漂白竹浆碱抽提制备溶解浆的研究

以漂白竹浆为原料,通过碱抽提技术制备竹溶解浆,并用X射线衍射仪研究竹浆中纤维素晶型结构的变化,用场发射扫描电镜(FE-SEM)观察纤维表面形貌的变化,采用凝胶渗透色谱(GPC)分析碱抽提后竹浆相对分子质量分布(MWD)。经碱抽提后,采用盐酸进行酸处理,以调控溶解浆的聚合度、灰分和白度。研究结果表明:在浆质量分数10%条件下,Na OH质量分数10%,温度30℃,时间60 min,半纤维素脱除率可达66.71%;FE-SEM观察到半纤维素的去除减少了纤维表面原纤化现象,增大纤维横向宽度,增加了纤维柔软性及卷曲性;GPC分析表明多分散系数(PDI)随半纤维素的去除逐渐下降,由7.71降至4.43,竹浆相对分子质量增加,提高了相对分子质量分布的均一性。酸处理过程使残余半纤维素质量分数降至7.02%,竹溶解浆纤维素纯度高达94.25%。     

微波辐射法竹浆纤维素的中性TEMPO氧化及表征

采用微波辐射法和中性2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)自由基氧化工艺来预处理竹浆纤维素,之后用超声波机械处理制备微纤化纤维素。实验结果表明,在60℃下,TEMPO用量为0.15 mmol/g(以绝干浆计,下同),Na Cl O2用量为10 mmol/g,Na Cl O用量为1 mmol/g,微波氧化2 h,其羧基含量最高到达0.729 mmol/g,氧化效果最佳,超声波处理后微纤化纤维素得率高达85.7%。FT-IR分析表明纤维素氧化后引入羧基官能团;XRD结果揭示纤维素氧化反应只发生在纤维素的无定型区或结晶区表面;纤维素氧化前后的聚合度(Dp)结果表明相对于碱性氧化,微波辐射和中性TEMPO氧化对纤维的降解程度低,从而有效地保持了纤维素原本的长度。     

乙酸预处理对木质纤维素结构及性能的影响

对木质纤维素进行乙酸预处理及三段磨浆,分析了不同试样的化学组分,并进行了结构表征。结果显示,经乙酸预处理及三段磨浆后,相思木木片表面出现大量坍塌、裂纹及孔洞,纤维间的结合也变得更为疏松,木片超微结构受到不同程度的破坏。试样中半纤维素含量显著降低,纤维素及木质素所占比例相对增加,纤维素的结晶度指数有所降低。核磁共振波谱(P31NMR)分析结果表明,经预处理及磨浆后,试样中木素的脂肪族羟基含量降低,酚羟基含量增加,酚型/非酚型木素值增加,S/G(紫丁香基/愈创木基型木素)值增加,且随着预处理温度的升高,酚型/非酚型值下降,S/G值增加。热重-红外(TG-IR)分析结果表明,经预处理及磨浆后,DTG曲线在280℃左右少一个肩峰,半纤维素的降解产物木聚糖的特征吸收峰大幅降低,纤维素降解产物的特征吸收峰强度略微增强,木质素热解产物的特征吸收峰强度略有下降。为探讨预处理及磨浆对木质纤维素孔结构的影响,采用低温氮气吸附法(BET)对试样进行分析,结果显示,试样的比表面积增大,大孔所占比例减小,介孔所占比例增加。     

中国竹材制浆造纸及高值化加工利用现状及展望

竹材是一种优良的纤维原料,可用于制浆造纸和提取竹原纤维。竹材的纤维形态、化学成分基本介于针叶木和阔叶木之间,漂白竹浆的品质与木浆相当。虽然竹子存在半纤维素和灰分含量较高等不足,但其α-纤维素含量较高,可制取高得率级溶解浆。竹浆是中国造纸工业鼓励发展的浆种,目前产能在200万t/a以上,且今后几年将出现快速增长势头。竹浆厂每年产生大量的纤维类废弃物。以竹浆生产为主线,提供多种高附加值产品,将是未来竹浆企业获得可持续健康发展的盈利模式。生产溶解浆、生活用纸等新型差异化终端产品,并对制浆过程产生的纤维类废弃物进行高附加值综合利用,制备阻燃型保温材料、乙醇和丁醇等生物质燃料,以及纳米纤维素微晶产品,是现在竹浆企业可供选择的发展路径。竹原纤维具有天然抗菌抑菌性、吸湿除臭、抗紫外光、隔音隔热性等功能特性,是生产高档服装、吸附材料和隔热隔音材料的良好纤维原料。竹原纤维的生产目前已实现工业化,但产业规模有待提高,产品标准亟待制定和完善。     

制备竹LYOCELL纤维对原料竹浆的要求

简要介绍了竹Lyocell纤维的制备原理和工艺,阐述了原料竹纤维素的聚合度对其在氧化甲基吗啉溶剂中溶解性能的影响,介绍了制取竹Lyocell纤维的竹浆原料的精制纯化方法,并提出制备竹Lyocell纤维对竹浆原料--竹纤维素的要求.     

漂白竹浆疏水改性纳米纤丝化纤维素的制备和表征

纳米纤丝化纤维素(NFC)通过化学改性的方法可以赋予其特殊表面性质。研究以漂白竹浆为原料,采用机械(球磨机和高压均质机)和化学改性相结合的方法,制备改性纳米纤丝化纤维素(m-NFC)。在球磨中使用丁酰氯为酰基化试剂,N,N-二甲基甲酰胺(DMF)为分散剂,降低纤维尺寸的同时对纸浆纤维进行化学改性,再经高压均质机处理制备了取代度为2.07的m-NFC。利用激光粒度分析仪、原子力显微镜(AFM)、傅里叶红外光谱(FTIR)、X射线衍射仪(XRD)对m-NFC的结构和形态进行表征。均质20次最高压力80 MPa制备的mNFC微纤丝长度为316.9 nm,直径分布在25~80 nm范围内,强物理机械力作用改变了m-NFC的晶体结构。改性后的m-NFC在低极性溶剂丙酮中具有较好的分散稳定性。研究结果可为纳米纤丝化纤维素应用于疏水性生物基质材料制备提供依据。     

麦草化学机械制浆预处理方法研究

使用麦草原料制取漂白化学机械浆,为了后续多段漂白能够获得高白度的纸浆,研究了3种不同的化学药品用于预浸渍阶段对未漂白浆的光学和物理性能的影响,包括成浆白度、成浆强度指标、纤维筛分级分,并比较了磨浆的比能耗和废水污染负荷.研究结果表明,与碱性过氧化氢(2.0%NaOH、1.5%H2O2、0.4%DTPA)处理(P工艺)磨浆相比亚硫酸钠(2.0%Na2SO3、2.0%Na2CO3、0.4%DTPA)预处理(S工艺)磨浆比能耗降低了33%,果胶酶(10IU/g以绝干浆计)/碱性过氧化氢(2.0%NaOH、1.5%H2O2、0.4%DTPA)预处理(Pe/P工艺)也可以降低磨浆比能耗10%,P工艺预处理与S工艺预处理均能提高成浆白度,Pe/P工艺预处理成浆呈现暗红色;P工艺预处理成浆物理强度高于其他两种浆;S工艺预处理磨浆段废水化学耗氧量(COD)发生量较高,达到84.09kg/t(以绝干浆计).     

打浆过程预添加CMC对杨木APMP浆悬浮液屈服应力的影响

为考察打浆过程中添加羧甲基纤维素钠(CMC-Na)对杨木碱性过氧化氢化学机械浆(APMP浆)悬浮液屈服应力的影响,在分析杨木APMP浆打浆度与屈服应力关系的基础上,先添加一定量的CMC-Na对杨木APMP浆进行预处理10 min后,再分别用瓦利打浆机和PFI磨打浆处理,分析不同打浆方式以及添加CMC-Na预处理后对杨木APMP浆的打浆度和屈服应力的影响。结果表明:对于相同打浆度的杨木APMP浆,屈服应力(τ_y)随着浆料质量分数(C_m)的增加而迅速增加,且符合指数方程τ_y=aC_m~b,其中a与b值与打浆方式和打浆度的大小密切相关;经低浓度游离状的瓦利打浆机处理的浆料,其屈服应力随着打浆度的增加而减小,而中高浓度黏状的PFI磨打浆处理结果则相反。打浆过程预添加CMC-Na时,浆料打浆度随CMC-Na添加量(以绝干浆质量计)的增加先升高后降低;当CMC-Na添加量为2%并预处理10 min时,经瓦利打浆机处理的浆料打浆度可由45°SR提高到48°SR,而经PFI磨处理的浆料打浆度可由40°SR提高到50°SR,并且浆料悬浮液的屈服应力均达到最低值,分别为16.4和22.8 Pa(浆料质量分数为3%)。     

球磨对胡桑木粉可及度影响的研究

为了提高木粉改性反应时试剂对木粉的可及度,采用行星式球磨机对胡桑木粉进行球磨预处理,研究了干磨、加水湿磨以及球磨时间对木粉的粒度、结晶度和可及度的影响。研究结果表明:胡桑枝条木粉干磨4 h粒度达到最低值,中位径(D50)为8.982μm,纤维素结晶度明显降低;4 h后由于发生团聚现象,粒度反而随球磨时间延长而增大,结晶度不再变化;干磨木粉的粒度越小,木粉的可及度越高。湿磨时,由于水的分散阻聚作用,粒度随球磨时间的延长逐渐减小,球磨12 h原料D50达到4.357μm;木粉湿磨后不同干燥方式对木粉的结晶度和可及度影响很大:湿磨木粉经烘箱干燥后的结晶度显着高于冷冻干燥的;烘箱干燥的湿磨木粉可及度比未球磨木粉小,且随湿磨木粉粒度的减小而降低;冷冻干燥的湿磨木粉可及度与未球磨木粉相比明显提高,而且高于干磨时间相同的木粉。     

离子液体预处理对纸浆酶漂效果的研究

以杨木碱性过氧化氢机械浆(APMP)、化学热磨机械浆(CTMP)、硫酸盐浆(KP)和麦草CTMP 4种浆为原料,对纸浆在应用生物酶漂白前利用离子液体进行温和预处理,控制离子液体BmimC l用量为1.0%(以绝干纸浆质量计,下同)、EmimD MP用量为1.2%,研究发现离子液体预处理可明显改善纸浆的酶漂效果,且EmimD MP的效果更优。表现为应用离子液体预处理后成纸的光学性能及物理强度明显改善,EmimD MP预处理后杨木KP浆白度可提高4.27%(ISO),不透明度增加了2.46%,麦草CTMP成纸的抗张指数、耐破指数、环压指数、撕裂指数及耐折度分别增加12.21%、29.80%、22.45%、44.82%和52.50%。纤维质量分析仪(FQA)、X射线衍射(XRD)和扫描电镜(SEM)分析结果显示,离子液体处理后4种纸浆纤维质量提高,平均长度增加,细小纤维含量降低,纤维结晶度提高,其中EmimD MP处理后杨木KP浆结晶度提高了11.21%,纸浆表面发生明显分丝帚化,增加了药液的渗透能力。     

两种商品木浆的纸浆性能研究

选取市场上具有代表性的两种商品针、阔叶木浆进行PFI打浆处理,研究在不同打浆度下浆料纤维质量、动态滤水性能、Zeta电位、微观结构等方面的变化,并对不同比例配抄条件下的成纸性能进行考察,结果表明:针、阔叶浆的打浆度与打浆转数之间的关系均符合线性分布:y=17.7503+0.0015x,R^2=0.9914(针叶浆);y=8.8986+0.00275x,R^2=0.9734(阔叶浆);经PFI打浆后,两种木浆纤维长度、宽度变化较小,细小组分含量变化明显;随着打浆度的升高,两者的滤水性能下降,Zeta电位先上升然后基本保持不变;初始打浆度下,随着针叶浆比例的减少、阔叶浆比例的增加,成纸的抗张强度先下降再增大,厚度逐渐下降至不变,定量逐渐增加,柔软度逐渐下降;随着打浆度的升高,成纸的抗张强度增大,厚度、定量逐渐下降,针叶浆成纸柔软度逐渐下降,阔叶浆成纸柔软度先升高再逐渐降低。     

A morphological study on the behavior of bamboo pulp fibers in the beating process

Summary Bamboo pulp fibers respond to beating more rapidly than do wood fibers. This is probably due to the difference in secondary wall structure between the fibers. In the present paper, the behavior on beating of pulp fibers from Bambusa polymorpha Munro was investigated from a morphological point of view. The secondary wall of bamboo fibers consists of alternately arranged broad and narrow layers. During the beating process, a number of transverse and concentric cracks are generated in the broad layers, which causes an internal fibrillation. The outer broad layers with their numerous cracks separate from the inner layers and swell highly toward the outside. The outer secondary wall layer of bamboo fibers has a microfibril angle of about 20° with respect to the fiber axis which is much smaller than that of the S1 layer of wood fibers. As a result this layer appears to offer little resistance to prevent the external swelling of the broad layers.Part of this work was financially supported by a Grand-in Aid for Scientific Research, Ministry of Education, Japan, 57470095Currently with the Japan Pulp and Paper Research Institute, Inc., Tsukaba, Japan     

竹原纤维和竹粉纤维形态和化学成分分析

以3年生毛竹材为原料,研究了毛竹竹粉和竹原纤维的纤维形态和化学成分。纤维形态分析结果表明:竹原纤维的宽度(143μm)与竹粉(136μm)相当,长度(22.63 mm)远高于竹粉(0.61 mm),使其长宽比(158.25)远高于竹粉(4.49)。化学成分分析表明:竹原纤维的纤维素含量(65.6%)比竹粉(37.3%)高得多,聚戊糖含量(17.1%)略低于竹粉(20.1%)。竹粉中的木质素含量为24.5%,是竹原纤维中木质素含量(11.5%)的2倍多。竹原纤维的高纤维素含量和低木质素含量是其广泛应用于制浆造纸行业的重要原因。     

竹浆纤维红外光谱分析及再生纤维素纤维市场简析

通过有效检测竹浆中的纤维素纤维的红外吸收光谱,并利用红外光谱仪等多种专业仪器来分析多种纤维素纤维的差别,可以得出纤维素纤维的结构差异性,从而有助于将其利用在工业化量产之后,结合其自身特性来区分应用方向。同时对再生纤维素纤维市场进行简析,为相关行业企业尽早做好应对贸易摩擦造成的负面影响准备提供参考。     

Acetic acid pulping of wheat straw under atmospheric pressure

Atmospheric acetic acid pulping of wheat straw was carried out. Pulping conditions and their effects on pulp properties were investigated in detail, and a comparison between acetic acid (AcOH) pulp and soda-anthraquinone (AQ) pulps of wheat straw was made of the chemical composition, strength, and fiber morphology of the pulps. Wheat straw was successfully pulped and fractionated into pulp (cellulose), acetic acid lignin, and sugars (monosaccharides from hemicellulose), making it easy to utilize them. It was found that among the pulping conditions the dosage of H₂SO₄ as catalyst was the most notable, and the extent and rate of delignification could be controlled by varying the amount of the catalyst. The results also showed that acetic acid pulp was quite different from soda-AQ pulp. About 70% of the ash or 90% of the silica in wheat straw were kept in AcOH pulp. The ash might function as filler and be beneficial to the printability of paper. It was known that many epidermal cells existed in AcOH pulp in bundles or in single cells. These ash-rich nonfiber cells seemed to hinder the bonding between fibers. AcOH pulp had lower strength than soda-AQ pulp, which might result mainly from the chemical damage of fibers caused by acid, not from the depolymerization of cellulose.Part of this paper was presented at the 65th Pulp and Paper Research Conference of Japan TAPPI, Tokyo, June 1998     

竹三醋酸纤维素酯的研制

一、前言三醋酸纤维素酯(以下简称CTA)广泛应用于感光片基、人造丝、香烟过滤嘴丝束、反渗透膜、超滤膜、塑料、涂料、电气绝缘材料、火药助剂、透明薄膜等。不同产品性能对CTA品质的要求也有所区别,对CTA品质要求最高的是感光片基,高质量的CTA应用于感光片基,能使片基的透明性优良、尺寸稳定、机械强度适中、使用安全。国内外醋酸纤维厂家生产CTA时,绝大部分是以棉短绒为原料,用竹材作为原料制备CTA,国内尚未见报导。我们     

Characterization and acetylation behavior of bamboo pulp

In the present study, the chemical–physical properties of bamboo pulp prepared with a sequential totally chlorine-free procedure were analyzed and compared with that of commercial wood pulp by SEM, FTIR, TGA, and X-ray. α-Cellulose content was determined to be 95%, a little less than that of commercial wood pulp. But the crystallinity of bamboo pulp is lower than wood pulp. Acetylation activity of bamboo pulp was determined to be higher than that of wood pulp, which was carried out in heterogeneous media with sulfuric acid as catalyst. The cellulose acetate prepared with bamboo pulp can be quickly dissolved in acetone without distinct difference with that of cellulose acetate prepared with wood pulp. The results indicate the potential utility of bamboo as an alternative to wood pulp for cellulose derivate fiber material.     

球磨-酶解法制备纳米竹纤维的结构表征

采用机械球磨对竹纤维进行预处理,再经纤维素酶水解制备纳米竹纤维。通过光学显微镜(OM)、透射电子显微镜(TEM)、傅立叶红外光谱仪(FTIR)和X射线衍射仪(XRD)对竹纤维的形貌、组成、光谱学性能以及晶体特性进行了表征。实验结果表明:球磨法和酶解法在一定程度上都可以细化竹纤维;球磨预处理有助于竹纤维的酶解过程,且球磨-酶解法制备的纳米竹纤维粒径在100 nm左右;所制备的纳米竹纤维仍然保持竹纤维的基本化学结构,但球磨处理破坏了纤维素的结晶结构,其结晶度由64.15%降低到了38.55%。     

Accessibility, reactivity and supramolecular structure of E. globulus pulps with reduced xylan content

The correlation of structural assembly on a molecular level with macroscale properties such as accessibility and reactivity was investigated. A series of TCF-bleached E. globulus kraft dissolving pulps was prepared aiming at a specification suitable for viscose application. The removal of xylan to a comparable level was achieved by different pre- and post-treatments. Solid-state CP-MAS ¹³C NMR was used to determine the degree of order and the lateral fibril dimensions of cellulose fibrils. The results of the NMR measurements were related to the processability of these pulps during viscose manufacture, expressed in terms of filterability of the viscose dope and its amount of undissolved particles. The cellulose crystallinity did not affect the pulp reactivity. It was noticed that the cold caustic extracted (CCE) pulps revealed both large fibril aggregate width as determined from NMR data and low reactivity toward xanthation at the same time. These pulps exhibited significantly higher amounts of alkali-resistant xylan than those prepared by prehydrolysis kraft cooking.