CN100575597C - 南方松硫酸盐纤维的化学活化和精制 - Google Patents

南方松硫酸盐纤维的化学活化和精制 Download PDF

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CN100575597C
CN100575597C CN200480027582A CN200480027582A CN100575597C CN 100575597 C CN100575597 C CN 100575597C CN 200480027582 A CN200480027582 A CN 200480027582A CN 200480027582 A CN200480027582 A CN 200480027582A CN 100575597 C CN100575597 C CN 100575597C
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谭征
春·阮
卡伦·L.·莫勒
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Abstract

一种改变纤维素纤维，特别是针叶木纤维的形态的方法，其包括：(a)使纤维经受在约1-9，优选3-7的pH下进行的金属离子激活的过氧化物处理，和(b)使处理过的纸浆经受精制处理，由此在许多方面使SW纤维转化成与HW类似的纤维。已知所述的金属离子激活的过氧化物处理对纸浆纤维素和半纤维素产生作用，导致纤维素纤维的氧化和氧化降解。只对纸浆进行化学处理不足以获得希望的纤维形态改进，然而，随后进行的旨在取得一定程度的纤维精制的对经化学处理的纤维的精制或类似的机械处理将需要明显更少的精制能量即可达到精制所需的终点并赋予纸浆其它希望的性能。另外，本发明还披露了改性SW纤维以及HW纤维和改性HW纤维的混合物的纸浆。

Description

南方松硫酸盐纤维的化学活化和精制
背景技术
本发明涉及造纸，特别是涉及在使用处理过的材料制备纸幅材料之前对纤维素材料的处理。
正如本领域所熟知的那样，纸张通常由木材制得。通常，工业上将造纸用木材分成两类；即阔叶木和针叶木。针叶木纤维(tracheids)来自带针状叶的针叶树，如松树、云杉、洛杉矶冷杉和花旗松。阔叶木纤维来自各种落叶树。
在阔叶木(HW)纤维和针叶木(SW)纤维之间明显的差别包括：(a)木材单根纤维素纤维的长度，(b)纤维的粗糙度和(c)纤维的挺度或压溃性。
针叶木纤维的形态往往会限制由其所生产纸张潜在的应用。在本发明中所使用的“纸张”包括：纸幅或纸页，对其尺寸或定量没有任何限制。例如，HW或SW纸张可以用作“漂白纸板”(例如用于消费品包装)或“盒纸板”或“挂面纸板”(例如用于瓦楞纸箱)。纸张的适印性能是纸张最终使用主要考虑的问题。SW纤维众人皆知的问题在于由其生产的纸张的适印性能，这是因为SW纤维纸张往往是无规律多孔的、硬挺并且必须进行特殊处理以获得适合印刷的纸张表面。
本领域熟知的是，HW和SW必须经受特殊的处理以便将木材转化成用于形成纸幅的纤维浆料。针叶木更为丰富且更易恢复，如通过树木耕作。针叶木通常较为廉价。因此，只要可能，在造纸中希望用SW纤维替代HW纤维。作为可能的替代品，通常对南方松或阔叶木和针叶木的混合物进行研究，以便替代迄今为止利用阔叶木制备的最终产品。
迄今为止，一直试图将SW纤维用于印刷纸张，业已提出用水解酶对成浆的纤维进行处理。业已采用了酶处理纤维的精制，以便改变其尺寸、形状、细纤维化程度等等。酶处理存在酶对处理条件敏感的问题，并且有失活和/或被带入造纸设备中的倾向。成本-效率的不理想也是长期存在的问题。
为了木浆的漂白或增亮，通常在碱性条件下进行化学处理，如过氧化氢处理。使漂白最大化的条件通常与使氧化作用最大化的最佳条件并不相关。
此外，平滑度和匀度也是纸张适印性能的量度。在此作为纸张特性所使用的“匀度”通常是在一定间距如5-20毫米规模内相对一致性的同义词。通过从背面利用光线对其进行观察以及其它手段，可以判断其匀度。此外，平滑度和匀度均影响纤维长度、形态和压溃性。
发明内容
根据本发明的一方面，业已发现，通过如下处理将改变纤维素纤维，特别是针叶木纤维的形态：(a)使纤维经受在约1-9，优选3-7的pH下进行的金属离子激活的过氧化物处理，和(b)使处理过的纸浆经受精制处理，由此在许多方面使SW纤维转化成与HW类似的纤维。已知所述的金属离子激活的过氧化物处理对纸浆纤维素和半纤维素产生作用，导致纤维素纤维的氧化和氧化降解。只对纸浆进行化学处理不足以获得希望的纤维形态改进，然而，随后进行的旨在取得一定程度的纤维精制的对经化学处理的纤维的精制或类似的机械处理将需要明显更少的精制能量(例如约少30-50％)即可达到精制所需的终点。根据本发明处理过的纸浆明显缩短了纤维长度或纤维长度分布，由此当通过匀度或组织进行测量时，能够使纸页(纸幅)结构具有更好的均匀性。此外，处理过的纤维在纸页固化期间更易压溃(collapsible)，由此带来明显改善的纸张表面性能如平滑度。在这些方面，就其在造纸中的应用而言，根据本发明处理过的SW纤维其功能基本上等同于HW纤维。本发明的处理可以应用于化学木浆(或纸浆混合物)，所述纸张何以具有不同的处理过程如制浆、漂白或酸水解，或将木材加工成适合供至造纸机的纸浆的各种处理的其它组合。
在一实施方案中，本发明可以应用于已经过精制(例如化学处理、酶处理、微纤维化和/或酸水解)的纸浆，以便增加纸浆的游离度或改善造纸过程中的脱水性和/或降低纤维素颗粒悬浮液粘度并改善流动特性。
在另外的实施方案中，可以采用在pH 3-9，优选pH 3-8下的次氯酸盐处理并将次氯酸用作主活化剂，然后对处理过的纸浆进行精制来获得本发明的优点。
此外，可以单独地将金属离子激活的过氧化物或次氯酸处理应用于精制的纤维以增加游离度/脱水性，或者应用于微纤维化的纤维素材料以降低悬浮液粘度。此外，可以在从纤维素材料的初始蒸煮至(包括)纸浆悬浮液供入造纸机之间的任何不同的位置，采用任一实施方案作为控制纸浆悬浮液粘度的手段。本发明的后一方面可用于纸浆的溶解，以便例如生产粘胶丝(viscose)。在某些例子中，本发明的有利影响列于由处理过SW纤维或HW纤维和处理过SW纤维混合物形成的纸幅或纸页的列表中。
在另一实施方案中，对于特定纤维部分的处理，本发明可以与纤维分级处理相结合。
采用本发明处理过的纸浆生产的纸张显示出HW水平的撕裂强度，且抗张强度几乎没有变差。由于增加的游离度，因此还改善了纸页内纤维的结合。
附图说明
本发明的上述特征在结合附图阅读本发明的详细说明之后将变得更为清楚，其中：
图1是描述当对南方松纸浆进行精制时归因于本发明的节能的曲线图；
图2是描述当根据本发明对南方松纸浆进行处理时所取得的纤维长度缩短的曲线图；
图3是描述根据本发明的处理过的和未处理的针叶木浆之间纤维长度分布改变的曲线图；
图4是描述未经处理的松木纤维的显微照相；
图5是描述根据本发明处理过的松木纤维的显微照相；
图6是描述阔叶木浆、未经处理的松木纸浆和处理过的松木纸浆的松厚性对平滑度关系的曲线图；
图7是描述图6所示纸浆的松厚性对游离度关系的曲线图；
图8是描述图6所示纸浆的撕裂度对游离度关系的曲线图；
图9是描述未经处理的阔叶木浆、未经处理的松木纸浆以及阔叶木浆和针叶木浆的不同混合物的松厚性和平滑度关系的曲线图；
图10是描述未经处理的松木浆和采用低密度盘磨精制的根据本发明处理的纸浆纤维长度缩短的曲线图；
图11是描述当对处理过和未经处理的松木浆进行处理时，与用作本发明组成部分的盘磨精制有关的节能曲线图；和
图12是描述在对未经处理的纸浆和根据本发明处理的纸浆进行精制时纤维长度下降和使用的能量之间关系的曲线图。
具体实施方式
根据本发明的一方面，提供了一种将针叶木纤维，特别是南方松纤维转变成与阔叶木类似的纤维的方法。所述方法采用如下步骤：(a)在约1-9的pH下使用包含过渡金属离子和过氧化物的溶液处理包含纤维素和半纤维素的SW纸浆，处理时间足以使纤维素/半纤维素的大部分氧化并使纤维素纤维氧化降解，(b)对处理过的纸浆进行精制处理。当在造纸机上形成纸幅时，如此处理的纸浆显示出许多类似阔叶木的性能，如形成纸幅的总体可成形性，所述纸幅具有与采用传统造纸技术由阔叶木纤维形成的纸幅相似的表面性能。
在本发明的一实施方案中，采用硫酸盐法，使得由针叶树(特别是南方松树)获得的针叶木纤维转化成纸浆，其中正如本领域所熟知的那样，纤维在加热的碱液中进行处理从而使纤维从其木质素粘结剂中分离出。尽管南方松纤维特别适合于采用本发明的处理，但已经认识到也可以采用由其它针叶树得到的纤维。此外，本发明可以有利地采用SW和HW纤维的混合物，例如，包含约50-90重量％SW纸浆和约10-50重量％HW纸浆的混合物。
SW纸浆或SW和HW纸浆的混合物，在采用本发明进行处理之前，可以包括在蒸煮步骤之后没经过任何常规处理的纸浆。然而，本发明可用于处理这样的纸浆，其在蒸煮之后已经受通常使用的纸浆处理，如用于除去hexauronic acid的酸水解、使用氧和/或过氧化物或臭氧对纸浆进行氧化/漂白、和/或对纸浆进行机械处理，即精制。在最为通常预期的处理中，经受本发明处理的纸浆或纸浆混合物是经过蒸煮并且至少已通过洗涤除去黑液的纸浆。
根据本发明的一方面，在约40-120℃的温度下使用过渡金属-激活的过氧化物溶液对纸浆溶液进行约10-60分钟的处理。通常，较高的处理温度将需要较短的停留时间，反之亦然。优选的是，所述处理在70-90℃下进行，停留时间在30-180分钟。所述处理(连续或间歇)可在漂白塔、高密度塔、碎浆机(re-pulper tanker)或任何具有足够混合和停留时间的合适的容器中进行。
在优选的实施方案中，且与其中避免或消除过渡金属离子以避免由羟基自由基所引起的纸浆损坏或降解的传统的纸浆过氧化物处理相反，以纸浆计，本发明的处理溶液包括约0.2-5重量％的过氧化氢和约0.002-0.1重量％的过渡金属离子。铁(III)盐如三氯化铁，或铁(II)盐如硫酸亚铁和氯化亚铁尤其适用作金属离子源。其它金属离子，如铜(II)、钴(II)也可以使用。在所指出的任何情况下，为取得本发明有利的结果，仅仅需要痕量的过渡金属离子，所述金属离子的用量优选为约0.002-0.01重量％。
此外，与其中过氧化物处理是在很高pH下进行漂白的纸浆传统的过氧化物处理相反，在本发明中，在约1-9的pH，优选在约2-7的pH下进行纸浆处理。
业已发现，在约40-120℃和约1-9的pH下，使针叶木浆经受本发明溶液的处理将导致长、硬挺且粗的硫酸盐纤维(kraft fiber)的氧化和氧化纸浆的降解。在对纤维进行所述化学处理之后，对处理过的纸浆进行机械处理，例如采用传统盘磨机进行精制，从而就阔叶木浆而言，使纤维形态发生改变且纸张性能得以提高。本领域熟练技术人员应当理解的是，也可以采用对纸浆提供等效精制的其它机械处理装置。
利用以纸浆计1％的过氧化氢和以三氯化铁形式添加的0.01％的铁，在pH 4下对得自International Paper-Augusta纸浆厂的漂白南方硫酸盐纸浆进行处理。所述处理在80℃进行1小时。利用PFI盘磨对处理过的和对比(未经处理的)松木纸浆进行精制。PFI游离度和平均纤维长度的数据列于表I中。
表I
Figure C20048002758200081
如图1所示，盘磨转速(表示精制能量)与游离度发展的关系表明：对纸浆实施铁催化的过氧化氢处理大大地促进了纸浆的精制，对于相同游离度的读数大大地节省了能量。
图2示出了通过精制缩短了纤维长度(长度-加权平均值)，并且表明在精制之前利用催化的过氧化氢处理，在随后的精制之后纤维长度将大大缩短。而作为对比，未经处理的纸浆(对比纸浆)通过PFI精制纤维长度几乎没有缩短。
图3进一步阐明了示于图2中的纤维长度缩短。在图3中，示出了在同样的精制下，处理过的南方松木浆和未经处理的南方松木浆(对比)的纤维长度分布曲线。由此可以看出，与对比例相比，所述处理将使纤维长度明显地向更短范围改变。
实施例2
利用以纸浆计1％的过氧化氢，在pH为4的情况下，利用源自硫酸亚铁0.006％的铁(II)，对用于实施例1的漂白南方松纸浆进行处理。所述处理在70℃进行1小时。与实施例1相同，对处理过的纸浆和对比纸浆进行PFI精制。由这些纸浆制备TAPPI手抄纸。
为阐明纤维形态(不只是纤维长度分布)和纤维压溃性，获得由处理过的针叶木浆和对比(未经处理的)针叶木浆制得的手抄纸表面的SEM(扫描电子显微术)图像，在4000转的PFI精制下进行比较。这些显微照片描述于图4(未经处理的)(对比例)和图5(处理过的)中，并且表明：与对比例的纤维相比，处理过的松木纤维更容易压溃或变平。压溃(collapsed)且平坦的纤维适于制备具有优异表面和印刷性能的纸张或纸板。另外，还可从处理过的手抄纸的SEM观察到某些断裂或切断的纤维(纤维端部)，这表明纤维被缩短了。
实施例3
如上面实施例2所述，利用由0.006％铁(II)催化的1％的过氧化氢，在pH为4的情况下对漂白南方松纸浆进行处理。对处理过的纸浆进行PFI精制，并制成手抄纸以便进行纸张物理性能评估。结果列于表II中。
表II
Figure C20048002758200101
根据此表，需要指出的是，在精制至约560CSF或更低的游离度(也使纤维缩短)之后，处理过的松木纤维显示出了改善的松厚-平滑度。这也示于图6中。图7描述了在给定游离度的松厚性，其指出了将处理过的松木纤维精制至更低的游离度如400CSF(取决于脱水性能或纸机配料混合物的要求)的好处。
就机械性能而言，该处理将明显地对撕裂强度产生影响，使其降低至阔叶木浆的水平(图8)。当在纸张配料中用处理过的松木纤维替换阔叶木纤维时这将是可接受的。撕裂强度的降低是由于纤维长度的明显缩短和化学影响所造成的。
其它机械性能仅仅稍微地受到影响，并且仍然明显高于阔叶木浆配料。有趣的是，如表II所示，处理过的松木纤维的弹性挺度甚至可以高于对比松木纤维的弹性挺度。
实施例4
也将如上述实施例3的精制至560CSF的处理过的松木纸浆与游离度在一定范围内的阔叶木浆进行混合，以便观测混合配料的纸张性能，如松厚性和平滑度。结果列于表IH中。
表III
图9绘制了混合纸浆配料的松厚性-平滑度曲线(表III数据)，以及100％松木浆和阔叶木浆的曲线(表II数据)。显而易见的是，处理过的松木纸浆可用来替换大部分的阔叶木浆。然而，在造纸厂中精确的阔叶木浆置换量可能多少还受其性质、种类和工业盘磨机的最佳化的影响。
实施例5
Voith LR 1盘磨机用来精制漂白南方松纸浆，所述纸浆已用由铁(III)催化的1％的过氧化氢在pH为4下处理过。所述盘磨机的单位刃口负荷设在0.8Ws/m。由表IV和图10可以看出，节能和纤维长度的缩短得到了证实。
表IV
Figure C20048002758200131
实施例6
VoithLR 1盘磨机用来精制漂白南方松纸浆，所述纸浆已用由铁(II)催化的1％的过氧化氢在pH为4下处理过。所述盘磨机的单位刃口负荷设在4km。
由表V以及图11和12可以看出，节能和纤维长度的缩短得到了证实。
表V

Claims (8)

1.一种调节针叶木纤维形态的方法，其包括下述步骤：
使所述纤维经受10分钟至10小时的在1至9的pH下和在40℃-120℃的温度下进行的过渡金属离子激活的过氧化物处理；和
使处理过的纤维经受精制处理。
2.权利要求1的方法，其中所述过渡金属离子是铁。
3.权利要求1的方法，其中所述pH在3和7之间。
4.权利要求1的方法，其中所述针叶木纤维是纸浆纤维。
5.权利要求4的方法，其中以纸浆计所述过氧化物用量为0.2重量％-5重量％。
6.权利要求4的方法，其中以纸浆计所述过渡金属离子用量为0.002重量％-0.1重量％。
7.针叶木纤维，其通过使纤维经受10分钟至10小时的在1至9的pH下和在40℃-120℃的温度下进行的过渡金属离子激活的过氧化物处理而获得。
8.权利要求7的针叶木纤维，其中所述针叶木纤维是纸浆纤维。
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WO2005028744A1 (en) 2005-03-31
EP1668180A1 (en) 2006-06-14
US20070119556A1 (en) 2007-05-31
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ATE368766T1 (de) 2007-08-15
DE602004007942T2 (de) 2008-04-17
US8262850B2 (en) 2012-09-11
CN1856616A (zh) 2006-11-01
DE602004007942D1 (de) 2007-09-13
EP1862587A3 (en) 2010-01-27
US20090054863A1 (en) 2009-02-26
CA2539095A1 (en) 2005-03-31
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US20160024713A1 (en) 2016-01-28
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US20130098571A1 (en) 2013-04-25

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