CN101124362A - 环糊精用于降低纸浆和纸的泛黄/返黄的应用 - Google Patents
环糊精用于降低纸浆和纸的泛黄/返黄的应用 Download PDFInfo
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Abstract
本发明涉及在纸生产期间形成颜色从而导致纸浆或纸的泛黄/返黄问题。使用本发明的方法可以降低这些泛黄/返黄，该方法涉及降低纸浆和纸的泛黄，包括在洗涤之前或期间在纸浆中添加或形成环糊精。
Description
发明领域
本发明涉及一种用于防止或降低纸和纸浆的泛黄(yellowing)/返黄(色退)(brightness reversion)的方法。
发明背景
作为第一步，纸的生产涉及从木材形成纸浆。在常规的硫酸盐法制浆(kraft pulping)工序中，将原木片或预处理的木片在碱和硫化物的存在下在高压和高温下蒸煮以溶解在单个木材纤维之间的聚合木质(lignaceous)物质。释放出的纤维仍然在纤维壁内包含相当量的有色木质物质，通过常规的漂白工序/化学作用可以不同程度地除去这些木质物质。取决于木材的种类、制浆的条件和漂白方法，漂白木纤维可以包含不同量的残留木质素和抽出物(例如树脂酸，脂肪酸，甘油三酯，萜烯，萜类化合物，蜡等等)。由漂白纤维制备的包含痕量残留木质素和/或抽出物(extractive)的纸和纸浆伴随着对高温时的回色/返黄的增加的敏感度。当漂白纤维转变为最终的纸制成品时，在常规的运输和存储操作期间或在干燥部内和在纸张卷纸机(reel winder)处可能遇到上述极端的高温。
在这些温度，热敏的发色团前体，如木质素、抽出物以及源自碳水化合物的氧化、缩合和环化产物(例如，2-糠醛，羟甲基糠醛等等)可以转变为发色团，导致最终产品的泛黄(回色)或返黄，而这是不希望的。因此优选在整个制浆、漂白和造纸工序的洗涤阶段去除上述发色团前体。目前，需要更强烈的洗涤工况来去除上述形成颜色的组分，这是通过新设备的投资和/或现有设备升级来实现的。通常这不仅相应增加水和能量的消耗，而且额外的洗涤可能增加得率的损失。降低发色团前体浓度的另一个方法是在漂白序列中引入另外的步骤，这不仅需要显著的资本支出，而且需要增加化学药品的使用。即使经过所述处理，某些形成颜色的物质仍然可能保留在洗涤的纸浆中(尤其是源自碳水化合物的那些)。
发明概述
现已发现，不希望的发色团前体，被截留环糊精配合物内时，可以在形成纸浆的洗涤阶段去除。
因此本发明涉及用于在常规应用(例如贮存、载运，纸的生产、存档、等等)相关的条件中降低或防止纸浆和纸泛黄/返黄的方法，该方法包括将纸浆中存在的发色团前体截留在环糊精的环内和除去所得的包合配合物，如在常规的洗涤期间通过在洗涤之前或期间添加或形成环糊精。
因此本发明的一方面涉及用于降低纸浆和纸的泛黄/返黄的方法，该方法包括直接将环糊精添加到纸浆中或原位形成环糊精，然后通过随后的洗涤步骤除去形成的环糊精包合配合物。
发明详述
本发明涉及纸的制造和减小纸浆或纸产品的泛黄和/或返黄。
制造纸张的第一步是形成纸浆。纸浆可以在如上所述的常规硫酸盐制浆工序中由木材(原浆)(virgin pulp)或由回收纸来制备。往往，纸浆是由两种纤维源组合构成的。
对于本发明，任何种类的造纸方法是适当的，并且/或者可以使用任何造纸纸浆。
在具体的实施方案中，基于回收纸张的纸浆用量相对于纸浆的总量为至少2％、或至少4％、或至少6％、或至少8％、或至少10％、或至少15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90或至少95％。
非来源于回收纸张的纸浆部分可以来源于机械制浆(mechanicalpulping)、化学制浆(chemical pulping)和其任何混合，如化学机械制浆(chemi-mechanical pulping)、热磨机械制浆(thermo-mechanical pulping)、化学热磨机械制浆(chemi-thermo-mechanical pulping)等等。
为了由包括回收(或废)纸(也称为二次纤维)的材料制备纸浆，将该材料混合、分散或悬浮在水中。这称为制浆(pulping)的过程。由此从这些纤维中去除至少部分墨水和其它的污染物如胶水、粘合剂、涂料等等。造纸纸浆往往包括回收纸和新鲜的所谓原浆。
回收纤维源可以是本领域已知的任何级别的回收供料(recycledfurnishes)或其混合物、以及回收纤维与原纤维的混合物。主要级别的回收纤维供料是例如MOW(mixed office waste，混合办公废物)、SOW(sortedoffice waste，经拣选的办公废物)、ONP(old newsprint，旧报纸)、OMG(oldmagazine，旧杂志)和OCC(old corrugated container，旧瓦楞纸箱)。
在形成纸浆期间，将原木片或预处理的木片在碱和硫化物的存在下在高压和高温下进行“蒸煮”以溶解单独木材纤维之间的聚合木质物质。释放出的纤维在纤维壁内仍然包含大量的有色木质物质，通过一系列常规漂白工序/化学作用能够不同程度地去除这些木质物质。取决于木材的种类、制浆的条件和漂白方法，漂白的木纤维可以包含不同量的残留木质素和抽出物(例如树脂酸、脂肪酸、甘油三酯、萜烯、萜类化合物、蜡等等)。
在造纸过程期间抽出物如疏水的脂肪酸和酯是非常成问题的。它们能够在加工设备上产生严重的沉积。另外，这些抽出物化合物的存在与增加的热-返黄敏感性有关。即使在脂肪酶处理之后，新形成的长链脂肪酸仍然还是过于疏水而不能溶于工艺用水。
在常规制浆和漂白的木材供料(furnishes)内的可能的热敏性发色团分子前体包括残留木质素和抽出物，以及来源于碳水化合物的氧化、缩合和环化产物(例如2-糠醛、羟甲基糠醛等等)。响应于高温的发色团形成最终表现为最终产物的“泛黄”或“返色”。大多数情况下，发色团前体是亲脂性的，在工艺用水内溶解度有限。
在本文中，发色团包括任何会导致纸浆或纸着色的化合物。尤其，发色团可以在高温下由发色团前体形成。
环糊精可以有效地截留发色团和/或发色团前体并且提高它们在水中的溶解度。与此相应地，在洗涤阶段发色团/发色团前体从纸浆的去除得以提高。另外，许多前体不利地影响纸的某些物理特性(即，撕裂(tear)、拉伸(tensile)、松厚度(bulk)等等)但是通过吸附在纤维表面上而物理性地破坏纤维间的相互作用。通过与环糊精形成配合物而增强的去除能够在一定程度上恢复任何数量的这些受影响的性能。
环糊精最重要的特征是它们具有形成固体包合配合物(主体-客体配合物)的能力。环糊精分子的亲脂腔提供微环境，适当尺寸的非极性部分可以进入所述微环境以形成包合配合物。环糊精中的包合对客体分子的生理化学性能产生深刻的影响，因为当客体(guest)分子暂时被关闭(caged)或锁定(locked)在主体腔内时导致客体分子一些独特的有益的改性。这些性能包括高度不溶解的客体的溶解度的增强、不稳定的客体对降解的稳定化、遮蔽味道和药物和味道的控释。在本发明中尤其利用截留的发色团/发色团前体分子的溶解度的增强。
环糊精可以有效地截留那些疏水的物质并增加它们在水中的溶解度。环糊精还可以与脂肪酶和其它的酶一起工作以改进效率。
根据本发明，造纸方法包括下列步骤：
a)由木材和/或包括回收纸的材料来制备纸浆；
b)添加或原位形成环糊精；
c)洗涤；
d)从处理后的纸浆生产纸。
除步骤a)-d)之外可以包括可任意选择的附加的步骤，例如，一个或多个下列步骤：
e)用一或多种酶处理该纸浆；
f)脱墨，例如通过在碱性水溶液，任选包含过氧化物化合物如过氧化氢的存在下，将纤维制浆；
g)将这些纤维与污染物分离，例如通过筛选(粗和/或细)；
h)离心净化；
i)浮选，例如使用一或多种表面活性剂；
j)洗涤，例如使用一或多种表面活性剂；
k)分散；例如使用一或多种表面活性剂；和/或
i)如果需要，使酶失活，例如通过热处理步骤。
可以包括任何个数的这些附加的步骤，并且顺序没有必要按照a-b-c-d-e-f-g-h-i-j-k-l所示的顺序。可以在制浆之前、在制浆步骤期间、在备料(stock preparation)期间或备料以前、优选正好在备料之前、或者在浮选或脱墨步骤之后引入酶。
因此本发明的目的是提供降低纸浆和纸泛黄的方法，包括在纸浆中添加或原位形成环糊精，然后通过随后的洗涤步骤从纸浆中去除形成的环糊精包合配合物。环糊精包合配合物的形成还可以破坏截留的发色团前体的转变。
可以以α-、β、和γ-环糊精的形式使用环糊精。
在一个具体的实施方案中，环糊精是α-环糊精。
环糊精优选地应该存在于纸浆洗涤期间，但是可以在更早的阶段添加环糊精。在一个实施方案中，在形成纸浆期间添加环糊精。在另一个实施方案中在形成纸浆之后但是在洗涤之前添加环糊精。在又另一个实施方案中，在洗涤期间添加环糊精。
在发色团前体是脂肪酸的情况下，在一个实施方案中脂肪酸对环糊精的比值是10∶1到1∶100、具体为5∶1到1∶75、更具体为2∶1到1∶50。
也可以不添加环糊精，而是原位形成环糊精，例如由淀粉和糖基转移酶(CGTase)在纸浆中形成环糊精。
因此在一个实施方案中，从淀粉和糖基转移酶原位形成环糊精。
可以使用如造纸领域熟知的其它种类的酶处理，它包括选自下列酶的酶：蛋白酶、淀粉酶、支链淀粉酶、脂肪酶、半纤维素酶、内切葡聚糖酶、角质酶和果胶酶；以及其任何组合。
因此本发明涉及纸浆的酶处理与环糊精添加的结合。适合的酶是那些会促进发色团或发色团前体的释放和配合物生成的酶。
作为能够降低纸浆和纸泛黄的酶，木聚糖酶是本领域已知的。在本发明具体的实施方案中，将纸浆的环糊精处理与木聚糖酶处理结合。
实施例
实施例1.通过添加α-环糊精来改进漂白桉树硫酸盐纸浆(bleached
eucalypt kraft pulp，BEKP)的热稳定性
工序：
1.(6)准备包含400g的5％w/w稠度BEKP(在施加环糊精之前不调节纸浆的初始pH)的1.2L不锈钢Launder-Ometer烧杯(Launder-Ometer(AtlasElectric Devices Company，Chicago，IL，USA)是在纺织工业中使用的一件标准设备，它在预热的、充水的室内翻滚地(end-over-end)旋转烧杯。)。
| LOM烧杯 | ID/剂量 | 纸浆稠度(w/w％) | 温度(℃) | 时间(min) | pHpre |
| 1 | 对照物 | 5 | 55 | 120 | 4.1 |
| 2 | 0.01w/w％α-环糊精 | 5 | 55 | 120 | 4.1 |
| 3 | 1.0w/w％α-环糊精 | 5 | 55 | 120 | 4.1 |
2.根据上表在每个烧杯中加入等份的α-环糊精以获得期望的终浓度。
3.然后在恒定搅拌下在Launder-Ometer中在55℃温育烧杯120分钟。
4.在温育之后，调节烧杯内容物的pH，然后稀释到4 L(0.5％稠度)。
5.然后搅拌纸浆液2分钟。
6.(3)从每份纸浆制备2odg的手抄纸(handsheet)，根据TAPPI标准程序将它couch并放置在两个干燥垫板(blotter pad)之间(在这个具体的手抄纸制备期间不使用镀铬(chromed)板)
7.在TAPPI条件下干燥纸页过夜。
8.为了模拟更强烈的洗涤阶段，在配备有125P筛的动态排水罐(dynamicdrainage jar)内洗涤(10 L DIH2O)初始手抄纸形成后的剩余纸浆。洗涤过的纸浆的pH应该接近中性)。
9.(3)然后从每份洗涤的纸浆制备2odg的手抄纸，然后如前所述couch和干燥。
10.用Technidyne ColorTouch PC(Technidyne Corporation，New Albany，IN)分析所有手抄纸的ISO亮度、CIE&Hunter白度指数、E313和DIN6167泛黄指数和CIE颜色空间坐标(color space coordinates)、L、a*和b*。
11.然后将手抄纸在160℃“老化”15分钟，重复测定光学性质。
研究结果在下表1中给出，结果表明通过添加α-环糊精改进了BEKP的热稳定性，从而降低了纸浆垫的泛黄。
表1.与洗涤前后的对照物相比在加速的老化之后泛黄降低和亮度损失的百分数
| 相对于未经处理的对照，E313泛黄指数降低的％ | ||
| 处理 | 没有洗涤 | 洗涤 |
| 对照物 | 0.00 | 0.00 |
| 0.01％α-环糊精 | 1.47 | 9.72 |
| 1.0％α-环糊精 | 5.35 | 6.36 |
| 相对于未经处理的对照，ISO亮度损失降低的％ | ||
| 对照物 | 0.00 | 0.00 |
| 0.01％α-环糊精 | 0.00 | 1.07 |
| 1.0％α-环糊精 | 0.51 | 0.87 |
| 相对于未经处理的对照，CIE b*降低的％ | ||
| 对照物 | 0.00 | 0.00 |
| 0.01％α-环糊精 | 1.42 | 9.88 |
| 1.0％α-环糊精 | 5.35 | 6.23 |
实施例2.通过α-环糊精从溶液中去除脂肪酸
通过去除亚油酸来测试通过添加α-环糊精从溶液中去除脂肪酸。亚油酸是木材抽出物中最丰富的脂肪酸并且形成潜在的发色团。如下制备0.1％亚油酸悬浮液和1.0％的α-环糊精溶液：
1.将250微升的亚油酸转入250毫升的容量瓶中。
2.慢慢添加去离子水，同时在回旋混合器上搅拌。
3.只要持续搅拌亚油酸溶液就保持悬浮。
将2g的α-环糊精在200ml去离子水中溶解，制备1.0％的α-环糊精溶液。
将0.1％的亚油酸悬浮液与1.0％的环糊精溶液以脂肪酸对环糊精的不同比值混合，测定浊度的增加。结果在下表2中给出。
表2.脂肪酸(FA)和环糊精(CD)混合物的浊度(NTU，比浊法浊度单位)测量结果
| 试验管 | 脂肪酸0.1％ | 体积(ml) | 环糊精，1.0％ | 体积(ml) | 水(ml) | 比值FA∶CD | 浊度(NTU) |
| 1 | 亚油酸 | 0 | - | 0 | 30 | - | 0 |
| 2 | 亚油酸 | 20 | α | 1 | 9 | 2∶1 | 64 |
| 3 | 亚油酸 | 20 | α | 10 | 0 | 1∶5 | 168 |
| 3b | 亚油酸 | 20 | - | 0 | 10 | - | 72 |
| 4 | 亚油酸 | 10 | α | 10 | 10 | 1∶10 | 252 |
| 5 | 亚油酸 | 10 | α | 20 | 0 | 1∶20 | 378 |
| 5b | 亚油酸 | 10 | - | 0 | 20 | - | 40 |
| 6 | 亚油酸 | 6 | α | 24 | 0 | 1∶40 | 414 |
| 6b | 亚油酸 | 6 | - | 0 | 24 | - | 24 |
| 7 | 亚油酸 | 4 | α | 20 | 6 | 1∶50 | 342 |
| 7b | 亚油酸 | 4 | - | 0 | 26 | - | 20 |
浊度的增加反映了截留FA的沉淀。
结果表明通过亚油酸的举例说明，通过截留在环糊精中而从溶液中去除脂肪酸是可能的。
Claims (7)
1.降低纸浆和纸泛黄的方法，包括在洗涤之前或期间在纸浆中添加或形成环糊精。
2.根据权利要求1的方法，其中环糊精包括α-、β-和γ-环糊精。
3.根据权利要求2的方法，其中环糊精是α-环糊精。
4.根据权利要求1的方法，其中通过原位酶促产生环糊精来提供环糊精。
5.根据权利要求4的方法，其中该酶包括CGTase。
6.根据权利要求1的方法，其中通过去除发色团前体来降低泛黄，所述发色团前体包括木质素脂肪酸、树脂酸和/或糖寡聚物。
7.根据权利要求1的方法，其中将环糊精处理与木聚糖酶处理结合。
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| CA2633615A1 (en) * | 2005-02-15 | 2008-06-17 | Georgia Tech Research Corporation | Method for improving the consolidation and dewatering of suspended particulate matter |
| US8512523B2 (en) * | 2006-02-14 | 2013-08-20 | Georgia Tech Research Corporation | Method for altering the tack of materials |
| CN101784722A (zh) * | 2007-06-28 | 2010-07-21 | 巴科曼实验室国际公司 | 使用环糊精控制造纸污泥中的臭味以及脱臭污泥和产品 |
| JP6694651B2 (ja) * | 2014-11-07 | 2020-05-20 | 日本食品化工株式会社 | 油性インク除去剤及びその製造方法 |
| JP7131296B2 (ja) * | 2018-10-26 | 2022-09-06 | 王子ホールディングス株式会社 | 微細繊維状セルロース含有組成物およびその製造方法 |
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| US1717799A (en) * | 1924-04-16 | 1929-06-18 | Robert A Marr | Pulp product |
| US3426011A (en) * | 1967-02-13 | 1969-02-04 | Corn Products Co | Cyclodextrins with anionic properties |
| US3453259A (en) * | 1967-03-22 | 1969-07-01 | Corn Products Co | Cyclodextrin polyol ethers and their oxidation products |
| JPS636196A (ja) * | 1986-06-26 | 1988-01-12 | 柴内 裕子 | 紙の製造方法 |
| US5176796A (en) * | 1988-12-13 | 1993-01-05 | Jujo Paper Co., Ltd. | Avoiding pitch troubles using acylgerol lipase |
| US5354424A (en) * | 1989-02-10 | 1994-10-11 | Rha Chokyun | Paper composition and methods therefor |
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| US5776842A (en) * | 1994-06-23 | 1998-07-07 | Cellresin Technologies, Llc | Cellulosic web with a contaminant barrier or trap |
| EP1000032A1 (en) * | 1997-07-23 | 2000-05-17 | Ciba SC Holding AG | Inhibition of pulp and paper yellowing using nitroxides and other coadditives |
| ATE266764T1 (de) * | 1998-09-22 | 2004-05-15 | Alfred Pohlen | Verfahren zur eliminierung von klebrigen verunreinigungen aus aufbereitetem altpapier enthaltende papierbreie mittels hydrophobierten mineralien |
| US6689378B1 (en) * | 1999-12-28 | 2004-02-10 | Kimberly-Clark Worldwide, Inc. | Cyclodextrins covalently bound to polysaccharides |
| US7094748B2 (en) * | 2001-02-12 | 2006-08-22 | The Procter & Gamble Company | Soil redeposition inhibition agents and systems |
| US6849156B2 (en) * | 2001-07-11 | 2005-02-01 | Arie Cornelis Besemer | Cationic fibers |
| DE10149313A1 (de) * | 2001-10-05 | 2003-04-17 | Bayer Ag | Verwendung wässriger Aufhellerpräparationen zum Aufhellen von natürlichen und synthetischen Materialien |
| US20050107282A1 (en) * | 2002-11-14 | 2005-05-19 | The Procter & Gamble Company | Wipes and their use |
| US7282113B2 (en) * | 2004-11-17 | 2007-10-16 | Tritexco, Inc. | Method for enzymatic deinking of waste papers, the waste papers so treated and the treating composition |
| US20060124266A1 (en) * | 2004-11-23 | 2006-06-15 | Novozymes North America, Inc. | Use of cyclodextrins for reducing deposits during paper production |
| US20060142432A1 (en) * | 2004-12-29 | 2006-06-29 | Harrington John C | Retention and drainage in the manufacture of paper |
| JP2008537983A (ja) * | 2005-04-13 | 2008-10-02 | ノボザイムス ノース アメリカ，インコーポレイティド | 二酸化塩素関連の腐食を軽減する方法 |
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