摘要
论文以尾巨桉为原料,测定其材性,并采用不同制浆方法、生物预处理及不同漂白程序,添加表面活性剂和干强剂,对其制浆适应性进行了系统研究,为尾巨桉的工业应用提供数据和理论指导。
对尾巨桉材性和APMP制浆工艺及其机理进行研究,结果发现:尾巨桉相比于其它桉木的综纤维素含量高(75.8%),木材色泽较浅,基本密度比较小(0.487g/cm~3),纤维长宽比最大61,柔性系数比较大;得到尾巨桉APMP较适宜的化学预处理条件,尾巨桉APMP的白度达到了66%ISO,运用NOSA统计软件对试验结果进行了方差分析,得出了尾巨桉APMP裂断长、白度与化学预浸条件的回归方程。
对不同立地条件下尾巨桉KP-AQ的制浆工艺进行研究。研究发现东门和雷州尾巨桉材性差别不大。得出东门和雷州尾巨桉尾巨桉KP-AQ制浆的蒸煮工艺条件比较相近。
对雷州尾巨桉KP-AQ浆进行漂白研究,得出常规D_1-E-D_2-P漂后浆白度为81.1%,黏度为972mL/g。通过丙酮抽滤后,白度上升到83.2%;用Mg(OH)_2代替NaOH的漂后浆白度为81.0%,黏度为931mL/g;原浆经氧漂后白度为58.4%,黏度为914mL/g,卡伯值为7.76;O-D_1-E-D_2漂后纸浆白度为86.0%,黏度为872mL/g;O-D-E-P漂后纸浆白度为85.4%,黏度为883mL/g。
用T.lanuginosus产木聚糖酶预处理雷洲尾巨桉KP-AQ浆,得出最佳工艺条件为:木聚糖酶用量10U/g,反应时间90min,处理温度60℃,pH值6.0,浆浓度10%。纸浆白度为55.2%,卡伯值为8.38。纸浆黏度有所提高,木聚糖酶助漂后纸浆物理强度有所增加。研究生物漂白机理得出:木聚糖酶处理后,浆中聚戊糖的含量下降了3.51%,酸不溶木素含量下降了0.12%。经X射线衍射仪分析,木聚糖酶处理前后纤维素的结晶度变化不大。扫描电镜分析得出,未经木聚糖酶预处理纸浆纤维表面比较光滑,结构紧密。经过预处理浆纤维表面出现了孔隙。对照浆和酶解浆的红外光谱和酶解液紫外光谱分析得出,木聚糖酶生物处理后纤维上产生游离羟基,增加了纤维间的氢键结合。木聚糖酶降解了纸浆中的部分木聚糖,溶出纸浆中的少量木素。与其它木聚糖酶相比,由T.lanuginosus产木聚糖酶预处理浆料黏度提高,酶用量少。
雷洲尾巨桉KP-AQ浆TCF漂白的O-X-Mn-P中,纸浆白度达到80%,而黏度在800mL/g以上;轻(超轻)ECF工艺漂白尾巨桉KP-AQ浆,O-X-A-D_1-Ep-D_2漂白效果较好。总用氯量为0.95%时,纸浆白度达到85%以上。比达到相同白度的常规ECF(O-D_1-E-D_2)节省60%ClO_2,比O-D_1-Ep-D_2漂白工艺节约40%ClO_2,降低了漂白废水污染负荷。
研究了表面活性剂在尾巨桉AS-AQ制浆及其各段漂白中的作用及机理。得到了添加LAS尾巨桉AS-AQ蒸煮的最佳条件,LAS能够使纸浆得率增加,白度提高,黏度增加,保水值增加,苯醇抽出物降低;加入LAS并没有使蒸煮液中蒽醌颗粒的粒径减小,蒸煮液中小于0.45μm粒径的蒽醌浓度在常温下比无LAS要低35%;LAS使木片内部的蒽醌含量大幅度的增加,使100℃和120℃的磺酸基数量提高了。
在氧漂过程中最优的助剂为复合型表面活性剂(0.25%LAS和0.25%AEO-9)使白度增加3.6度,卡伯值降低1.3,黏度稍有降低;木聚糖酶在Tween80加入量20mg/mL时,酶活达到最大并提高27%;H_2O_2漂白的最佳助剂为NP系列,加入0.25%NP-10和0.75%NP40时,HLB值为16.1时效果最佳;在O-X-Q-P各段均加入助剂,可以使白度增加5.1度,手抄片纸浆物理强度增加。
研究了添加壳聚糖类和淀粉类干强剂的效果。通过壳聚糖接枝共聚物的合成,将其应用在尾巨桉KP-AQ浆中。结果表明,CTSAD(壳聚糖-丙烯酰胺-二甲基二烯丙基氯化铵)比CTS(壳聚糖)各项物理强度指标提高明显,且用量较少。电子显微镜下看出,加入助剂后纤维交织状况更加密集,尤其加CTSA后,纤维交织的密集程度较之空白纸样有很大提高。
探讨了阳离子淀粉-丙烯酰胺二元接枝共聚物、CTSAD三元接枝共聚物及混合使用工艺条件及其增干强效果。接枝率为35.59%阳离子淀粉-聚丙烯酰胺应用效果很好。用量在0.8%,打浆度在46°SR附近,成纸的撕裂指数由4.7mN·m~2/g提高到9.5mN·m~2/g,耐折度由229次提高到278次,抗张指数由74.70N·m/g提高到147.94N·m/g。对于混合增强剂,在反应温度40℃,pH8.5,阳离子淀粉-丙稀酰胺二元接枝共聚物与C他SAD三元接枝共聚物之比为5:5时,纸张的撕裂度、耐折度、抗张指数分别得到显著提高,并为碱性造纸和低定量造纸提供可能。
Using E.urophylla×grandis as the material,this research systematically studied the pulpability with different pulping methods,bio-pretreatment and bleaching sequence,by adding surfactant and reinforcing agent,which can be very useful for the industry application of E.urophylla×grandis.
The study of the physical properties of E.urophylla×grandis and APMP pulping process showed that E.urophylla×grandis contained more homocellulose(75.75%),had lighter color and lower base density(0.487g/cm~3) with the length-width ratio of 61.0 and a fairly large flexibility index.The appropriate APMP chemical pretreatment conditions for E.urophylla×grandis were as follows:for the 1~(st) stage presoak,5.5%of NaOH,1%of H_2O_2,1%of Na_2SiO_3,0.5%of MgSO_4,0.3%of EDTA,were added,and the process lasted 45min at 75℃with the wood to liquor ratio at 1:4;for the 2~(nd) stage presoak,2.5%of NaOH,5%of H_2O_2,3%of Na_2SiO_3,0.5%of MgSO_4,0.3%of EDTA were added,and the process lasted 45min at 75℃with the wood to liquor ratio at 1:5.The brightness of E.urophylla×grandis APMP pulp reached 66%ISO,NOSA statistic software was applied to analyze the variance of data,the regression equation of breaking length,brightness,and presoak condition were obtained.
The study of the pulpability of E.urophylla×grandis KP-AQ was studied at different planted distance.It was found that the physical properties of Dongmen E.urophylla×grandis and Leizhou E.urophylla×grandis were almost same.So the KP-AQ cooking condition of E.urophylla×grandis Dongmen and Leizhou E.urophylla×grandis in southern China was quite similar.
The study of the bleachability of Leizhou E.urophylla×grandis KP-AQ showed that after D_1-E-D_2-P bleaching,pulp brightness was 81.1%and the viscosity was 972mL/g.Brightness increased to 83.2% after it was extracted treatment by acetone.Pulp brightness reached 81.0%and its viscosity was 931mL/g when NaOH was replaced by Mg(OH)_2.GE brightness reached 58.4%,viscosity was 914mL/g and Kappa number was 7.76 after the D_1-E-D_2-P bleaching.Brightness and viscosity became 86.0%and 872mL/g respectively after the O-D_1-E-D_2 bleaching.After O-D-E-P bleaching,they were 85.4%and 883mL/g respectively.
The optimum conditions to pretreat Leizhou E.urophylla×grandis by using T lanuginosus were:10 U xylanase/g pulp,reaction time 90 min,temperature 60℃,pH 6.0 and consistency 10%.Pulp brightness was 55.2%,its kappa number decreased to 8.38 and the viscosity rose slightly.The strength properties increased slightly after bleaching.After studying bleaching mechanism,it was found that xylan in pulp decreased by 3.51%,and its acid indissoluble lignin decreased by 0.12%.XRD did not show considerable change in crystallinity.The SEM study showed the pulp had a more compact structure and smoother surface without xylanase pretreatment.IR and UV spectra proved that free hydroxyl may increase hydrogen bonding.Xylanse degraded some xylan and dissolved small bit of lignin.Compared with other xylan,the viscosity of the pulp increased after the treatment of T lanuginosus,and the amount of the xylan decreased.
KMnO_4 charge was 0.6%in TCF(O-X-Mn-P) bleaching of Leizhou E.urophylla×grandis KP-AQ. The pulp brightness reached 80%and viscosity was more than 800mL/g.Light(superlight) ECF bleaching of KP-AQ had better effect by O-X-A-D_1-Ep-D_2.The pulp brightness reached over 85%at a total chlorine charge of 0.95%,which saved 60%and 40%ClO_2 respectively compared with the O-D_1-E-D_2 and O-D_1-Ep-D_2.
The study of the effect and mechanism of surfactants in AS-AQ pulping and bleaching showed that the optimum conditions by adding LAS were as follows:12-13%of NaOH(as NaOH),16-18%of Na_2SO_3(as NaOH),0.06-0.1%of AQ,0.2-0.3%of LAS,120-140 min at maximum temperature.Pulp yield,brightness,viscosity and WRV were increased by adding LAS,while benzene-alcohol extractives were decreased.The addition of LAS did not decrease the particle size of anthroquinone in cooking liquor.The concentration of anthroquinone whose diameter is smaller than 0.45μm is 35%lower at room temperature than the cooking liquor without LAS.The amount of anthroquinone increased tremendously by adding LAS,which led to the increasing of sulfite at 100℃and 120℃.
The best additive in oxygen bleaching was compound surfactants(0.25%LAS and 0.25%AEO-9), which can increase brightness by 3.6%and decrease kappa number and viscosity by 1.3 and 36mL/g respectively.Xylanase activity reached its maximum value and increased by 27%at the presence of 20mg/mL Tween80.NP series was the best additives for peroxide bleaching;the maximum effect was reached with an addition of 0.25%NP-10 and 0.75%NP40 with a 16.1 of HLB value.Pulp brightness increased by 5.1%and the hand sheets had better physical strength properties by adding the additive in the different stages of O-X-Q-P.
The effects of different strength agents were studied.Grafting copolymer with chitosan was applied in KP-AQ pulping.The results showed that the pulp properties improved more appreciably with the application of CTSAD than CTS,and the amount of CTSAD used was smaller than that of CTS. Microscopic graph showed more compact fiber interweaving after the application of these additives, especially the application of CTSA.The density of the fiber interweaving increased dramatically compared with the control samples.
The study of the strength enhancing effect of Starch-PAM bi-copolymer,CTSAD tri-copolymer and their mixture showed that the better strength enhancing effect achieved when grafting ratio of starch-PAM was 35.59%.At a dosage of 0.8%and 46oSR of beating degree,the tearing index increased from 4.7mN·m~2/g to 9.5mN·m~2/g,folding endurance enhanced from 229 to 278 times,tensile index rose from 74.70N·m/g to 147.94N·m/g.As for their mixture,tearing index increased by 14.9%,the folding times enhanced by 96.0%;the tensile index improved by 82.7%when the reaction temperature was 40℃,pH8.5,and starch-PAM grafting bi-copolymer to CTSAD grafting tri-copolymer ratio was 5:5,which will be very helpful to the basic and low weight papermaking.
引文
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