CN104105827B - 预处理纤维素浆料的方法 - Google Patents
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Abstract
本发明涉及在纳米原纤化的纤维素制备中预处理天然纤维素浆料,并且涉及可由该方法得到的纳米原纤化的纤维素产物。
Description
发明领域
本发明涉及制造纳米原纤化的纤维素的方法,尤其是涉及在纳米原纤化的纤维素制造中纤维素浆料的预处理,并且涉及可通过所述方法得到的纳米原纤化的纤维素产品。
背景
通常通过使用合适的崩解设备进行的纤维素浆料的机械崩解得到纳米原纤化的纤维素(NFC)。机械崩解是消耗能量的操作,其中生产能力是有限的。因此已经提出了几种措施来改善研磨或原纤化工艺,诸如在崩解之前改性浆料。所述改性可以包含浆料的化学改性以产生带阴离子电荷或阳离子电荷级别的纳米原纤化的纤维素(NFC)。所述化学改性可以基于例如纤维素分子的羧甲基化、氧化、酯化或醚化。然而,所述化学改性方法产生各级别的NFC,其并不在所有应用中需要并且因此已经研究了替代方法,诸如预研磨、羧甲基纤维素吸收和酶处理。
因此,存在对提供NFC制备中的浆料进行预处理的改良方法和NFC制备的改良方法的需要。
发明内容
本发明基于对机械崩解之前的纤维素浆料的预处理的研究。发现可以增强机械崩解,尤其是原纤化,并且可以得到具有改良性质的NFC产品。
预处理纤维素浆料的方法包含以下步骤,其中天然纤维素浆料的水性悬浮液与无机或有机酸接触并且搅拌得到悬浮液的pH低于4,之后去除水并且用水洗涤固体物质,形成固体物质的水性悬浮液,然后向形成的悬浮液中加入NH4 +、碱金属、碱土金属或金属中的至少一种的水溶性盐,之后搅拌,用无机碱将悬浮液的pH调节至超过7,之后去除水,并且用蒸馏水或去离子水洗涤固体物质。
制备纳米原纤化纤维素的方法包含预处理天然纤维素浆料的步骤,所述预处理包含以下步骤,天然纤维素浆料的水性悬浮液与无机或有机酸接触并且搅拌得到悬浮液的pH低于4,之后去除水并且用水洗涤固体物质,形成固体物质的水性悬浮液,然后向形成的悬浮液中加入NH4 +、碱金属、碱土金属或金属中的至少一种的水溶性盐,之后搅拌,用无机碱将悬浮液的pH调至超过7,之后去除水,并且用蒸馏水或去离子水洗涤固体物质,形成固体物质的水性悬浮液并且崩解该固体物质。
可通过所述方法得到NFC产物,所述产物具有低于200 NTU的浊度和超过15000mPas的布氏(Brookfield)粘度(适于用1.5%,10 rpm测定)。
因此,本发明提供了以更高效和经济的方式制备具有改良性质的NFC的方法。
本发明的特征在所附的权利要求中。
附图简要说明
图1说明了在崩解前预处理纤维素浆料对NFC产物中纳米材料的量的影响。
图2显示了未预处理的原纤化纤维素产物(a)和预处理的NFC(b)的显微照片。
图3显示了NFC样品的浊度随原纤化中能量消耗的变化。
图4显示了NFC样品的粘度随原纤化中能量消耗的变化。
定义
除非另有说明,本说明书和权利要求中使用的术语具有在浆料和造纸工业领域中常用的含意。具体地,以下术语的含义说明如下。
本文使用的术语“纳米原纤化的纤维素”或NFC理解为包括全部的微原纤化纤维素(MFC)和原纤维纤维素。另外,纳米原纤化的纤维素有几个广泛使用的同义词。例如:纤维素纳米纤维、纳米原纤纤维素(CNF)、纳米原纤纤维素(NFC)、纳米级原纤化的纤维素、微原纤纤维素或纤维素微原纤。
机械崩解在本文中表示用于对纤维素纤维进行崩解或原纤化以得到NFC的任意方式。可以使用,例如石研磨、精研机、研磨机、均化器、胶化器、超质量胶化器、磨擦研磨机、超声波破碎器、流化器(诸如微流化器、大流化器或流化器型均化器)进行原纤化。
本文中术语“天然纤维素浆料”是指并未经过化学改性的任意纤维素浆料。
本文中术语“悬浮液”是指含有固体颗粒的非均相流体并且其也包括浆液和分散体,通常是水性液体。
发明详述
令人惊讶地发现可以改善纤维素浆料的机械崩解,从而可以用较少的能量得到较高产量的需要的纳米原纤化的产物。另外,同时改善了最终NCF产物的性质。
因此,在机械崩解之前用酸和碱预处理纤维素浆料。通过将纤维素浆料经过温和的酸处理,以去除带正电的离子,之后用含有限定的带正电的离子的碱处理用于取代早先的离子,来使得预处理产生效果。随后崩解预处理的纤维素浆料。该预处理提供了具有出色的凝胶性和透明性的最终产物。
预处理纤维素浆料的方法包含以下步骤,其中天然纤维素浆料的水性悬浮液与无机或有机酸接触并且搅拌得到悬浮液的pH低于4,之后去除水并且用水洗涤固体物质,并形成固体物质的水性悬浮液,然后向形成的悬浮液中加入NH4 +、碱金属、碱土金属或金属中的至少一种的水溶性盐,之后搅拌,用无机碱将悬浮液的pH调至超过7,之后去除水,并且用蒸馏水或去离子水洗涤固体物质。
制备纳米原纤化纤维素的方法包含预处理天然纤维素浆料的步骤,所述预处理包含以下步骤,其中天然纤维素浆料的水性悬浮液与无机或有机酸接触并且搅拌得到悬浮液的pH低于4,之后去除水并且用水洗涤固体物质,并形成固体物质的水性悬浮液,然后向形成的悬浮液中加入NH4 +、碱金属、碱土金属或金属中的至少一种的水溶性盐,之后搅拌,用无机碱将悬浮液的pH调至超过7,之后去除水,并且用蒸馏水或去离子水洗涤固体物质,形成固体物质的水性悬浮液并且崩解该固体物质。
在所述方法中,合适地以一定的量使用NH4 +、碱金属、碱土金属或金属的水溶性盐得到0.001-0.01 M(0.1-1 mol/kg纤维或固体材料),尤其是0.002-0.008 M的浓度。
在预处理方法中,在悬浮液中固体物质的含量范围可以是0.1-20重量%,合适地为0.5-3重量%。
无机或有机酸合适地为可以易于洗去、不在产物中留下不需要的残留物并且具有-7到7的pKa-值的酸。
有机酸可以选自短链羧酸,诸如乙酸、甲酸、丁酸、丙酸、草酸和乳酸。本文中短链羧酸是指C1-C8酸。无机酸可以合适地选自盐酸、硝酸、氢溴酸和硫酸。
以0.001-5 M水性溶液的稀释形式合适地使用酸,其可以方便地加入悬浮液中。合适地,酸的添加时间为0.2-24小时。
用酸将pH调至低于4,合适地低于3。
在该方法中使用的水可以是自来水、蒸馏水、去离子水、纯水或灭菌水。合适地使用蒸馏水或去离子水,尤其在pH调至超过7之后的洗涤步骤中。
可以通过任意合适的方式来从悬浮液或浆液中去除水,例如,用卷筒纸压制(webpress)、压力式过滤、抽滤、离心和螺旋压制。
在酸处理后可以用水洗涤固体物质1-5次,合适地2-3次以去除过量的酸。
可以在水去除步骤之后适当地使用相同的设备来用水洗涤固体物质。
NH4 +、碱金属、碱土金属或金属(合适地为NH4 +、Na、K、Li、Ag和Cu)的水溶性盐可以选自H4 +、碱金属、碱土金属或金属的无机盐、配合物和与有机酸形成的盐。该无机盐合适地为硫酸盐、硝酸盐、碳酸盐或碳酸氢盐,诸如NaHCO3、KNO3或AgNO3。M是指碱金属、碱土金属或金属。按照一个合适的实施方式,水溶性盐是钠盐。
无机碱选自NaOH、KOH、LiOH和NH3。
用无机碱将悬浮液的pH调至超过7,合适地为7.5-12,特别合适地为8-9。
在用无机碱调节pH之后,进行水去除并且用蒸馏水或去离子水洗涤固体物质。合适地重复或进行洗涤直至用过的洗涤液体,诸如滤液的电导率低于200 μS/cm,合适地低于100 μS/cm,特别合适地低于20 μS/cm。
在向悬浮液加入组分(酸、盐、碱)之后,可以搅拌形成的混合物并且在继续该方法之前静置。
所得的预处理的固体物质,合适地作为水性悬浮液,在粉碎机中经机械崩解得到纳米原纤化的纤维素产物。合适的粉碎机选自石研磨、球磨、精研机、研磨机、均化器、高压均化器、胶化器、超质量胶化器、磨擦研磨机、超声波破碎器、流化器、微流化器、大流化器、高压流化器、超高压流化器或流化器型均化器。
任选地,预处理的固体物质可以在机械崩解之前经过预研磨。可以使用任意标准的研磨机或磨具。如果流化器型均化器用于机械崩解,其特别适于预研磨预处理的固体物质。可以使用任意合适的研磨设备来进行预研磨。
机械崩解适于进行1-10次,特别合适地为1-5次。
可以通过所述方法得到NFC产物,所述NFC产物包含机械崩解的天然纤维素,具有低于200 NTU,甚至低于150 NTU的浊度。所述产物具有超过15000 mPas,合适地超过30000mPas,特别合适地超过40000 mPas的布氏粘度(1.5%,10 rpm)。
适于用布氏粘度计(布氏粘度)或其他相应的设备测量NFC的表观粘度。合适地使用桨式转子(73号)。有几种市售的用于测量表观粘度的布氏粘度计,这几种粘度计都是基于相同的原理。合适地在设备中使用RVDV弹簧(布氏 RVDV-III)。作为结果,得到具有变化的剪切速率的粘度图。低旋转速度是合适的,诸如10 rpm。在布氏粘度方法中,在液体(合适地为水)中搅拌稀释NFC样品,至0.1-2.0重量%的浓度范围(在实施例中为1.5%)。
可以使用光学浊度测量仪器定量地测量浊度,其以两种不同的物理原理工作:测量穿过液体的光束的强度的衰减(比浊法)和测量散射辐射(光)的强度(浊度法)。散射是由颗粒造成的。也可以通过反射法确定浊度。存在几种可用于定量测量浊度的商用浊度计。在本发明的案例中,使用基于浊度法的方法。来自校准的浊度计的浊度的单位被称为比浊法浊度单位(NTU)。
通常用标准校准样品校准并控制测量设备(浊度计),之后测量稀释的NFC样品的浊度。
在所述方法中,用液体,优选水性介质(诸如水)来将原纤维纤维素样品稀释至低于所述原纤维纤维素的胶凝点的浓度,并且测量经稀释的样品的浊度。合适地,所述浓度的范围是0.001-1重量%,合适地为0.1-1重量%,并且测量浊度。从所得的结果计算平均值和标准偏差,并且所得的结果以NTU单位表示。
可以通过基于精确高分辨率显微镜和图像分析的方法进行纤维的分析,这适于NFC的微米级和纳米级纤维的定量测定,从而在原纤维纤维素中确定未原纤化纤维样的材料。测量已知量的浆料样品中可检测的纤维或纤维样颗粒的量并且剩余的样品然后被认为属于不可检测的类别,例如,微米级和纳米级颗粒。可以使用商业纤维分析仪来表征原纤维纤维素中未原纤化的纤维样材料。例如,Kajaani Fiberlab和FS-300装置是合适的。然而,也可以使用其他相似的具有相似检测分辨率的纤维分析仪。
纤维分析包括以下步骤,其中测定样品的干质量用于分析中,之后是在稀释和取样期间的体积缩放,样品的崩解。如果需要,可以使用比常规浆料样品大的样品尺寸。可以从推荐的尺寸增加用于测量的样品尺寸来增加在分析期间检测到的纤维的量。
为简明起见,使用颗粒/毫克的定量测量。
在上层相中纳米材料的量见述于图1,其通过如下方法确定:在50 ml管中称量1.6g/L固体的湿样品,之后在20℃的温度下离心2小时。在离心之后,样品经过干燥并称重,并且计算上层相中的纳米材料的量。样品原纤化的程度越高,在上层相中发现的纳米颗粒的量越大。这可以在图2中看到,与未预处理的产物相比,其中预处理的产物含有几乎2倍的纳米颗粒的量。
可以在所述方法中使用来自任意植物来源,从任意基于植物的纤维素原料得到的任意天然纤维素。
术语“纤维素原料”表示含有可以在纤维素浆料、精制浆料或原纤维纤维素的生产中使用的纤维素的任意基于植物的纤维素原料(植物材料)来源。
植物材料可以是木材并且所述木材可以来自软木树如云杉、松树、冷杉、落叶松、花旗松或铁杉,或来自硬木树如桦树、白杨、杨树、桤木、桉树或刺槐,或者来自软木和硬木的混合物。非木材材料可以来自农业残料、草或来自棉花、玉米、小麦、燕麦、黑麦、大麦、稻、亚麻、大麻、马尼拉麻、剑麻、黄麻、苎麻、洋麻、甘蔗渣、竹或芦苇的其它植物物质,如稻草、树叶、树皮、种子、壳、花、蔬菜或果实。
术语“纤维素浆料”表示使用化学、机械、热机械或化学热机械的制浆工艺从任意纤维素原料中分离的纤维素纤维。
植物来源的纤维素浆料,尤其是木材(软木或硬木浆料,例如漂白的桦木浆料)并且在上述的方法之一中产生纤维素分子的情况下,易于使用任意机械崩解方法将纤维素浆料崩解为原纤维纤维素。
术语“纳米原纤化的纤维素”或NFC表示来自纤维素原料的分离的纤维素微原纤(纳米纤维)或微原纤束的集合。微原纤通常具有高的长宽比:长度超过1 μm,而数均直径通常小于200 nm(1-200 nm,合适地1-100 nm)。微原纤束的直径也可以更大,但通常小于1 μm。最小的微原纤类似于所谓的初级原纤,通常直径为2-12纳米。原纤或原纤束的尺寸取决于原料和崩解方法。
NFC的特征在于非常高的保水值,高度化学可及性和在水或其他极性溶剂中形成稳定的胶的能力。NFC产物通常是高度原纤化的纤维素的致密网络。NFC也可能含有一些半纤维素;其量取决于植物来源和制浆条件。
已经使用各种生产技术开发了几种不同等级的NFC。根据制备方法、原纤化的程度和化学组成,这些等级具有不同的性质。这些等级的化学组成也有变化。根据原料来源,例如,HW对比SW浆料,在最终NFC产物中存在不同的多糖组合物。
可以在使用之前对NFC进行灭菌,合适地以胶的形式进行。另外,如果需要,在原纤化/机械崩解之前,可以在漂白阶段之后(当浆料仍然无菌时)立即从制浆厂中无菌地收集纤维素浆料。
所得的NFC具有出色的胶凝能力,这表示其在水性介质中以低稠度就已经形成水凝胶。
预处理通常产生M+形式的天然纤维素浆料。M是碱金属、碱土金属或金属,合适地为Na、K、Li、Cu或Ag,尤其是Na。所得的M+形式的天然纤维素浆料向由此制备的NFC提供了益处,尤其对于原纤化工艺和所得的纳米原纤化的纤维素产物的质量。具体地,当与没有预处理步骤制备的相似NFC(即使原纤化能量无限增加,例如,增加在机械粉碎机中的次数)比较时,可以实现对天然NFC,同时对透明性和粘度的质量改善。
预处理的NFC产物也适于生物化学、药物和分子科学应用,因为该产物不含像例如化学改性的NFC那样的试剂残留物,其是生物相容的并且与各种组分相容。所述的残留物被认为在药物递送应用中、在处理高灵敏分析和测定生物化学化合物的应用中是潜在毒性或有害的。由于NFC不是聚合产物,在产物中没有留下单体残留物。对于核酸分析和分离,可以避免或至少明显降低潜在的计数和检测问题的风险。其没有不良影响并且不干扰DNA分离或PCR分析。
预处理的NFC是非毒性产物,其易于制备,易于处理并且不需要来自终端使用者的专门预防措施。
当与未处理的产物比较时,预处理的NFC产物至少提供了以下的益处:
-原纤化的M+形式的天然纤维素浆料含有较高量的纳米材料
-较细材料的量更高并且NFC材料更均匀
-可以用预处理的NFC实现具有低于200 NTU,甚至低于150 NTU的浊度的产物
-可以用原纤化Na+形式的纤维素浆料实现较高的粘度,该粘度超过15000 mPas,合适地超过30000 mPas(1.5%,10 rpm)。
-不用化学预处理或不需要添加剂就可以得到中性、高度透明和高粘性的产物
-改善了NFC产物的可胶凝能力
-按照纤维分析(Fiberlab测试),预处理的NFC产物含有低于5000颗粒/mg,合适地低于1000颗粒/mg(大颗粒),甚至低于200颗粒/mg。
-NFC产物的纯度高(含有较少的杂质并且不含盐),并且质量是可重复的。
-该方法使用相同或更低的能量输入提供了较高质量的NFC产物
实施例
以下的实施例是本发明的示例性实施方式,如上述,并且它们并不旨在以任意方式限制本发明。
实施例1:纤维素浆料的预处理,之后原纤化
1500 g从漂白的桦木浆料得到的湿天然纤维素浆料经过滤并且用0.01 M HCl水溶液稀释固体物质得到具有大约1-1.2重量%的干物质含量的悬浮液。悬浮液静置大约15分钟并偶尔搅拌。悬浮液然后经过滤、用去离子水洗涤2次并且过滤。然后将固体物质悬浮在0.005 M的NaHCO3水溶液中,得到具有大约1-1.2重量%的干物质含量的悬浮液,用1 MNaOH水溶液将所得悬浮液的pH调节至8-9并且所得的悬浮液静置15分钟并偶尔搅拌。悬浮液经过滤并且用去离子水洗涤固体物质直至滤液的电导率低于20μS/cm。
使用含有MKGA10-80研磨石的Masuko超质量胶化器对所得的固体物质的样品进行原纤化(机械崩解)1-5次。未预处理的样品也在含有MKGA10-80研磨石的Masuko超质量胶化器中经过原纤化。
所得的固体物质的样品也经预研磨,之后在微流体流化器中原纤化,通过APM+200μm腔室一次并且通过APM+100 μm腔室1-10次。来自预处理的和2、3和4次通过以及未预处理的样品经离心并且测量在上层相中纳米材料(纳米级材料)的量。
在图1中所示的结果显示预处理的材料(流化器Na)在预研磨和流化之后含有更多纳米材料。按照测试,其含有59重量%的纳米级材料而未处理的样品(流化器参比)含有35重量%的纳米级材料。
图2以光学显微照片显示了在原纤化(4次)后预处理(2b)和未处理(2a)的材料中原纤化之间的差异。
图3提供了随着在超质量胶化器(Masuko)或流化器中原纤化之后预处理的样品和未处理的样品的能量消耗变化的浊度结果。在没有预处理的情况下,没有得到浊度低于200的产物。预处理明显降低了浊度值。使用光学方法测量浊度,其中使用所谓的比浊法和浊度法。使用HACH P2100-装置在0.1%浓度下进行测量。以一定方式用水稀释NFC样品,使得小心地混合299.5 g水和0.5 g NFC(以NFC计算)。
预处理的原纤化产物和未处理的原纤化产物的布氏粘度测量的结果示于图4(在微流体流化器中原纤化)。预处理的样品得到较高的粘度。使用具有73号桨式转子的布氏粘度计,装备有布氏RVDV-III弹簧,旋转速度10 rpm和1.5%浓度。按照纤维分析(FiberlabKajaani设备),通过3次的预处理的原纤化产物(在微流体流化器中原纤化)包含9410颗粒/g并且通过6次的原纤化产物包含86颗粒/g。通过3次的相应的未处理的产物包含14029颗粒/g并且通过6次的未处理的产物包含692颗粒/g。
预处理的原纤化产物和未处理的原纤化产物(用Masuko超质量胶化器原纤化)通过2次后的布氏粘度分别是67329 mPas和44763 mPas。
虽然已相对于包括现在优选的实施本发明的优选模式的具体实施例对本发明作了描述,但是本领域的技术人员可以理解,对上述实施方式的许多变化和变换在所附权利要求的范围之内。应理解本发明并不限于其在本文所述的组分的构建和排布细节中的应用。前述的变化和修饰在本发明的范围内。
Claims (13)
1.一种制备纳米原纤化的纤维素的方法,所述方法包含预处理天然纤维素浆料的步骤,所述预处理包含以下步骤,其中天然纤维素浆料的水性悬浮液与无机或有机酸接触并且搅拌得到悬浮液的pH低于4,之后去除水并且用水洗涤固体物质,形成所述固体物质的水性悬浮液,然后向所述形成的悬浮液中加入NH4 +、碱金属、碱土金属或金属中的至少一种水溶性盐,之后搅拌,用无机碱将所述悬浮液的pH调至7.5-12,之后去除水以产生固体物质,并且用蒸馏水或去离子水洗涤所述固体物质产生预处理的天然纤维素浆料;并且之后形成所述预处理的天然纤维素浆料的水性悬浮液并且机械崩解该悬浮液。
2.如权利要求1所述的方法,其特征在于,所述有机酸选自C1-C8羧酸,并且所述无机酸选自盐酸、硝酸、氢溴酸和硫酸。
3.如权利要求1或2所述的方法,其特征在于,所述有机酸选自乙酸、甲酸、丁酸、丙酸、草酸和乳酸。
4.如权利要求1或2所述的方法,其特征在于,使用所述酸将pH调至低于3。
5.如权利要求1或2所述的方法,其特征在于,所述NH4 +、碱金属、碱土金属或金属的水溶性盐选自NH4 +、碱金属、碱土金属或金属的无机盐、配合物和与有机酸形成的盐。
6.如权利要求1或2所述的方法,其特征在于,所述NH4 +、碱金属、碱土金属或金属的水溶性盐是NH4 +、Na、K、Li、Ag或Cu的盐。
7.如权利要求1或2所述的方法,其特征在于,所述碱金属、碱土金属或金属的水溶性盐是NaHCO3、KNO3或AgNO3。
8.如权利要求1或2所述的方法,其特征在于,所述无机碱选自NaOH、KOH、LiOH或NH3。
9.如权利要求1或2所述的方法,其特征在于,用所述无机碱将所述悬浮液的pH调至8-9。
10.如权利要求1或2所述的方法,其特征在于,所述机械崩解包含预研磨步骤。
11.如权利要求1或2所述的方法,其特征在于,所述机械崩解进行1-10次。
12.一种可通过权利要求1-11中任一项所述的方法得到的纳米原纤化的纤维素产物,所述产物包含天然纤维素并具有在0.1%浓度下低于200NTU的浊度和在1.5%浓度下超过15000mPas的布氏粘度。
13.如权利要求12所述的纳米原纤化纤维素产物,其特征在于,所述产物具有在0.1%浓度下低于150NTU的浊度和在1.5%浓度下超过30000mPas的布氏粘度。
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