CN105051289B - 纸或纸板的生产方法 - Google Patents
纸或纸板的生产方法 Download PDFInfo
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Abstract
本发明涉及用于纸或纸板的生产的方法，其包括提供包含纤维素纤维的浆料、向浆料添加包含微纤化纤维素和强度添加剂的混合物、在所述混合物添加之后向浆料添加微粒、将浆料在造纸网上脱水以形成纸幅、和干燥纸幅。
Description
发明领域
本发明涉及用于纸或纸板的生产的方法。
背景技术
在造纸工业领域中存在不断的尝试以寻找减少生产纸或纸板时的成本而不损害纸或纸板的性能（例如强度）的方法。例如通过增加纸或纸板的填料含量已减少了成本。当增加填料含量时，在纸或纸板中的纤维的量可减少。另一方面，纸或纸板中大量的填料降低其强度。
通过改善纸或纸板中的纤维之间的纤维粘合性能，强度的降低可得到补偿，因此维持强度。用于改善纸或纸板的强度的主要的处理已是在形成纸页的操作之前向浆料（也称配料）加强度添加剂，例如淀粉（阳离子淀粉）。已添加至浆料的阳离子淀粉分子可通过静电吸引粘附于天然阴离子纸浆纤维，并因此被保留在湿纤维垫中并留在最终的纸或纸板中。
通过向浆料中添加大量的阳离子淀粉，以获得高纸张强度，问题出现了。阳离子淀粉分子倾向于使纤维素纤维上的阴离子电荷饱和，因此对于可添加至液体浆的阳离子淀粉的量设定了限制。若添加过量的阳离子淀粉，仅一部分添加的淀粉将保留在纸页中，其余将在造纸或纸板机白水系统中循环。此外，由过量阳离子淀粉添加造成阳离子性的纤维将不能吸收通常添加至液体浆的其它阳离子添加剂，例如施胶剂和助留剂。大量的淀粉也常导致生产过程期间的流动性和发泡问题。
向纸或纸板添加微纤化纤维素(MFC)，也称作纳米纤维素，将增加产品的强度。这可能是归因于改善的纤维粘合。
微纤化纤维素典型地是由木材纤维素纤维制造的材料。其也可由微生物源、农业纤维、溶解纤维素或CMC等制造。在微纤化纤维素中，个体微纤丝已部分或完全互相分离。
WO 2011/068457公开了用于生产含有微纤化纤维素的纸或纸板产品的方法。所述方法包括以下步骤：提供包含纤维的配料、向所述配料添加淀粉、向所述配料添加微纤化纤维素、及将所述配料传导至造纸网以形成纸幅(web)，其中所述淀粉和微纤化纤维素分开添加至配料。所述配料包含2-15重量%的量的淀粉及1-15重量%的量的微纤化纤维素。
微纤化纤维素具有非常高的保水能力，其因此非常难以减少包含微纤化纤维素的浆液的水含量。包含微纤化纤维素的浆液的高水含量也阻碍了微纤化纤维素在许多不同应用中的使用，在所述应用中要求具有高固相的微纤化纤维素。
在纸和纸板应用中使用微纤化纤维素将产生密度更大的纸张结构，但是具有更差的脱水性能。滤水时间随着微纤化纤维素的量而增加。
因此，存在对于改善的及更加有效的从含有微纤化纤维素、具有改善的脱水性能的浆料生产纸或纸板的方法的需要。
发明概述
本发明涉及根据权利要求1的用于纸或纸板的生产的方法。
已令人惊奇地发现微粒，例如膨润土和二氧化硅，证明对于改善含有微纤化纤维素(MFC)的浆料的脱水性能是真正有效的。
通常微粒需要阳离子助留聚合物在助留系统中以发挥作用，但是令人惊奇地发现MFC中的高含量的强度添加剂是足够的。
另外，令人惊奇地发现向浆料添加组分的顺序影响含有MFC的浆料的脱水性能。通过首先将强度添加剂和MFC预混合，随后将预混合物与浆料混合，随后添加微粒，显著改善了含有MFC的浆料的脱水性能。
发明详述
本发明提供用于纸或纸板的生产的方法，其包括：提供包含纤维素纤维的浆料、向所述浆料添加包含微纤化纤维素和强度添加剂的混合物、在所述混合物添加之后向浆料添加微粒、将浆料在造纸网上脱水以形成纸幅、和干燥所述纸幅。
令人惊奇地发现向浆料添加组分的次序影响脱水性能。与分开添加或全部一起添加组分(MFC、强度添加剂和微粒)的方法相比较，通过首先将MFC和强度添加剂预混合在一起，随后向浆料添加所述预混合物，随后添加微粒增强了含有MFC的浆料的脱水性能。
在滤水前向浆料添加MFC和强度添加剂的预混合物，以及微粒，以使预混合物在微粒之前添加。例如, 可在滤水前90秒添加预混合物并在滤水前20秒添加微粒。
在优选的实施方案中，将MFC和强度添加剂的预混合物添加至造纸机的浓浆流中，其浓度优选为2–6重量%、更优选3–5重量%。
在另一优选的实施方案中，将微粒添加至造纸机的短循环中，其浓度优选为0.2–2.0重量%、更优选0.3–1.5重量%。
在预混合物和微粒添加之后，将浆料在造纸网上脱水以形成纸幅。通过本领域已知的任何方法进行在造纸网上的脱水。脱水之后通过本领域已知的任何方法干燥形成的纸幅。
所述浆料也可包含通常用于纸或纸板的制造的另外的化学品。
所述纤维素纤维可以是硬木纤维和/或针叶木纤维。所述纤维素纤维可经机械处理、化学机械处理和/或化学处理。所述纤维素纤维也可包含回收纤维，例如脱墨纸浆(deinked pulp)。所述纤维素纤维可以未经漂白和/或经漂白。
如用在本说明书中的术语“微纤化纤维素”，也表示为MFC，包括微纤化/微纤丝纤维素和纳米纤化/纳米纤丝纤维素(NFC)，其材料也称为纳米纤维素。
如上所述，MFC是从纤维素源材料，通常从木浆，来制备。可用于MFC生产的合适的纸浆包括所有类型的化学木基纸浆，例如漂白的、半漂白的和未漂白的亚硫酸盐、硫酸盐和碱法浆。也可使用具有低含量、典型地低于5%的半纤维素的溶解浆。
使用高压匀浆器将MFC纤丝从木基纤维中分离。匀浆器用于使纤维的细胞壁脱层并释放微纤丝和/或纳米纤丝。有时使用预处理减少高能量消耗。此类预处理的实例为酶预处理/机械预处理及如通过羧甲基化或TEMPO介导的氧化引入带电基团。MFC纤维的宽度和长度取决于具体的制造工艺而改变。也可用细菌生产MFC。
MFC的典型宽度为约3至约100 nm、优选约10至约30 nm，典型长度为约100 nm至约2 µm、优选约100至约1000 nm。
通常以很低的固体含量生产MFC，常在介于1重量%和6重量%之间的浓度。但是，可通过脱水生产具有更高固体含量的MFC。在将MFC添加至浆料前也可对其进行改性，从而可能改变其与其它物质的相互作用和亲和力。例如，通过向MFC引入更多阴离子电荷，MFC的纤丝和纤丝聚集物的稳定性增加了。
在优选的实施方案中，所述微纤化纤维素(MFC)是阴离子性的。
在另一优选的实施方案中，将在干燥的基础上以每吨浆料干燥固体5–100 kg、优选10–80 kg、更优选15–70 kg并最优选15–50 kg的量添加所述微纤化纤维素(MFC)。
浆料在造纸网上的滤水时间随着MFC量而增加，因而使用强度添加剂以降低MFC用量而不牺牲高强度性能是有益的。
所述强度添加剂是改善纸张强度例如强度、压缩强度、耐破度和抗张强度的化学品。强度添加剂用作纤维的粘合剂并因此也增加纤维之间的相互连接(interconnections)。
在优选的实施方案中，所述强度添加剂包括淀粉、合成聚合物、壳聚糖、瓜尔胶、羧甲基纤维素(CMC)或它们的混合物。
优选的合成聚合物包括聚丙烯酰胺(C-PAM)、阴离子聚丙烯酰胺(A-PAM)、乙二醛交联丙烯酰胺(glyoxylated polyacrylamide) (G-PAM)、两性聚丙烯酰胺、聚二烯丙基二甲基氯化铵(聚-DADMAC)、聚丙烯酸酰胺(polyacrylic amide) (PAAE)、聚乙烯胺(PVAm)、聚环氧乙烷(PEO)、聚乙烯亚胺(PEI)或这些聚合物中的两种或更多种的混合物。优选地，所述合成聚合物是C-PAM。
所述合成聚合物的平均分子量为在100000–20000000 g/mol、典型地300000–8000000 g/mol、更典型地300000–1500000 g/mol的范围。
所述强度添加剂优选选自淀粉、合成聚合物或它们的混合物，例如淀粉和C-PAM的混合物。
在优选的实施方案中，在干燥的基础上以每吨浆料干燥固体5-100 kg、优选10–80kg、更优选15–70 kg并最优选15–50 kg的量添加所述强度添加剂。
微粒可改善浆料的脱水性能。微粒的功能看来包括(a)从聚电解质桥中释放出水，引起它们收缩，和(b)用作桥的连接，所述桥包括吸附在不同的纤维或细颗粒上的高分子。这些作用创造出更加流线型的通道让水围绕纤维流动。微粒增强单程留着率的倾向将倾向于对初期脱水速率具有积极的影响。
令人惊奇地发现，所述微粒对于改善含有微纤化纤维素(MFC)的浆料的脱水性能也是有效的。通常微粒需要阳离子助留聚合物在助留系统中以发挥作用，但是根据本发明，MFC中强度添加剂的高的量是足够的。
用于本说明书中的术语“微粒”包括纳米尺寸或微米尺寸的固态的、水溶性的、无机颗粒。胶体微粒典型的平均粒径为10-6 mm至10-3 mm。
所述微粒包括无机胶体微粒。优选无机胶体微粒包括基于二氧化硅的微粒、天然硅酸盐微粒、合成硅酸盐微粒、或它们的混合物。
典型的天然硅酸盐微粒是如，膨润土、锂蒙脱石、蛭石、贝得石(baidelite)、滑石粉和锌蒙脱石。
典型的合成硅酸盐微粒是，如火成二氧化硅或合金(alloyed)二氧化硅、二氧化硅凝胶和合成金属硅酸盐，例如Mg和Al类型的硅酸盐。
在优选的实施方案中，所述微粒是基于二氧化硅的微粒、天然硅酸盐微粒，例如膨润土或锂蒙脱石、合成硅酸盐微粒、或它们的混合物。更优选所述微粒是基于二氧化硅的微粒或膨润土。
典型地，在干燥的基础上以每吨浆料干燥固体0.1–4 kg、优选0.2–2 kg、更优选0.3–1.5 kg、再更优选0.33–1.5 kg、甚至更优选0.33–1 kg、最优选0.33 – 0.8 kg的量添加基于二氧化硅的微粒。
在优选的实施方案中，在干燥的基础上以每吨浆料干燥固体至少0.33 kg、优选0.33–4 kg、更优选0.33–2 kg、及最优选0.33–1.5 kg的量添加所述基于二氧化硅的微粒。
典型地，在干燥的基础上以每吨浆料干燥固体0.1–10 kg、优选1–8 kg、更优选2–5kg的量添加天然或合成的基于硅酸盐的微粒。
纸制品的实例为超级压光(SC)纸、超低定量涂布(ULWC)纸、轻量涂布(LWC)纸和新闻纸，但是纸制品不限于这些。
纸板制品的实例为挂面箱纸板、瓦楞箱纸板、折叠箱纸板(boxboard) (FBB)、漂白浆挂面粗纸板(WLC)、全硫酸盐漂白浆(SBS)纸板、全硫酸盐未漂白浆(SUS)纸板和液体包装纸板(LPB)，但是纸板制品不限于这些。纸板可具有120至500g/m2的（每平方米）克重，且它们可100 %基于原纤维(primary fibers)、100 %回收纤维、或原纤维和回收纤维之间的任何可能的混合。
本发明通过以下实施例说明，不以任何方式或因此被限制。
实验
原材料：
桦木浆 (肖伯尔瑞格勒值(Schopper-Riegler number) (SR) 25)和10 %沉淀碳酸钙(PCC)。
设备：
动态滤水分析仪(DDA)，4.1版 (beta) 2009年6月；制造商：AB AkribiKemikonsulter Sundsvall Sweden。
组分：
强度添加剂：
-湿部马铃薯淀粉 (从Chemigate公司商业可获得，产品名Raisamyl 50021)
-Fb 46 (从Kemira公司商业可获得，产品名Fennobond 46 (基于阳离子聚丙烯酰胺的树脂 ))。
MFC:MFC浆液从微晶纤维素(MCC)-水混合物制得（如WO 2011/154601中所述制备），其通过三次经过在2000巴的操作电压下的微射流机(Microfluidizer) M-110P(Microfluidics Corporation)制备
微粒:
-膨润土（从Kemira公司商业可获得，产品名Altonit SF）
-二氧化硅（从Kemira公司商业可获得，产品名 Fennosil 517）
-C-PAM：阳离子聚丙烯酰胺，电荷8 mol-%，Mw约6000000 g/mol。
试验步骤
保持浆料在DDA混合容器中混合。根据表1将组分添加至浆料中。表1中的“延迟时间”意为滤水开始前多少秒将组分添加至浆料。滤水在300 mPas真空度下进行且脱水时间从滤水开始直至空气进来经过形成的纸幅来测量。
表1. 添加至浆料的组分
参考实施例1
强度添加剂和MFC对于脱水的影响
根据表1分开添加所用的组分。参考实施例1根据上述试验步骤进行。组分及组分的量在表2中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表2 强度添加剂和MFC对于脱水的影响
如从表2中可见，单独的强度添加剂对滤水性能没有显著影响。MFC严重恶化脱水性能。
参考实施例2
强度添加剂、MFC和助留化学品(C-PAM)对于脱水的影响
根据表1分开添加所用的组分。参考实施例2根据上述试验步骤进行。组分及组分的量在表3中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表3. 强度添加剂、MFC和助留化学品(C-PAM)对于脱水的影响
如从表3中可见，C-PAM轻微改善了脱水性能。
参考实施例3
强度添加剂、MFC和微粒（膨润土）对于脱水的影响
根据表1分开添加所用的组分。参考实施例3根据上述试验步骤进行。组分及组分的量在表4中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表4. 强度添加剂、MFC和微粒（膨润土）对于脱水的影响
如从表4中可见，膨润土优于C-PAM。
参考实施例4
强度添加剂、MFC和微粒（二氧化硅）对于脱水的影响
根据表1分开添加所用的组分。参考实施例4根据上述试验步骤进行。组分及组分的量在表5中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表5. 强度添加剂、MFC和微粒（二氧化硅）对于脱水的影响
如从表5中可见，二氧化硅在高用量时不如膨润土（效果）好，但是略优于C-PAM。
参考实施例 5
与浆料混合前将所有组分预混合的影响
将所有组分预混合在一起之后将预混合物添加至浆料中。于90 s的延迟时间添加所述预混合物。DDA混合容器和条件如以上试验步骤所述。组分及组分的量在表6中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表6. 与浆料混合前将所有组分预混合的影响
如从表6中可见，将所有组分预混合之后将预混合物与浆料混合没有改善脱水，却起到了反作用。脱水时间与没有膨润土或二氧化硅添加或C-PAM处于相同的水平。
实施例1
将强度添加剂和MFC预混合之后将预混合物与浆料混合，随后添加膨润土、二氧化
硅或C-PAM的影响
将强度添加剂和MFC预混合并于90 s延迟时间将其添加至浆料中，之后于20 s延迟时间分开添加二氧化硅或膨润土或C-PAM。DDA混合容器和条件如以上试验步骤所述。组分及组分的量在表7中公开。组分的量在括号内，且在干燥的基础上以每吨浆料干燥固体kg公开。
表7. 将强度添加剂和MFC预混合之后将预混合物与浆料混合，随后添加膨润土、二氧化硅或C-PAM的影响
试验号29-32和32’-32’’’代表本发明。如从表7中可见，通过以下步骤，可观察到脱水时间的显著改善： 首先将强度添加剂和MFC预混合、将所述预混合物与浆料混合、随后添加微粒。与使用C-PAM相比，使用二氧化硅或膨润土获得改善的脱水时间。
Claims (30)
1.用于纸或纸板的生产的方法，其包括：
提供包含纤维素纤维的浆料，
向所述浆料添加包含微纤化纤维素(MFC)和强度添加剂的混合物，
在所述混合物添加之后向所述浆料添加微粒，
将所述浆料在造纸网上脱水以形成纸幅，和
干燥所述纸幅，
其中所述微粒添加至造纸机的短循环中，浓度为0.2–2.0重量％。
2.权利要求1所述的方法，其中所述强度添加剂包括淀粉、合成聚合物、壳聚糖、瓜尔胶、羧甲基纤维素(CMC)或它们的混合物。
3.权利要求2所述的方法，其中所述合成聚合物包括阳离子聚丙烯酰胺(C-PAM)、阴离子聚丙烯酰胺(A-PAM)、乙二醛交联丙烯酰胺(G-PAM)、两性聚丙烯酰胺、聚二烯丙基二甲基氯化铵(聚-DADMAC)、聚丙烯酸酰胺(PAAE)、聚乙烯胺(PVAm)、聚环氧乙烷(PEO)、聚乙烯亚胺(PEI)或这些聚合物中的两种或更多种的混合物。
4.权利要求2或3所述的方法，其中所述合成聚合物的平均分子量为在100000–20000000g/mol的范围。
5.权利要求4所述的方法，其中所述合成聚合物的平均分子量为在300000–8000000g/mol的范围。
6.权利要求4所述的方法，其中所述合成聚合物的平均分子量为在300000–1500000g/mol的范围。
7.权利要求1所述的方法，其中所述微粒包含无机胶体微粒。
8.权利要求7所述的方法，其中所述微粒包含基于二氧化硅的微粒、天然硅酸盐微粒、或合成硅酸盐微粒。
9.权利要求8所述的方法，其中所述天然硅酸盐微粒为膨润土或锂蒙脱石。
10.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.1–4kg的量添加所述基于二氧化硅的微粒。
11.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.2–2kg的量添加所述基于二氧化硅的微粒。
12.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.3–1.5kg的量添加所述基于二氧化硅的微粒。
13.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.33–1.5kg的量添加所述基于二氧化硅的微粒。
14.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.33–1kg的量添加所述基于二氧化硅的微粒。
15.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.33–0.8kg的量添加所述基于二氧化硅的微粒。
16.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体0.1–10kg的量添加所述天然或合成的基于硅酸盐的微粒。
17.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体1–8kg的量添加所述天然或合成的基于硅酸盐的微粒。
18.权利要求8所述的方法，其中在干燥的基础上以每吨浆料干燥固体2–5kg的量添加所述天然或合成的基于硅酸盐的微粒。
19.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体5–100kg的量添加所述微纤化纤维素。
20.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体10–80kg的量添加所述微纤化纤维素。
21.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体15–70kg的量添加所述微纤化纤维素。
22.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体15–50kg的量添加所述微纤化纤维素。
23.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体5-100kg的量添加所述强度添加剂。
24.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体10–80kg的量添加所述强度添加剂。
25.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体15–70kg的量添加所述强度添加剂。
26.权利要求1所述的方法，其中在干燥的基础上以每吨浆料干燥固体15–50kg的量添加所述强度添加剂。
27.权利要求1所述的方法，其中所述混合物添加至造纸机的浓浆流中，浓度为2–6重量％。
28.权利要求1所述的方法，其中所述混合物添加至造纸机的浓浆流中，浓度为3–5重量％。
29.权利要求1所述的方法，其中所述微粒添加至造纸机的短循环中，浓度为0.3–1.5重量％。
30.权利要求1所述的方法，其中所述微纤化纤维素是阴离子性的。
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| FI20135292A FI126216B (en) | 2013-03-26 | 2013-03-26 | Procedure for the manufacture of cardboard |
| PCT/FI2014/050173 WO2014154937A1 (en) | 2013-03-26 | 2014-03-07 | Process for production of paper or board |
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| Publication number | Publication date |
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| RU2667450C2 (ru) | 2018-09-19 |
| WO2014154937A1 (en) | 2014-10-02 |
| ES2682170T3 (es) | 2018-09-19 |
| RU2015128499A (ru) | 2017-04-28 |
| JP2016519225A (ja) | 2016-06-30 |
| US20160032530A1 (en) | 2016-02-04 |
| CA2908122A1 (en) | 2014-10-02 |
| FI20135292A (fi) | 2014-09-27 |
| EP2978894A1 (en) | 2016-02-03 |
| PT2978894T (pt) | 2018-08-03 |
| JP6620739B2 (ja) | 2019-12-18 |
| FI126216B (en) | 2016-08-31 |
| CA2908122C (en) | 2021-07-27 |
| US9605382B2 (en) | 2017-03-28 |
| EP2978894B1 (en) | 2018-05-02 |
| CN105051289A (zh) | 2015-11-11 |
| PL2978894T3 (pl) | 2018-10-31 |
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