CN102472013A - 生产微纤纤维素的方法 - Google Patents
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Abstract
本发明涉及处理纤维素纤维的方法,所述方法包括对纤维进行机械预处理,然后用酶处理纤维,将纤维与包含碱金属氢氧化物的溶液混合,随后对纤维进行机械处理以形成微纤纤维素,这样即有可能以改进的和高效节能的方式制备MFC。
Description
发明领域
本发明涉及通过处理纤维素纤维生产微纤纤维素的方法。
背景
纤维素纤维是由纤维素聚合物,即纤维素链构成的多组分结构。还可能存在木质素、戊聚糖和其他本领域已知的成分。纤维中的纤维素链互相附着形成原纤丝(elementary fibrils)。几个原纤丝结合在一起形成微纤维(microfibrils),几个微纤维形成束。纤维素链、原纤丝和微纤维之间的连接是氢键。
MFC可以由许多不同的方式产生。可能对纤维素纤维进行机械处理从而形成微纤维。然而,对于例如纤维的粉碎或精磨这是非常耗能的方法,因此不常用。
利用细菌生产纳米纤维素或微纤纤维素是另一种选择。与上述不同,这是一个以木纤维之外的其他原材料开始的生物合成方法。但是该方法成本昂贵和耗时。
还可以借助能够降解或溶解纤维的不同化学物质来生产微纤维。但是这样很难控制所形成的小纤维(fibrils)的长度,小纤维往往太短。
生产MFC的一个例子在WO2007091942中有描述。WO2007091942所描述的方法中,MFC是通过酶处理结合精磨而制备的。
但是,仍然有需要改进微纤纤维素生产方法。
发明概述
本发明的目的是提供以改良并且高效节能的方式生产微纤纤维素的方法。
根据权利要求1所述的方法可以实现这些目的和其他优势。通过对纤维素纤维进行机械预处理,然后进行酶处理并添加包含碱金属氢氧化物的溶液,以及最终进行另外的机械处理,有可能以非常高效节能的方式制备微纤纤维素(MFC)。通过独立权利要求可以实现这一点,从属权利要求中限定了所述方法的优选实施方案。
本发明涉及处理纤维素纤维的方法,所述方法包括对纤维进行机械预处理,然后用酶处理纤维,其后将纤维与包含碱金属氢氧化物的溶液混合以使纤维膨胀。膨胀的纤维然后经机械处理形成微纤纤维素。这样有可能以改进和高效节能的方式生产MFC。
碱金属氢氧化物的浓度按重量可以在4-18%之间,优选按重量在5-9%之间。碱金属氢氧化物的浓度在最终的机械处理前调节纤维的膨胀程度。所述碱金属氢氧化物优选是氢氧化钠。
包含碱金属氢氧化物的溶液还可以包含锌盐。碱金属氢氧化物和锌盐的组合已显示能够提高纤维的膨胀。锌盐优选是氧化锌。锌盐的浓度按重量可以在0.1-2%之间,优选按重量在0.5-1.3%之间。
预处理优选是粉碎或精磨纤维。预处理在用酶和包含碱金属氢氧化物的溶液进行处理之前打开纤维结构。这样酶处理以及用包含碱金属氢氧化物和锌盐的溶液进行的处理将更有效,纤维的膨胀提高,从而MFC的生产也得以提高。
精磨过程中纤维的稠度按重量优选在2.5-30%之间。
也可以在预处理之前或之中添加酶来分解纤维结构。优选使用能够作用于或者破坏半纤维素的酶,例如木聚糖酶,但也可以使用纤维素酶,例如内切葡聚糖酶。
用溶液进行的处理期间的温度可以在0-15℃之间。较低的温度显示能够增加纤维的膨胀。
所述方法中使用的酶优选是纤维素酶,该酶能够分解纤维素纤维并提高纤维的可得性和活性,从而也提高了微纤纤维素的生产。
纤维素纤维优选是硫酸盐浆(kraft pulp)纤维。
发明详述
本发明涉及以改进和高效节能的方式生产微纤纤维素的方法。
结合机械预处理和之后的酶处理以及添加包含碱金属氢氧化物的溶液显示能够以温和和可控制的方式使纤维膨胀。此外,还表明可以进一步对膨胀的纤维进行机械处理从而产生微纤纤维素。通过这样的方法,有可能以完全受控制的和成本效益好的方式生产MFC。
酶处理和之后添加包含碱金属氢氧化物的溶液使得纤维膨胀,正是通过这一处理可以控制纤维的膨胀。通过使用酶和提到的化学物质,可能对例如浓度进行小的调整,这样就能够以非常精确的方式控制和调节纤维的膨胀程度。纤维膨胀是由于纤维素链之间的氢键被削弱。虽然处理使得氢键减弱,纤维在其他方面并没有太受影响。因此,纤维的强度不会象为了达到相同的纤维长度使用单纯机械处理后下降的那样。
所述酶会分解纤维初生层,从而增加纤维的可得性,然后能够穿透纤维的结构到达小纤维之间。然后因为纤维初生层被削弱,包含碱金属氢氧化物的溶液就能够以更有效的方式作用于纤维结构。处理过程中,一些纤维会被包含碱金属氢氧化物的溶液溶解。当此后碱金属氢氧化物含量下降,溶解的小纤维将回到固态。当小纤维回到固态,它们将象胶水一样作用,从而增加纤维和小纤维之间的结合。因此,产生的MFC将具有很好的成膜性能。
处理前用酶和包含碱金属氢氧化物的溶液对纤维素纤维进行预处理。优选在酶处理前将纤维切碎或精磨以增加纤维的比表面积,从而促进和提高酶处理的效果。切碎或精磨可以在按总重量为2-40%之间的稠度进行。然而,通常优选高稠度,优选总重量15-40%之间的稠度。较低的稠度(例如在总重量2-6%)或中等稠度(例如在总重量10-20%)也可以使用。
还可能在预处理过程中添加酶。然后优选使用能够破坏半纤维素的酶,比如木聚糖酶,但也可以使用诸如纤维素酶(例如内切葡聚糖酶)的其他酶。可以添加酶来进一步提高预处理效果,并能减少机械处理的延续时间,从而保持纤维强度和节约所需能量。
除了精磨和切碎,还可以利用诸如打浆、汽爆、纤维分离、均质化、超声波处理、干式切削或其他已知机械纤维处理法的其他机械预处理来软化纤维,使它们在下面的处理前活性和反应性更高。
预处理后,向纤维中加入酶,纤维处于浓度大约4-5%的浆体形式。酶是在处理开始时或者整个反应过程中边搅拌边加入。酶处理的目的是打破浆体中存在的微纤维之间的氢键,从而使纤维膨胀。酶提高了纤维的可得性和活性,并能改善用溶液进行的后续处理。
所用的酶可以是能够分解纤维素纤维的任何木材降解酶。优选使用纤维素酶,但可以使用的酶的其他例子是木聚糖酶和甘露聚糖酶。所述酶通常是酶制剂,除了制剂中的主要酶,可能还包含小部分的其他酶活性。用于酶处理的温度可以在30-85℃之间。但是这个温度取决于所用的酶和具体酶的最佳工作温度以及处理过程中诸如时间和pH的其他参数。如果是使用纤维素酶,处理过程中的温度可以是大约50℃。
酶处理可以持续30分钟-5小时。所需时间取决于被处理的纤维素纤维和酶活以及处理过程的温度和pH。酶的活性可以是10-1000nkat/克。
通过升高温度或pH使酶变性,可以终止酶处理。作为替代方案,如果包含碱金属氢氧化物的溶液是直接添加到处理过的纤维中,没有必要单独将酶变性,因为碱金属氢氧化物溶液的pH值足以终止酶处理。酶处理期间的pH优选在4-6之间。
然后向酶处理过的纤维加入包含碱金属氢氧化物的溶液以形成浆体。浆体优选具有为总重量1-7%之间的浓度。碱金属氢氧化物的浓度可以在总重量的4-18%之间,优选是总重量的5-9%之间。总重量是指浆体的总重量,即溶液和浆粕的总重量。
溶液还可能包含锌盐。碱金属氢氧化物和锌盐的组合显示能够非常有效地膨胀纤维。锌盐的浓度可以在总重量的0.1-2%之间,优选总重量的0.5-1.3%之间。
如果溶液既包含碱金属氢氧化物也包含锌盐,碱金属氢氧化物的浓度和锌盐浓度是互相依赖的。例如,当碱金属氢氧化物的浓度高时,需要的锌盐减少。碱金属氢氧化物和锌盐的量应在其上述确定的范围内以非逐级方式(stepless manner)进行调整,以便达到最佳结果。因此碱金属氢氧化物的浓度和锌盐浓度对于纤维素纤维的膨胀效果是互相依赖的。
用所述溶液进行的处理过程的温度可以在0-15℃之间。较低的温度显示能增加纤维的膨胀。然而,重要的是不要使温度下降太多,因为随着温度下降纤维溶解增加。因为不希望纤维发生溶解,所以必须控制温度和其他参数,从而使纤维只膨胀而不溶解。
碱金属氢氧化物优选是氢氧化钠,但也可以使用其他碱金属氢氧化物,比如氢氧化钾或氢氧化钠和氢氧化钾或其他碱金属氢氧化物的混合物。锌盐优选是氧化锌,但可以使用其他锌盐,比如氯化锌或不同锌盐的混合物。
用包含碱金属氢氧化物或者包含碱金属氢氧化物和锌盐的溶液进行的处理的pH值优选高于13。取决于浆体在处理过程中是否被混匀,用包含碱金属氢氧化物的溶液对纤维进行的处理可以持续5分钟到2小时之间。
当用溶液进行的处理完成时,溶液可以用水或酸冲走。在加入水或酸之前,可以添加低浓度的氢氧化钠或另一种碱金属氢氧化物,以除去溶解纤维素的部分(如果有的话)从而能够进一步使用该部分。
当碱金属氢氧化物含量降低时,溶解的小纤维或颗粒将回到固态(如前所述)。溶解的小纤维或颗粒的这种再生在碱金属氢氧化物含量下降时会发生。所述下降可以在纸或纸板机的湿端,通过加入水或酸,或者通过将产生的包含MFC的浆体与另一种硫酸盐浆体混合来实现。
溶解的纤维素是澄清的或稍混浊的溶液,其包含溶解的纤维素物质和纳米颗粒。然而,我们称为溶解的溶液中的固体颗粒的大小应当在光学显微镜下不可见。因此,溶解的部分也包含纳米大小的纤维,所用也要回收和使用。
按照发明所述方法得到的固体部分和溶解的部分可以进一步一起或者单独地进行处理。
加水或酸的缺点是纤维往往发生部分收缩,防止这种收缩是有益的。例如可以通过在加水或酸之前使纤维发生纤维分解,或者通过在加水或酸之前借助机械手段制成纳米纤维素来防止收缩的发生。还可以加入能防止收缩的化学物质。化学物质的选择与膨胀纤维的最终用途有关。例如,表面活性成分;通过添加膨润土或TiO2、通过添加CMC或淀粉或表面活性剂来机械预防以便在加水或酸之前将纤维结构“冻结”。
此后,对纤维进行机械处理以形成微纤纤维素。该处理过程的时间和温度根据被处理的纤维以及先前的处理而不同,并且要进行控制以获得具有所需纤维长度的纤维。所述机械处理可以在精磨机、纤维分解机、打浆机、摩擦研磨机、高剪切纤丝化机器(比如手提式超声波焊机(cavitron)转子/定子系统)、分散均质机(比如高压微射流均质机(microfluidizer))或其他已知的机械纤维处理设备中进行。
发明所述方法中使用的纤维素纤维优选是硫酸盐浆纤维,也就是说,它们已经按照硫酸盐制浆法进行了处理。硫酸盐浆中的纤维的初生壁显示经常会阻碍纤维膨胀。因此,有必要在膨胀处理前,除去初生壁。通过加强纤维的预处理可以去除纤维初生壁。因此,增加精磨,优选高稠度精磨已表明是非常有效的。此外,可以单独或者与精磨(优选高浓精磨)结合使用作用于半纤维素的酶。也可能在精磨纤维之前用酶处理纤维。但是也可以使用其他化学浆粕、机械浆粕或化学机械浆粕,一个例子是亚硫酸盐浆。这些纤维还可以漂白或不漂白,虽然优选漂白,因为这样木质素含量下降,纤维更容易膨胀。
纤维素纤维可以是硬木和/或软木纤维。当按照本发明进行处理时,与桉木和桦木硫酸盐浆相比,亚硫酸盐浆和松树硫酸盐浆能解体成更小的部分。因此,优选用发明所述方法处理软木纤维。
按照发明生产的纤维素材料可用于制作膜。按照本文描述的方法由软木硫酸盐浆生产的MFC显示出优良的成膜性能。
微纤纤维素(MFC)通常也被称为纳米纤维素。已经原纤维化的纤维,和表面含有微纤维的纤维,以及已被分离并位于浆体水相中的微纤维,都包含在MFC的定义中。
实施例
据此处理桦木硫酸盐浆:
-于20%浆粕稠度机械粉碎5小时
-用250nkat/g的纤维素酶,于pH 5、50℃酶处理3小时。
然后使浆粕于10℃接触9wt%NaOH,而不立刻干燥来研究其膨胀能力。将湿浆粕(浓度20%)于10℃加入NaOH,混合物的最终成分是5wt%浆粕和9wt%NaOH。混合物以1000rpm搅拌15分钟,然后在相同温度静置1小时45分钟。然后在光学显微镜下观察样品,测量可溶纤维素部分。
通过加入4%NaOH、将混合物离心并分开澄清/微浑浊上清将膨胀的样品纯化。上清用10%H2SO4处理来沉淀溶解的纤维素。之后,经过纯化的未溶解部分和被沉淀的溶解部分都进一步用水经透析清洗。结果显示42%的纤维被溶解。
未溶解部分和被沉淀的溶解部分都进一步在大约1.5%稠度进行10分钟高剪切混合以便生产MFC。
按照本实施例的描述生产MFC时,总能耗大约0.3MWh/t。
现有技术表明借助机械处理生产MFC的能耗是大约2-3MWh/t。
所以能耗显著下降。
Claims (12)
1.处理纤维素纤维的方法,所述方法包括:
-对纤维进行机械预处理,
-用酶处理纤维,
-将纤维与包含碱金属氢氧化物的溶液混合以使纤维膨胀,和
-膨胀的纤维经机械处理形成微纤纤维素。
2.如权利要求1所述的方法,其特征在于碱金属氢氧化物的浓度在总重量的4-18%之间,优选总重量的5-9%之间。
3.如权利要求1所述的方法,其特征在于所述溶液包含锌盐。
4.如权利要求3所述的方法,其特征在于锌盐的浓度在总重量的0.1-2%之间,优选在重量的0.5-1.3%。
5.如前述权利要求中任一项所述的方法,其特征在于纤维通过切碎或精磨进行了预处理。
6.如权利要求5所述的方法,其特征在于切碎或精磨过程中纤维在总重量2.5-40%的稠度被处理。
7.如前述权利要求中任一项所述的方法,其特征在于用溶液进行的处理期间的温度在0-15℃之间。
8.如前述权利要求中任一项所述的方法,其特征在于所述碱金属氢氧化物是氢氧化钠。
9.如权利要求3-8所述的方法,其特征在于锌盐是氧化锌。
10.如前述权利要求中任一项所述的方法,其特征在于所述酶是纤维素酶。
11.如前述权利要求中任一项所述的方法,其特征在于所述在纤维机械预处理之前或之中加入诸如木聚糖的作用于半纤维素的酶,或者诸如纤维素酶的作用于纤维素的酶。
12.如前述权利要求中任一项所述的方法,其特征在于所述纤维是硫酸盐浆纤维。
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