XU Zhi-hong1 HUANG Feng2
(1. Shandong Key Lab of Pulp and Paper Engineering, Shandong Institute of Light Industry, Ji’nan,
Shandong Province, 250353; 2. State Key Lab of Microbial Technology, Shandong University,
Ji’nan, Shandong Province, 250100)
(*E-mail: shaming007@163.com)
Abstract：The experiment of chemi-mechamical pulping of leaf-free corn stalks with bio-pretreatment by using the fungi was carried out the brightness of the unbleached pulp was 27.1%ISO and the unscreened pulp yield was 85.7%, the brightness reached 71.2%ISO after bleaching. The bleached pulp proved quite good strength performance. Pulp strength was improved further when some modified pith of corn stalk was added, colour reversion value of the pulp declined slightly. Tensile strength and burst strength of the bleached pulp increased 27.75% and 17.39% respectively compared with the control pulp when the dosage of the modified pith of corn stalks was 20% in similarly the tensile strength and burst strength of the bleached pulp increased by 96.76% and 83.33% respectively when the content of the pith of corn stalks in pulp was 30%. In addition, the folding endurance of the paper was also improved sharply. Finally the manufacture of corrugating medium with corn stalks as raw material, and the adhesion mechanism of modified pith of corn stalks.
Key words:corn stalks;bio-pretreatment;chemi-mechamical pulp
（责任编辑：刘振华）
纤维素酶预处理降低高得率浆磨浆能耗的研究
张升友1 陈夫山1，2 王高升1 齐临东1
（1.天津科技大学天津市制浆造纸重点实验室，天津，300457；
2.青岛科技大学化工学院,山东青岛，266042）
摘 要：研究了在精磨前用纤维素酶预处理杨木一段盘磨化学机械浆对降低磨浆能耗的影响，探讨了该酶的酶学性质以及在不同反应体系下对能耗、纸浆物理性能和纤维形态的影响。结果表明，纤维素酶在pH值4.8和温度50℃条件下，各组分酶活较高；当纤维素酶在用量0.5 IU/g、温度50℃、pH值5、处理时间为1 h的条件下，酶处理效果较好，可以有效降低磨浆能耗。但是由于纤维长度下降，纸浆的物理强度性能都有不同程度的降低。
关键词：纤维素酶；酶处理；磨浆；物理性能；纤维形态
中图分类号：TS752
文献标识码：A
文章编号：1000-6842（2009）01-0020-05
Reduction of Energy Consumption in High-yield Pulp Production by Cellulase Treatment of
the Pulp from First Stage Refiner
ZHANG Sheng-you1，* CHEN Fu-shan1,2 WANG Gao-sheng1 QI Lin-dong1
(1. Tianjin Key Lab of Pulp & Paper, Tianjin University of Science & Technology, Tianjin, 300457; 2. Qingdao University of Science and Technology, Qingdao, Shandong Province, 266042)
(*E-mail: shengyou2008@yahoo.com.cn)
Abstract：The effect of cellulase treatment of the pulp from the first stage refiner on the reduction of energy consumption of poplar chemi-mechamical pulp production was studied. The effects of temperature and pH value on enzyme activities of cellulase were investigated, and the effects of cellulase on the refining performances, physical properties and fiber morphology of the pulp in different reaction conditions were discussed. The results showed that the cellulose has good activity in the condition of 50℃ and pH value 4.8, and the cellulase can effectively improve the refining efficiency in the conditions of 0.5 IU/g, 50℃, pH value 5 and 1 hour. However, the result showed that enzymatic treatment has negative effect on the pulp strength properties and the fiber length.
Key words:cellulose;enzymatic treatment;refining;physical properties;fiber morphology
（责任编辑：常 青）
绿色糖单孢菌复合胞外酶漂白纸浆的机理
张 勇1,2 蒲俊文1,* 吴玉英1 吕卫军2
（1.北京林业大学材料科学与技术学院，北京，100083；2.中国制浆造纸研究院，北京，100020）
摘 要：以经过绿色糖单孢菌复合胞外酶漂白的纸浆为研究对象，首次采用SEM、GC、FT-IR、CP/MAS 13C-NMR、XRD等仪器分析手段全面阐释由一种菌同时产生的两种酶（木聚糖酶和木素过氧化物酶）协同漂白纸浆的作用机理。结果发现该复合胞外酶漂白，对纸浆中的木聚糖和聚阿拉伯糖降解显著；可断裂部分残余木素和木素-碳水化合物复合体，减少或改变纸浆中的发色和助色基团；使纤维结构变得疏松，增强后续漂剂的渗透，促进木素的溶出；漂白对纸浆纤维素的破坏主要集中在无定形区，对结晶区影响较小。
关键词：绿色糖单孢菌；复合胞外酶；纸浆；协同漂白；机理
中图分类号：TS745；Q55
文献标识码：A
文章编号：1000-6842（2009）01-0025-06
Mechanism of Synergistic Bleaching Utilizing Compound Enzyme from Saccharomonospora Viridis
ZHANG Yong1,2 PU Jun-wen1,* WU Yu-ying1 LV Wei-jun2
(1. College of Materials Science and Technology, Beijing Forestry University, Beijing, 100083;
2. China National Pulp and Paper Research Institute, Beijing, 100020)
(*E-mail: jwpu@bjfu.edu.cn)
Abstract：The mechanism of synergistic bleaching utilizing compound-enzyme (contain xylanase and lignin peroxidase) from Saccharomonospora viridis was comprehensively studied by using SEM, GC, FT-IR, CP/MAS 13C-NMR and XRD. The results showed that xylan and poly-arabinose were degraded evidently after treating with compound enzyme. Dissolution of lignin and LCC resulted in a reduction of chromophoric groups in the pulp. After enzyme treatment, fiber structure became loosen and easy to penetrate during the following bleaching sequence. Additionally, XRD illustrated that the enzyme reacted with fiber not in crystalline area but in amorphous area.
Key words:saccharomonospora viridis;compound enzyme;pulp;synergistic bleaching;mechanism
（责任编辑：田风洲）
漆酶/木聚糖酶体系对OCC浆料改性的研究
尤纪雪 连海兰 周 楫 张秀芬 王 环
（南京林业大学江苏省制浆造纸科学与技术重点实验室，江苏南京，210037）
摘 要：用漆酶/木聚糖酶体系（LXS）对OCC浆料进行改性，以改善浆料强度；并探讨了酶改性后浆料强度与酶改性产生的自由基之间的关系，以及浆料强度提高的原因。结果表明：LXS对OCC浆料改性，能明显提高浆料强度。当酶用量10 IU/g时，与对照浆相比，抗张指数、环压指数和湿抗张指数分别提高了37.1%、23.2%和50.4%，其中湿抗张指数的提高更为显著。采用LXS改性时，产生的自由基浓度与纸浆强度成正比关系，即自由基浓度越大，纸浆强度越高。通过对LXS改性对纸浆自由基浓度、纤维结晶度、接触角和红外光谱影响的研究，从理论上解释了漆酶改性能提高浆料强度的原因。
关键词：漆酶/木聚糖酶体系（LXS）；抗张强度；环压强度；自由基；接触角
中图分类号：TS743+.14
文献标识码：A
文章编号：1000-6842（2009）01-0031-04
Modification of Old Corrugated Container Pulp with Laccace/Xylanase System
YOU Ji-xue* LIAN Hai-lan ZHOU Ji ZHANG Xiu-fen WANG Huan
(Nanjing Forestry University, Nanjing, Jiangsu Province, 210037 )
(*E-mail: yjxaxn@yahoo.com.cn)
Abstract：In this study the old corrugated container pulp was treated with laccace/xylanase system(LXS) to improve the strength of the pulp. The relation between the strength of enzyme modified pulp and the free radicals created from enzyme treatment as well as the reasons of the increase in pulp strength caused by enzyme modification were investigated. The results indicated that the strength of the pulp was obviously improved by LXS modification. Compared with control pulp, the tensile strength, ring crush strength and wet tensile strength was increased by 37.1%, 23.2% and 50.4% respectively at enzyme usage of 10 IU/g. The wet tensile strength was remarkably increased. It was found that the consistency of free radicals of the modified pulp was directly proportional to the pulp strength, namely the higher the consistency of free radicals, the higher the pulp strength. Based on the study of the effects of Laccase/Xylanase system treatment on consistency of free radicals, fiber crystallinity, contact angle and IR spectrum, the reasons of the increase of pulp strength by LXS modification were explained.
Key words:laccase/xylanase system;tensile strength;ring crush strength;free radicals;contact angle
（责任编辑：郭彩云）
漂白硫酸盐思茅松浆酶促打浆的研究
张正健 胡惠仁 徐建峰 赵 晶
（天津市制浆造纸重点实验室，天津科技大学材料科学与化学工程学院，天津，300457）
摘 要：采用酸性、中性及碱性纤维素酶对漂白硫酸盐思茅松浆的酶促打浆进行研究，探讨了各种酶在不同反应体系下对漂白硫酸盐思茅松浆打浆性能和物理性能的影响。结果表明，碱性纤维素酶预处理对纸浆的打浆度提高不明显，因此该酶不适合用于酶促打浆；用适量酸性和中性纤维素酶预处理后，纸浆物理性能有所降低，但打浆度得到明显提高，可降低打浆能耗，因此酸性和中性纤维素酶适用于酶促打浆。最后选择酸性和中性纤维素酶作为研究对象，考察了温度和pH值对酶促打浆的影响。结果表明，中性和酸性纤维素酶处理的最佳温度均为45~50℃、最佳pH值范围分别为4.8~5.8和2.8~5.8。
关键词：酶促打浆；酶活；纤维素酶；打浆度；纸浆物理性能
中图分类号：TS743+.4
文献标识码：A
文章编号：1000-6842（2009）01-0035-07
Effect of Enzymatic Treatment on Beating Performance of Simao Pine Bleached Kraft Pulp
ZHANG Zheng-jian* HU Hui-ren XU Jian-feng ZHAO Jing
(Tianjin Key Lab of Pulping and Papermaking Engineering, Tianjin University of Science & Technology, Tianjin, 300457)
(*E-mail: zzj9931214@yahoo.com.cn)
Abstract：In this paper, the effects of enzymatic treatment with acidic cellulase, neutral cellulase and alkaline cellulase on beating performance of Simao pine bleached kraft pulp were studied. The effects of those cellulases on beating performance and physical properties of Simao pine bleached kraft pulp in different conditions were discussed. At first, the effects of temperature and pH value on the activities of those three kinds of cellulases were investigated, and the enzymatic activities were measured. Then, the effects of dosage of the three cellulases on enzymatic beating of the pulp were discussed. The results showed that alkaline cellulase didn’t help much for pulp beating, and had somewhat adverse effect on pulp physical properties; acidic cellulase and neutral cellulase could improve pulp beating performance dramatically and the physical properties were slightly decreased. So that acidic cellulase and neutral cellulase were suitable for enzymatic beating of bleached softwood kraft pulp, and could reduce energy consumption of beating process. At last, the conditions of enzymatic treatment (temperature and pH value) of acidic cellulase and neutral cellulase in enzymatic beating were investigated. The optimized conditions were as follows: temperature 45~50℃, pH value 4.8~5.8 for the neutral cellulase and temperature 45~50℃, pH value 2.8~5.8 for the acidic cellulase.
Key words:enzymatic beating;enzymatic activity;acidic cellulase;neutral cellulase;alkaline cellulase;beating degree;pulp physical properties
（责任编辑：陈丽卿）
尾巨桉微/纳米粒子溶出规律的研究
彭万喜1 吴义强1 武书彬2 张党权3 陈 洪1
（1.中南林业科技大学材料科学与工程学院，湖南长沙，410004；
2.华南理工大学制浆造纸工程国家重点实验室，广东广州，510640；
3.中南林业科技大学经济林育种与栽培国家林业局重点实验室，湖南长沙，410004）
摘 要：采用单因素实验法，分析了尾巨桉新鲜木片与陈旧木片的溶出粒子特征及其微/纳米粒子在常规溶剂抽提和超声波、冷冻、微波预处理抽提中的溶出规律。结果表明，常规溶剂抽提时，新鲜木片溶出的纳米粒子（粒径<100 nm）在体积和粒子数上大于陈旧木片，而大于91.3 nm的粒子在体积和粒子数上小于陈旧木片；随着抽提时间的延长，尾巨桉新旧木片中抽提物的溶出量均呈增加趋势。超声波、冷冻与微波预处理可降低尾巨桉新旧木片溶出粒子的集聚程度，提高抽提物溶出量，其中超声波预处理的作用最为明显。
关键词：尾巨桉；微/纳米粒子；超声波；冷冻；微波
中图分类号：TS742
文献标识码：A
文章编号：1000-6842（2009）01-0042-04
Leaching Rules of Micro and Nano Particles from Eucalyptus urophydis Wood
PENG Wan-xi1,* WU Yi-qiang1 WU Shu-bin2 ZHANG Dang-quan3 CHEN Hong1
(1. School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha, Hu’nan Province, 410004; 2. State Key Lab of Pulp and Paper Engineering, South China University of Technology,
Guangzhou, Guangdong Province, 510640; 3. The Key Lab of Non-Wood Forest Products of State Forestry
Administration, Central South University of Forestry and Technology, Changsha, Hu’nan Province, 410004)
(*E-mail: pengwanxi@163.com)
Abstract：The characteristics of leached particles from Eucalyptus urophydis wood chips and the leaching rules of micro/nano particles by using the sorbitic-, supersonic-, freezing-, and microwave- extracting approaches were analyzed. The result showed that: (1) In sorbitic-extracting process, the volume and number of nano particles from fresh chips are more than those from old chips. However, the volume and number of the particles large than 91.3 nm from the fresh chips are less than those from old chips, and the extractive mass of micro and nano particles increases with the extracting time. (2) Supersonic extraction, freezing pretreatment and microwave pretreatment decrease the congregation of the leached particles from both fresh chips and old chips, and simultaneously increase the extractive mass. Among the four extracting approaches, the supersonic-extraction is the most effective, microwave pretreatment is the second, and freezing pretreatment is only a little better than sorbitic extraction.
Key words:eucalyptus urophydis;micro and nano particles;supersonic wave;freezing;microwave
（责任编辑：田风洲）
AFM和XPS揭示自催化乙醇法制浆木素沉淀现象与机理
徐永建1,2 张美云1 李可成2
（1.陕西科技大学造纸工程学院，陕西省造纸技术与特种纸品开发重点实验室，710021；
2.加拿大New Brunswick大学化学工程系，E3B2L2）
摘 要：研究了乙醇麦草浆纤维表面的形貌学特征、化学组成和木素的分布。AFM研究结果表明，未洗涤乙醇浆纤维表面被无定形的木素完全覆盖，木素颗粒的数量和大小随洗涤逐渐减少减小；洗涤四段的乙醇麦草浆纤维微细纤维清晰可见，但仍然可见木素颗粒。研究还表明，乙醇浆纤维表面木素为球状颗粒，这是木素分子内聚力作用的结果。木素在纤维表面沉积所产生的木素颗粒的大小、分布和形貌学特征与木素性质和浓度有关。XPS分析结果表明，乙醇麦草浆纤维表面O/C比远离纤维素O/C比的理论值而接近木素O/C比的理论值，证明乙醇浆纤维表面存在木素。同时对乙醇浆卡伯值的变化进行了测定，表明快速冷却洗涤法乙醇浆卡伯值高的原因主要是在蒸煮和洗涤过程中溶解木素在纤维表面二次吸附和沉积造成的。
关键词：乙醇制浆；木素沉淀；AFM；XPS；麦草
中图分类号：TS743＋.9
文献标识码：A
文章编号：1000-6842（2009）01-0046-05
Lignin Precipitation in Auto-catalyzed Ethanol Pulping Studied by XPS and AFM
XU Yong-jian1,2,* ZHANG Mei-yun1 LI Ke-cheng2
(1. Shaanxi Key Lab of Papermaking Technology and Specialty Paper, School of Papermaking Engineering,
Shaanxi University of Science and Technology, Xi’an, Shaanxi Province, 710021;
2. Chemical Engineering Department, University of New Brunswick, Canada, E3B2L2)
(*E-mail: xuyongjian@sust.edu.cn)
Abstract：The morphological characteristics, chemical composition and lignin distribution on the fiber surfaces of auto-catalyzed ethanol pulp were studied. The results obtained from the observation of AFM showed that lignin particles completely cover on the un-washed fiber surfaces, the amount and size of the lignin particles covered on the fiber surfaces become less and small in washing process. The fibrillar structure can be observed clearly but there still are lignin particles on the fiber surfaces after four-stage washing. It was found that lignin particles on the fiber surface look like globule due to the interaction between lignin molecules. XPS analyses results indicated that O/C ratio of ethanol wheat straw pulp fiber surface is higher than the theoretical O/C ratio of cellulose and close to the theoretical O/C ratio of lignin, and it proves there is lignin on the fiber surface. Kappa number measurement suggested high kappa number of ethanol pulp is mainly due to the precipitation of the dissolved lignin from the pulping liquor.
Key words:Ethanol pulping;lignin precipitation;AFM;XPS;wheat straw
（责任编辑：赵旸宇）
热置换乙醇法制浆溶出木素的分级提纯及其结构
张美云 岳小鹏 徐永建
（陕西科技大学造纸工程学院，陕西西安，710021）
摘 要：对热置换麦草乙醇法制浆黑液中的溶出木素进行了分级分离提纯，并采用FT-IR、13C-NMR等分析技术，对其进行了研究。结果表明，溶出木素中由于温度变化析出的部分占有很大比例，当温度降至50℃时，黑液中可溶解的木素达到了总量的29.7%。一部分β-O-4结构的木素随着木素大分子的溶出转移到乙醇溶液中，而不是在发生断裂后再溶于蒸煮液中。在溶出木素中，低分子质量部分中包含了更多的羟基和羰基结构，其中包括大量的共轭羰基结构。伴随着α-O-4键的断裂，部分Cα上发生了与芳香环的缩合反应。
关键词：溶出木素；分级；结构；乙醇法制浆；热置换
中图分类号：TS743
文献标识码：A
文章编号：1000-6842（2009）01-0051-05
Fractionation Purification and the Structure Study of Dissolved Lignin in RDH Ethanol Pulping
ZHANG Mei-yun* YUE Xiao-peng XU Yong-jian
(College of Papermaking Engineering, Shaanxi University of Science & Technology, Xi’an, Shaanxi Province, 710021)
(*E-mail: myzhang@sust.edu.cn)
Abstract：In this paper, the dissolved lignin in black liquid of RDH （Rapid Displacement Heating）wheat straw ethanol pulping was separated and fractionation purified according to the different solubility of lignin in ethanol solution. The configurations of fractions were studied by using the methods of FT-IR and 13C-NMR. The experiment showed that the lignin deposited by the change of temperature accounts for 29.7% of the dissolved lignin, part of β-aryl ether linkages are broken in the black liquor, not in the pulp; low molecular weight fraction of dissolved lignin contains more hydroxyl, carbonyl structure; condensation reaction occurs in part of Cαaccompanying with the broken of α-aryl ether linkages.
Key words:dissolved lignin;classification;configuration;ethanol pulping;RDH
（责任编辑：孙秋菊）
麦草浆氧脱木素中木素结构的变化
袁成强1，2 刘 玉1，3 陈嘉川1 杨桂花1 杨 猛2 黄 峰3
（1.山东轻工业学院制浆造纸科学与技术省部共建教育部重点实验室，山东济南，250353；
2.山东轻工业设计院，山东济南，205100；
3.山东大学微生物技术国家重点实验室，山东济南，250100）
摘 要：研究了麦草NaOH-AQ浆在氧脱木素过程中木素结构的变化。采用酶-弱酸解两段法提取浆中残余木素；利用酸析法从黑液中分离出溶出木素试样，经过弱酸解得到提纯的木素试样。通过凝胶渗透色谱（GPC）对所得的木素试样分别进行分子质量检测，得出各种木素的分子质量分布及变化，并对其进行了分析对比；利用磷谱核磁共振（31P-NMR）技术对木素结构中脂肪羟基、总酚羟基、羧基以及总酚羟基中各酚羟基等官能团进行定量分析对比，以全面了解木素结构在氧脱木素中的变化规律。
关键词：麦草浆；氧脱木素；木素分子质量；31P-NMR；木素结构
中图分类号：TS749+.2
文献标识码：A
文章编号：1000-6842（2009）01-0056-04
Change of Lignin Structure of Wheat Straw Pulp during Oxygen Delignification
YUAN Cheng-qiang1,2,* LIU Yu1,3 CHEN Jia-chuan1 YANG Gui-hua1 YANG Meng2 HUANG Feng3
(1. Key Lab of Paper Science and Technology of Ministry of Education, Shandong Institute of Light Industry, Ji’nan,
Shandong Province, 250353; 2. Shandong Light Industry Design Institute, Ji’nan, Shandong Province, 250100;
3. State Key Lab for Microbial Technology, Shandong University, Ji’nan, Shandong Province, 250100)
(*E-mail: ycqiang128@126.com)
Abstract：The change of lignin structure of wheat straw soda-anthraquinone pulp during oxygen delignification was studied. Different residual lignin samples were isolated from the pulps by using the two-stage method of enzyme-mild acidic hydrolysis solution. The acid-precipitating method was used to isolate the dissolved lignin from the black liquor and the crude lignin was purified by mild acidic hydrolysis. All of the lignin samples were analyzed by GPC, and the changes of molecular weight of the lignin were studied and compared. After derivation of the lignin samples, the 31P-NMR spectra of phosphorized were obtained and the functional groups of the lignin were quantitatively analyzed and compared in order to discover the change of lignin structures during oxygen deligninfication.
Key words:wheat straw pulp;oxygen deligninfication;lignin molecular;31P-NMR;lignin structure
（责任编辑：关 颖）
麦草烧碱-蒽醌法蒸煮中木素分子质量的变化
袁成强1，2 刘 玉1，3 陈嘉川1 杨桂花1 黄 峰3
（1.山东轻工业学院制浆造纸科学与技术省部共建教育部重点实验室，山东济南，250353；
2.山东轻工业设计院，山东济南，250100;3.山东大学微生物技术国家重点实验室，山东济南，250100）
摘 要：以麦草为研究对象，进行了常规烧碱-蒽醌法蒸煮。采用酶解-弱酸解两段法分别从原料和纸浆中分离出原料木素和纸浆残余木素；采用酸析法从黑液中分离出溶出木素试样，经弱酸解得到提纯的木素试样。通过凝胶渗透色谱（GPC）对所有的木素试样分别进行分子质量检测，得出各种木素的分子质量分布及变化，并对其进行了分析对比。结果表明，随着蒸煮的进行，麦草纸浆残余木素的平均分子质量先增大后减小，升温后期和保温初期是造成木素平均分子质量降低的主要阶段；黑液中溶出木素的平均分子质量则逐渐增大。
关键词：麦草；烧碱-蒽醌法制浆；木素分子质量
中图分类号：TS721+.3；TS743
文献标识码：A
文章编号：1000-6842（2009）01-0060-04
Change of Lignin Molecular Weight of Wheat Straw during Soda-anthraquinone Cooking
YUAN Cheng-qiang1,2,* LIU Yu1,3 CHEN Jia-chuan3 YANG gui-Hua1 Huang Feng3
(1. Key Lab of Paper Science and Technology of Ministry of Education, Shandong Institute of Light Industry,
Ji’nan, Shandong Province, 250353; 2. Shandong Light Industry Design Institute, Ji’nan, Shandong Province, 250100; 3. State Key Lab for Microbial Technology, Shandong University, Ji’nan, Shandong Province, 250100)
(*E-mail: ycqiang128@126.com)
Abstract：The wheat straw was used as the raw material in this research. Conventional soda-anthraquinone cooking was carried out. Different lignin samples were isolated from the raw material and the pulps by using the two-stage method of enzyme-mild acidic hydrolysis solution. The acid-precipitating method was used to isolate the dissolved lignin from the black liquor and the crude lignin was purified by mild acidic hydrolysis. All of the lignin samples were tested by GPC, and the changes of molecular weight of the lignin were studied and compared. It was found that the residual lignin molecular weight increased at first and then decreased, while the dissolved lignin molecular weight increased with increasing cooking time. Furthermore, the residual lignin molecular weight was higher than the dissolved lignin in various stages of cooking, which illustrated that the lignin was dissolved in the form of debris.
Key words:wheat straw;soda-anthaquinone cooking;lignin molecular weight
（责任编辑：常 青）
化学机械法制浆中段废水中有机污染物的降解
陈永静1 张继兵2，*
（1.赣州市环境科学研究所，江西赣州，341000；2.广州市环境监测中心站，广东广州，510030）
摘 要：采用水解酸化-接触氧化法处理广西某制浆厂化学机械法制浆中段废水,出水CODCr为352 mg/L,SS为84 mg/L。运用GC-MS联用仪对制浆中段废水中的有机物进行测定,共测得有机污染物41种,其中10种有机污染物被列入美国EPA环境优先控制污染物,在进水的30种有机物中,15种有机物被完全去除。通过分析制浆中段废水有机污染物在工艺流程中相对组分变化的规律,揭示了水解酸化-接触氧化法处理制浆中段废水过程中的污染物迁移和降解规律。
关键词：水解酸化;接触氧化;制浆中段废水;有机污染物;GC-MS
中图分类号：X793
文献标识码：A
文章编号：1000-6842（2009）01-0064-04
Degradation of Organic Pollutants in Bleaching/Washing Effluent of Chemi-mechamical Pulping
CHEN Yong-jing1 ZHANG Ji-bing2,*
(1. Ganzhou City Environmental Science Research Institute, Ganzhou, Jiangxi Province, 341000;
2. Guangzhou Environmental Monitoring Center Station, Guangzhou, Guangdong Province; 510030)
(*E-mail: zhangjb027@163.com)
Abstract：Hydrolysis and bio-contact oxidation process was adopted to treat bleaching and washing effluent from a chemical-mechanical pulping plant in Guangxi, China. The results showed that the average concentration of CODCr and SS of the effluent was 352 mg /L and 84 mg/L respectively, which could meet the national discharge regulation of GB 3544-2001. The organic pollutants in the bleaching and washing effluent were determined by GC-MS. 41 organic materials were detected totally, and there were 10 organic matters on the list of environmental priority pollutants prescribed by U.S. EPA. 15 organic matters were completely removed from the influent which contained 30 organic matters. The change of the component of the organic pollutants in hydrolysis and bio-contact oxidation process was analyzed, and the transfer and degradation law of organic pollutants was discovered.
Key words:hydrolysis-acidification;bio-contact oxidation;bleaching and washing effluent;organic pollutants;GC-MS
（责任编辑：梁 川）
Fe-CA仿酶-混凝法处理麦草化机浆综合废水的研究
高洪贵 谢益民 孙媛芳
（山东轻工业学院造纸科学与技术省部共建教育部重点实验室，山东济南，250353）
摘 要：造纸厂麦草化机浆综合废水经Fe-CA仿酶体系处理后，CODCr去除率非常显著，可达60%以上，木质素大量脱除，有效地提高了废水的可生化性，为难降解废水的后续处理创造了条件。铁与羧酸形成的螯合物（Fe-CA）性能稳定，价格低廉，在功能上能较好地模拟木质素过氧化物酶。研究表明，Fe-CA仿酶体系处理废水的最佳条件为：Fe-CA仿酶用量为10 mg/L废水，原水pH值调至中性，温度30℃，H2O2用量是0.15 g/L，硫酸铝加入量为0.4 g/L,沉降时间6 h。
关键词：Fe-CA仿酶；造纸废水；仿酶处理
中图分类号：X793
文献标识码：A
文章编号：1000-6842（2009）01-0068-04
Fe-CA Biomimetic-flocculation Treatment of Mixed Effluent from CMP of Wheat Straw
GAO Hong-gui* XIE Yi-min SUN Yuan-fang
(Key Lab of Paper Science and Technology of Ministry of Education, Shandong Institute of Light Industry,
Ji’nan, Shandong Province, 250353)
(*E-mail: gaohonggui1983@163.com)
Abstract：The CODCr of mixed wastewater from CMP of wheat straw is removed evidently by biomimetic treatment, and the removal of CODCr can reach more than 60%. Bio degradable property of the mixed wastewater is improved through the removal of lignin, and it creates condition for subsequent treatment of poor degradable wastewater. Fe-carboxyl acid complexes have stable characteristics and low price, and can simulate the function of lignin peroxidase very well. The best condition of wastewater treatment is as follows. Fe-CA 10 mg/L wastewater，the pH of original wasterwater is adjusted to neutral, the temperature of wastewater is 30℃, H2O2 0.15 g/L, Al2(SO4)3 0.4 g/L, sedimentation time 6 h.
Key words:Fe-CA biomimetic;paper mill effluent;biomimetic treatment
（责任编辑：王 岩）
球形木质素吸附剂吸附L-赖氨酸的性能研究
刘明华1,2 陈国奋1 姚梅宾1 杨 杰1
（1.福州大学环境与资源学院，福建福州，350002；
2.华南理工大学制浆造纸工程国家重点实验室，广东广州，510640）
摘 要：以硫酸盐木质素为原料，利用反相悬浮技术制备出球形木质素吸附剂，然后利用球形木质素吸附剂吸附L-赖氨酸，并进行吸附条件的优选实验。实验结果表明：吸附效果取决于吸附质溶液pH值、吸附质初始质量浓度、吸附时间、吸附温度以及无机盐盐浓度等。当吸附质溶液pH值为9.0时，吸附质初始质量浓度为300 mg/L，吸附时间为120 min，吸附温度为25℃时球形木质素吸附剂的平衡吸附容量可达60.0 mg/g。此外，氯化铵对球形木质素吸附剂吸附容量的影响大于氯化钠，而且随着盐浓度的增大，吸附容量从60.0 mg/g降至2.6 mg/g。同时进行了解吸再生和对比实验，发现用1.5 mol/L的氨水解吸时，解吸率可达93.3%。
关键词：球形木质素；吸附剂；吸附；L-赖氨酸；解吸
中图分类号：TQ028.1
文献标识码：A
文章编号：1000-6842（2009）01-0072-04
The Adsorption Performance of L-lysine on a Spherical Lignin Adsorbent
LIU Ming-hua1,2,* CHEN Guo-fen1 YAO Mei-bin1 YANG Jie1
(1. College of Environment & Resources, Fuzhou University, Fuzhou, Fujian Province,
350002;
2. State Key Lab of Pulp & Paper Engineering, South China University of Technology,
Guangzhou, Guangdong Province, 510640)
(*E-mail: mhliu2000@263.net)
Abstract：The spherical lignin adsorbent, denoted as SLA, was prepared by applying inverse-phase suspension polymerization technique with sulphate lignin as raw material. Then L-lysine was adopted as adsorbate to study the performance of SLA and the adsorption conditions were also optimized. The results indicated that the adsorption of L-lysine on SLA depends on the solution pH, initial concentration of the adsorbate, time, temperature and salt concentration. The equilibrium adsorption capacity could reach 60.0 mg/g under such conditions as 9.0 of solution pH, 300 mg/L of the initial concentration， 25℃ of the adsorption temperature and 120 min of the adsorption time. Moreover, NH4Cl and NaCl also showed great effect on the adsorption efficiency when existing in large amount. The adsorption capacity decreased from 60.0 mg/g to 2.6 mg/g with an increase of salt concentration in aqueous solutions among the concentration range of 0.5 and 1.5 mol/L. On the other hand, L-lysine could be desorbed with ammonia of 1.5 mol/L, and the desorption rate could reach 93.3%.
Key words:spherical lignin；adsorbent；adsorption；L-lysine；desorption
（责任编辑：马 忻）
脱墨污泥热分解特性及其热解动力学浅析
娄 瑞 武书彬* 谭 扬
（华南理工大学制浆造纸工程国家重点实验室，广东广州，510640）
摘 要：利用热重分析法和实验室自行设计的静态热解炉对脱墨污泥的热解行为及热裂解特性进行了研究，探讨了不同升温速率对脱墨污泥热解反应特性的影响，并根据微分热重曲线建立了动力学模型，计算热解反应的动力学参数。结果表明，脱墨污泥的热失重过程可分为水分析出、挥发物质析出、固定碳燃尽和碳酸钙热分解4个阶段，其热解反应动力学为3个三级反应。从利用电子探针显微技术、气相色谱和傅里叶红外分析方法对热裂解产物进行表征的结果来看，造纸脱墨污泥具有很好的资源化综合利用前景。
关键词：脱墨污泥；热解；动力学；TG-DTG
中图分类号：TS7
文献标识码：A
文章编号：1000-6842（2009）01-0076-05
Thermogravimetry and Kinetic Analysis of Deinking Sludge
LOU Rui WU Shu-bin* TAN Yang
(State Key Lab of Pulp & Paper Engineering, South China University of Technology, Guangzhou, Guangdong Province, 510640)
(*E-mail: shubinwu@scut.edu.cn)
Abstract：Pyrolysis characteristics of waste paper deinking sludge were studied by thermogravimetric analysis. The effects of different heating rates on the pyrolysis characteristics of the deinking sludge were investigated, and the dynamical model of this pyrolys, is process was also established. The results showed that the dynamical model of this pyrolysis process could be expressed by three third-order parallel reactions, and the non-isothermal weight-loss process of the deinking sludge was composed of four stages, including dewater stage, volatile matter releasing stage, carbon burnout stage, and Calcium carbonate decomposition stage. In the paper, the deinking sludge was decomposed in the static pyrolysis furnace that was designed by our laboratory; its pyrolysis products were characterized by EPMA, GC and FT-IR. The results showed that the comprehensive utilization of deinking sludge was considerably feasible.
Key words:deinking sludge;pyrolysis;kinetics;TG-DTG
（责任编辑：马 忻）
乳液型环氧树脂改性聚乙烯亚胺纸张增强剂的研究
魏军凤 李小瑞* 李刚辉
（陕西科技大学化学与化工学院，陕西西安，710021）
摘 要：通过乳液型双酚A环氧树脂（BAE）对聚乙烯亚胺（PEI）进行改性，制备出了具有强阳离子性和反应活性的改性PEI纸张增强剂。讨论了增强剂组成、添加量和助留剂添加量等因素对纸张强度的影响，并用SEM对纸样微观结构进行了表征。结果表明，BAE树脂的引入可增加聚乙烯亚胺分子与纸纤维的结合强度，改性PEI可使纸张湿强度从14.46%提高到21.65%，环压指数提高42%；SEM分析表明，纸张断裂是由纤维断裂引起的，为改性PEI可增加纤维间的结合强度提供了依据。
关键词：聚乙烯亚胺；环氧树脂；纸张增强剂；环压指数
中图分类号：TS727+.1
文献标识码：A
文章编号：1000-6842（2009）01-0081-04
Modified Polyethylene Imine with Epoxy Resin Emulsion as Papermaking Strength Agent
WEI Jun-feng LI Xiao-rui* LI Gang-hui
(College of Chemistry & Chemical Engineering, Shaanxi University of Science & Technology, Xi’an, Shaanxi Province, 710021)
(*E-mail: lixr@sust.edu.cn)
Abstract：A kind of cationic paper strength agent was prepared through the modification of polyethylene imine (PEI) with bisphenol A epoxy resin (BAE) emulsion. The influence of composition, additive amount and retention aid of cationic modified PEI on paper strength was discussed and the microstructure of paper sheet was characterized by scanning electron microscope (SEM). The results showed that the bonding strength between PEI and paper fiber was increased, the wet strength enhanced from 14.46% to 21.65%, and the ring crush index improved by 42% with the addition of modified PEI. SEM analysis indicated that paper fracture was caused by fiber breakage, which provided basis for the fact that the modified PEI can increase interfiber-bonding strength.
Key words:polyethylene imine;epoxy resin;paper strength agent;ring crush index
（责任编辑：常 青）
ACS对钙离子吸附性能的研究
叶春洪 戴红旗* 王淑梅 王忠良 袁广翔
（南京林业大学江苏省制浆造纸科学与技术重点实验室, 江苏南京，210037）
摘 要：自制的ACS是一种带有支链的改性天然高分子物质，其羧基取代度为0.57，阳离子取代度为0.02。吸附动力学研究表明，ACS对Ca2+的吸附速率快，两者之间有较强的吸附作用力，且吸附动力学曲线只出现一个“平台”。等温吸附研究表明，ACS对Ca2+的吸附符合Langmuir模式和Freundlich模式，为单分子化学吸附。吸附量随pH值的升高而增加，当pH值＞6.5，并基本保持不变时，在实验浓度范围内，吸附量随着Ca2+初始浓度的增加而升高，当Ca2+加入量为3.93 mmol/L，ACS用量为2.0 g/L，pH值为6.5±0.1时，25℃、45℃、65℃的平衡吸附量分别为0.687、0.743和0.826 mmol/g；当Ca2+初始浓度为0.983 mmol/L时，ACS的用量为2.0 g/L达到最佳效果，用量继续增加，吸附量反而下降。
关键词：ACS；钙离子；吸附
中图分类号：TS727
文献标识码：A
文章编号：1000-6842（2009）01-0085-06
Study on the ACS as Adsorbent of Calcium Ions
YE Chun-hong DAI Hong-qi* WANG Shu-mei WANG Zhong-liang YUAN Guang-xiang
（Nanjing Forestry University, Nanjing, Jiangsu Province, 210037）
(*E-mail: daihq@njfu.com.cn)
Abstract：The ACS, a modified natural high molecular polymer having 0.57 mol/mol DS of carboxyl groups and 0.02 mol/mol DS of cationic, was used as the calcium ions adsorbent that can adsorb and transfer calcium ions from aqueous solution to fibers. The study result of adsorbing dynamic indicated that the adsorption rate of calcium ions onto ACS was fast, and the adsorption equilibrium time was about 90 min. The kinetic curve had one “plateau”, which revealed that there was one single molecular adsorption mechanism. The equilibrium data were found according to the Langmuir and Freundlich adsorption isotherms. The adsorption capacity increased with increasing pH and became almost constant when pH above 6.5. When the initial concentration of calcium ion was 3.93 mmol/L, the equilibrium adsorption capacities were 0.687 mmol/g, 0.743 mmol/g, 0.826 mmol/g at 25℃, 45℃, 65℃ respectively. When the initial concentration of calcium ion was 0.983 mmol/L, the adsorption capacity reached the maximum at the dose 2.0 g/L of ACS.
Key words:ACS;Ca2+;adsorption
（责任编辑：孙秋菊）
树脂酸钙的形成及其影响因素
叶春洪 戴红旗* 王淑梅 王忠良 袁广翔
（南京林业大学江苏省制浆造纸科学与技术重点实验室，江苏南京，210037）
摘 要：通过对自制的水溶性松香树脂酸钠模型物与一定浓度Ca2+作用下的树脂酸钙生成量及其影响因素等进行研究，模拟造纸实际生产过程中树脂酸与湿部系统中Ca2+作用生成的树脂酸钙障碍物及其影响因素。结果表明，Ca2+与水溶性或胶体性的树脂酸钠进行离子交换，生成黏性高且有聚集成大颗粒倾向的树脂酸钙。溶液中Ca2+浓度越大、pH值和温度越高，树脂酸钙生成量越大，且生成树脂酸钙所需的时间越短。
关键词：树脂酸钠；Ca2+；树脂酸钙
中图分类号：TS727+.2
文献标识码：A
文章编号：1000-6842（2009）01-0091-04
The Formation of Calcium Resinate and Its Affecting Factors
YE Chun-hong DAI Hong-qi* WANG Shu-mei WANG Zhong-liang YUAN Guang-xiang
（Nanjing Forestry University, Nanjing, Jiangsu Province, 210037）
(*E-mail: daihq@njfu.com.cn)
Abstract：In this paper, the calcium resinate forming mechanism and the affecting factors were studied by using the model compound of sodium resinate and Ca2+ to simulate the wet-end chemistry process. The research results showed that Ca2+ can be able to exchange the Na+ of the sodium resinate either in soluble or colloidal forms, which will produce calcium resinate that has high viscosity and conglomerating trend. The higher of ca2+ concentration, the pH value and the temperature, the higher of calcium resinate production, and the shorter reaction time.
Key words:sodium resinate;calcium ions;calcium resinate
（责任编辑：马 忻）
改性纳米CaCO3水相分散体系流变行为及其流变参数拟合(Ⅰ)
——铝锆偶联剂用量对分散体系流变行为的影响
唐艳军1 李友明2 薛国新1
（1.浙江理工大学先进纺织材料与制备技术教育部重点实验室,浙江杭州，310018;
2.华南理工大学制浆造纸工程国家重点实验室,广东广州，510640）
摘 要：采用铝锆偶联剂对纳米CaCO3进行表面改性，对改性纳米CaCO3水相分散体系的流变数据进行测定，并借助非牛顿流体模型实现流变参数的拟合。结果表明，在低剪切速率下，改性纳米CaCO3水相分散体系的表观黏度随着剪切速率的增大而下降，即剪切变稀，呈现假塑性流体特性；在高剪切速率下，随着剪切速率的增大，分散体系的表观黏度变化很小，呈现近牛顿型流体特性。采用铝锆偶联剂对纳米CaCO3进行表面改性，可明显改善纳米CaCO3在水相体系中的流动性，使屈服应力、零剪切黏度及极限黏度都明显减小。根据Herschel-Bulkley模型拟合结果，未经表面改性的纳米CaCO3水相分散体系的流动特性指数和屈服应力分别为1.489和2.767 Pa，呈现剪切变稠流动趋势，表明分散体系的不稳定性，部分粒子发生团聚；而经2.0%铝锆偶联剂改性的纳米CaCO3水相分散体系的流动特性指数和屈服应力分别为0.880和1.250 Pa，呈现明显的假塑性流体特性，分散体系流动性较好。
关键词：纳米CaCO3；流变；拟合
中图分类号：TS727+.3
文献标识码：A
文章编号：1000-6842（2009）01-0095-05
Rheological Experiment and Parameter Fitting of Modified Nanosized CaCO3 Dispersion in Water——Effect of Zircoaluminate Coupling Agent Amount on Dynamic Rheological Properties for the Dispertion
TANG Yan-jun1,* LI You-ming2 XUE Guo-xin1
(1. Zhejiang Sci-Tech University, Hangzhou, Zhejiang Province, 310018;
2. State Key Lab of Pulp and Paper Engineering, South China University of Technology,
Guangzhou, Guangdong Province, 510640)
(*E-mail:tangjy@zstu.edu.cn)
Abstract：Rheological experiment of aqueous dispersion of nanonized CaCO3 modified with zircoaluminate coupling agent was carried out, and the rheological parameters of the dispersion samples were also studied. The results showed that, at low shear rate, the dispersion containing modified nanosized CaCO3 exhibited the behavior of pseudoplastic fluid, characterized as obvious shear thinning. At high shear rate, the rheological behavior of the dispersion was similar to Newtonian liquid. It was inferred that surface modification process had profound effect on the flow behavior of nanosized CaCO3 in water. According to Herschel-Bulkley model fitting result, it was found that the flow behavior index and yield stress of modified nanosized CaCO3 dispersion was 0.880 and 1.250 Pa, showing the flow behavior of shear thinning, which was attributed to the good dispersion stability. However, in the fixed detection range, the flow behavior index and yield stress of unmodified nanosized CaCO3 dispersion was 1.489, 2.767 Pa respectively, exhibiting the rheological behavior of shear thickening, which was ascribed to the intense dispersion agglomeration.
Key words:nanosized CaCO3;rheological behavior;fitting
（责任编辑：赵旸宇）
自交联苯丙乳液的无皂聚合及其结构与表面施胶性能
李 翾 沈一丁* 费贵强 王海花
（陕西科技大学化学与化工学院，陕西西安，710021）
摘 要：以N-羟甲基丙烯酰胺作自交联单体，聚乙烯醇（PVA）为高分子分散稳定剂，采用无皂种子聚合制备了稳定的自交联苯丙乳液。当软硬单体比例n（BA）/n（St）=1.0，w（PVA）=6%，w（ODA）=10%，w（NMA）=6%时，自交联苯丙乳液具有优异的施胶效果，当用质量分数为1%的苯丙乳液进行表面施胶时，纸张施胶度可达43.0 s，表面强度达3.2 m/s，耐折度88次，环压指数达7.38 N·m/g；苯丙乳液与淀粉有良好的适配性，并可取得优异的复合施胶效果。通过动态激光粒径分析（DLLS）、差示扫描量热（DSC）等对乳液粒径及其分布和共聚物热转变性能及微相结构进行了表征。
关键词：无皂乳液共聚；苯丙乳液；表面施胶；自交联；表面增强
中图分类号：TS727+.5
文献标识码：A
文章编号：1000-6842（2009）01-0100-04
Self-crosslinking Styrene-acrylate Latex: Soap-free Synthesis, Structure
Characteristic and Sizing Performance
LI Xuan SHEN Yi-ding* FEI Gui-qiang WANG Hai-hua
(*E-mail: ydshen@sust.edu.cn)
Abstract：Using N-hydroxymethyl Acrylamide (NMA) as self-crosslinking monomer, and polyvinyl alcohol (PVA) as polymeric colloid stabilizer, a kind of self-crosslinking surfactant-free copolystyrene-acrylat latex with good stability and excellent sizing performance was successfully synthesized by the free-radical copolymerization. At the same time, the synthesis process was optimized. The emulsion is endowed with excellent sizing performance when n(BA)/n(St)=1.0, w(PVA)=6%, w(ODA)=10%, and w(NMA)=6%, and with 1.0% polymer emulsion addition, the sizing value can reach 43.0 s, and surface strength of the paper approaches 3.2 m/s, folding endurance 88 times， ring crush index 7.38 N·m/g. The polymer emulsion is compatible with starch very well, the mixture has excellent sizing performance, and the emulsion particle size distribution and its copolymers thermal performance and microphase structures were characterized by the method of DLLS, DSC and so on.
Key words:surfactant-free emulsion copolymerization；styrene-acrylate copolymer latex；surface sizing;self-crossliniking；surface strengthing
（责任编辑：陈丽卿）
顶空固相微萃取-气相色谱法测定黑液中甲醇含量的研究
刘海学 刘秋娟* 杨志岩
（天津科技大学天津市制浆造纸重点实验室，天津，300457）
摘 要： 研究了顶空固相微萃取-气相色谱（HS-SPME-GC）法检测非木材植物纤维原料蒸煮黑液中的甲醇含量，优化了顶空固相微萃取的萃取条件及气相色谱的检测条件。结果表明：在气液平衡温度60℃，气液平衡时间30 min，萃取时间11 min，解吸温度280℃，解吸时间5 min的条件下检测结果最佳。
关键词：黑液；顶空固相微萃取；气相色谱；甲醇
中图分类号：TS77
文献标识码：A
文章编号：1000-6842（2009）01-0104-04
The Application of Headspace Solid Phase-microextraction Gas Chromatograph for
Determination of Methanol Content in Black Liquor
LIU Hai-xue LIU Qiu-juan* YANG Zhi-yan
(Tianjin Key Lab of Pulp and Paper, Tianjin University of Science and Technology, Tianjin, 300457)
(*E-mail: liuqiujuan@tust.edu.cn)
Abstract：A new method named “headspace solid - phase microextraction-gas chromatography” (HS-SPME-GC) was developed to determine methanol content in non-wood pulping black liquor. The extraction and chromatopraphic conditions were optimized. The optimum conditions were as follows: 60℃ temperature for vapour-liquid equilibrium, 30 min gas-liquid equilibrium time, 11 min extraction time, 280℃ desorption temperature, 5 min desorption time. The method has good sensitivity and precision.
Key words:black liquor;HS-SPME;GC;methanol
（责任编辑：常 青）
圆柱型水力旋流器筛分纸浆纤维的数值模拟和实验研究
赖艳萍1 赖 维2，* 卢晓江2 范树礼2
（1.天津城市建设学院，天津，300384，
2.天津科技大学，天津，300222）
摘 要：用圆柱型水力旋流器对针叶木BCTMP浆纤维进行了筛分的实验研究。借助Fluent软件，采用RNG k-ε方程对圆柱型水力旋流器的流场进行了数值模拟,把纤维球形化后，利用 DPM离散相模型来模拟纤维和水的分离情况。模拟结果表明，在溢流中长纤维所占比例较大，在底流中短纤维所占的比例较大，与实验情况基本吻合。
关键词：水力旋流器；纤维；筛分；数值模拟
中图分类号：TS71
文献标识码：A
文章编号：1000-6842（2009）01-0108-04
Numerical Simulation and Experimentation for Fiber Fractionation in the Cylinder Hydrocyclone
LAI Yan-ping1 LAI Wei2,* LU Xiao-jiang2 FAN Shu-li2
(1. Department of Energy and Mechanical Engineering, Tianjin Institute of Urban Construction, Tianjin, 300384;
2. College of Mechanical Engineering, Tianjin University of Science & Technology, Tianjin, 300222）
(*E-mail: laiwei@tust.edu.cn)
Abstract：The internal flow field in a cylindrical hydrocyclone was simulated by using commercial CFD software FLUENT and the RNG k-ε model. After the fiber was sphercized, the separation of fiber from water in hydrocyclone was stimulated using DPM model. It was found that most of long fibers were in the overflow stream, and most of short fibers were in the underflow stream, which agreed well with the experiment. The conclusion acquired in this paper is significant both in theory or engineering application.
Key words:hydrocyclone;fiber;fractionation;numerical simulation
（责任编辑：王 岩）
综 述
瓜尔胶的改性及其在造纸中的应用
刘小莉 曹春昱 彭建军
（中国制浆造纸研究院，北京，100020）
摘 要：概述了瓜尔胶的结构和性质，重点介绍了其化学改性方法及不同类型瓜尔胶衍生物在造纸工业中的应用。
关键词：瓜尔胶；半乳甘露聚糖；化学改性；造纸助剂；应用
中图分类号：TS753.9
文献标识码：A
文章编号：1000-6842（2009）01-0112-06
Chemical Modification of Guar Gum and Its Application in Papermaking
LIU Xiao-li* CAO Chun-yu PENG Jian-jun
(China National Pulp and Paper Research Institute, Beijing, 100020)
(*E-mail: lxj999lxj@yahoo.com.cn)
Abstract：The structure and characteristics of guar gum were summarized, and the various modification methods as well as the applications of the modified guar gum in papermaking were mainly introduced in this paper.
Key words:guar gum;galactomannan;chemical modification;paper additives;application
（责任编辑：郭彩云）
阳离子分散松香胶的松香补充剂
宋兆萍 刘温霞
（山东轻工业学院造纸科学与技术省部共建教育部重点实验室，山东济南，250353）
摘 要：介绍了常用的松香施胶补充剂的基本特点、作用。松香补充剂是制备稳定的阳离子分散松香胶和保证其稳定施胶作用的重要辅助材料，常见的松香补充剂包括石蜡、松香酯化物、石油树脂、脂肪酸、合成施胶剂等。
关键词：松香补充剂；阳离子分散松香胶；施胶
中图分类号：TS753.9
文献标识码：A
文章编号：1000-6842（2009）01-0118-04
Rosin Extenders of Cationic Dispersed Rosin Size
SONG Zhao-ping* LIU Wen-xia
（Key Lab of Paper Science and Technology of Ministry of Education, Shandong Institute of Light Industry,
Ji’nan, Shandong Province, 250353）
(*E-mail: pingzi221@163.com)
Abstract：Rosin extender is important auxiliary material for preparing stable and efficient cationic dispersed rosin size. The common rosin extenders include paraffin wax, rosin ester, petroleum resin, fatty acid and synthetic sizes. Their characters and performances are reviewed in this paper.
Key words:extender;rosin;dispersed cationic rosin;sizing
（责任编辑：王 岩）
打浆过程控制的新进展
汤 伟 罗 斌 周 红 王孟效
（陕西科技大学电子与信息工程学院，陕西西安，710021）
摘 要：全面介绍了打浆过程机理模型、打浆过程动态建模、成浆质量软测量技术、打浆过程在线检测仪表，以及打浆过程控制方案及算法的研究进展与应用现状，讨论了亟待解决的关键技术和对策，指出了努力方向及发展趋势。
关键词：打浆过程；动态建模；软测量；优化控制
中图分类号：TS752
文献标识码：A
文章编号：1000-6842（2009）01-0122-08
The Progress of Refining Process Control
TANG Wei* LUO Bin ZHOU Hong WANG Meng-xiao
(Faculty of Electronics and Information Engineering, Shaanxi University of Science and Technology, Xi’an, Shaanxi Province, 710021)
(*E-mail: wtang906@163.com)
Abstract：The study progress and application status of refining modeling, dynamic mathematical model for refining process, refined-pulp quality soft measurement technique, on-line measuring instrument of refining process and the control scheme and algorithms employed were comprehensively introduced, and the difficulties encountered in refining process control were discussed. Potential approaches for refining process control were presented.
Keywords:refining process;dynamic modeling;soft measurement;optimal control
（责任编辑：关 颖） | 
