CN111788347B - 制造包含微原纤化纤维素的组合物的方法 - Google Patents
制造包含微原纤化纤维素的组合物的方法 Download PDFInfo
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- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/02—Cellulosic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites
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- C—CHEMISTRY; METALLURGY
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
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- D—TEXTILES; PAPER
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Abstract
本发明公开了形成组合物的方法,该方法包括在碱金属硅酸盐的存在下使纤维原纤化以形成MFC,由此形成MFC和硅酸盐混合物。在纤维原纤化为MFC期间碱金属硅酸盐的存在,降低了粘度并且提高了释水性质,由此可在较高的浓度下实现原纤化并且实现了更均匀的MFC‑硅酸盐混合物(混合)。通过本发明的方法形成的组合物可例如用于纸或纸板生产、用于水泥生产或用作复合材料中的添加剂。
Description
技术领域
本发明涉及制造包含微原纤化纤维素的组合物的方法,根据所述方法生产的组合物及其用途。
背景技术
近期,在多种工业应用中使用微原纤化纤维素(MFC)的兴趣日益浓厚。在造纸和板制造中,MFC可用来提高产品的强度,以能够减少来源(source reduction)或用来提高留着。在水泥(结合剂)和混凝土应用中,MFC可用来提供强化、控制脱水或干燥或调节流变性质。MFC还可用于许多复合材料应用,比如粘合剂、涂料、膜、油漆(颜料,paints)和包装。
MFC通常由纤维素纤维通过使纤维原纤化而生产,例如通过使用均质化、微流化、研磨、精磨或打浆而使纤维原纤化。优选使用预处理,比如酶预处理、化学预处理或机械预处理来降低原纤化的能量或引入官能团和调整MFC的物理尺寸。已经提出了许多种不同的方法来增强原纤化或降低原纤化能量。WO2007091942公开了通过酶处理然后均质化来制造MFC的方法。在WO2014106684中,通过在多个步骤中在不同的稠度下使纤维浆(fibrouspulp)原纤化来生产MFC。WO2011004284公开了通过同时酶处理和机械处理来生产MFC的方法。
与MFC的工业使用相关的一个问题是其具有非常高的水结合能力并且因此缓慢地释放水。由于其特征性的物理和化学性质,MFC的生产导致具有非常低的固含量(典型地约为0.1-3重量%)的水性悬浮体。具有这样低的固含量的MFC的运输和处理(混合,脱水,干燥和泵送(pumping))是不可持续的或不是成本有效的。将MFC干燥或脱水至高固含量可进一步劣化其性质,例如导致湿角质化和改变其性能。
在水中并且在较高的浓度下(>1重量%),MFC形成凝胶。MFC凝胶的一个问题是将其混合入含有一种或多种其他反应性化学品的复合材料中需要高强度的混合和受控的反应条件。在MFC用作活性前体或用作试剂或载体材料的情况中,必须优化计量添加(dosing),以避免竞争性反应或副产物或其他中间化学品的形成。一种这样的反应性化学品的实例是硅酸钠,其与纤维素或改性纤维素的反应需要受控的条件。在某些应用中,以中等稠度或高稠度添加MFC是有益的,这使得MFC的分散成为了关键。分开的计量添加MFC和硅酸钠引起多种产物或中间体的形成,而所述的多种产物或中间体通常负面地影响最终产品的性质。
这样的一个实例是向处理流(工艺流)比如造纸原料添加低稠度MFC。与这样的添加相关的挑战是如何实现絮凝、受控的相互作用(比如定量留着)和添加剂和组分在悬浮体中以及由其形成的产物中的均匀分布。添加剂的不充分留着可引起运行性和质量问题。
WO2014132119公开了内联(在线,inline)生产留着剂的方法。该专利描述了在MFC的存在下水性硅酸盐聚合成胶体二氧化硅。可将MFC与硅酸盐和酸性介质的进料分开地进料至原料悬浮体或作为预混物进料至原料悬浮体
然而,仍需要使得MFC的工业生产和使用更高效以及提供MFC的改进的混合、再分散和处理。
发明内容
根据第一方面,本发明公开了制造组合物的方法,该方法包括在碱金属硅酸盐的存在下使纤维原纤化以形成MFC,由此形成MFC和硅酸盐混合物。优选在纤维悬浮体原纤化之前或在原纤化期间将碱金属硅酸盐添加至纤维悬浮体。
在纤维原纤化为MFC期间碱金属硅酸盐的存在降低了粘度并且改进了脱水效率,由此可在较高的浓度下实现原纤化以及实现更均匀的MFC-硅酸盐混合物(混合)。通过本发明的方法形成的组合物可因此包含比根据常规技术生产的MFC通常的固含量更高的固含量,这样的组合物的运输和处理由此更高效。另外,根据本发明生产的MFC-硅酸盐混合物使得组分能够受控添加至处理流中,由此避免了不期望的副反应。还已经显示出的是本发明的方法阻止了形成强MFC凝胶并且促进MFC再分散至水中。
碱金属优选为硅酸钠(水玻璃)。可替代地使用其他碱金属,比如钙、钾和/或锂。然而,由于钠的成本效益、反应性和碱度,其是优选的。
优选进行原纤化以产生SR(Schopper-Riegler)值高于40、优选高于50、或最优选高于60的MFC和硅酸盐混合物。
所述方法还可包括在原纤化之前和/或在原纤化期间将纤维与碱金属硅酸盐混合的步骤。在一个实施方式中,在混合和原纤化的步骤之前,待与碱金属硅酸盐混合和原纤化的纤维的SR值在15-80之间,优选在25-70之间或35-70之间。在此实施方式中,所述方法可包括在与碱金属硅酸盐混合之前的使纤维预原纤化的步骤。以此方式,所述方法可得到优化并且变得更有成本效益。
碱金属硅酸盐优选以1–99重量%的量存在,优选以1–90重量%的量存在,最优选1–80重量%,基于纤维的总固含量计。硅酸盐/纤维比例取决于最终用途。在一个实施方式中,碱金属硅酸盐优选以1–15重量%的量存在,比如在1–10重量%之间或5–10重量%。
在一个实施方式中,所述方法还包括将混合脱水至至少3重量%、至少5重量%、至少10重量%、或甚至至少15重量%或至少20重量%的固含量的步骤。最终固含量还取决于硅酸盐/MFC比例。在硅酸盐以至少1-10重量%的量存在的实施方式中,将混合物脱水至例如在3重量%-20重量%之间、或至少5–20重量%或10–20重量%的之间固含量,而在硅酸盐以更高的量存在的实施方式中,最终固含量还可更高。
在一个实施方式中,初始pH(即在原纤化方法(过程)开始时的pH)高于5,优选高于6或高于7。以此方式,纤维可被溶胀(swollen)并且对处理是更可及的。在一些实施方式中,在原纤化期间,pH在9.5–14之间或10–14之间,优选在10–13之间。
在另一实施方式中,初始pH低于5,比如范围为1-5。在此实施方式中,在添加水玻璃之后但在原纤化之前,可向纤维悬浮体添加酸。以此方式,抗脱水性甚至得到进一步降低。
在一个实施方式中,在原纤化期间,存在颜料,比如碳酸钙,高岭土,膨润土,塑料颜料,淀粉颜料,纳米粘土,PCC和/或滑石。
在原纤化步骤之后,可向MFC和硅酸盐混合物添加酸性介质,由此形成带有负电荷的胶体颗粒,其至少部分地沉淀在MFC纤维上。这些胶体颗粒可原样添加或与阳离子型聚合物组合添加至处理流,例如造纸配料。这形成了有效的留着体系。酸性介质可为任意一种矿物酸,比如硫酸、磷酸、盐酸;酸性金属盐,比如聚氯化铝(PAC)和/或二氧化碳。优选添加酸性介质以将pH降低至低于9,或低于7或低于6或低于5或甚至低于3。pH可例如降低至1-6之间,或1-5之间。任选地,在用酸性介质处理MFC和硅酸盐混合物之前或用酸性介质处理MFC和硅酸盐混合物的同时,将温度进一步升高至至少25℃,或至少45℃或至少65℃。原纤化期间和酸化之后的pH取决于添加的水玻璃和悬浮体中其他共添加剂的量。优选地,在酸化MFC和硅酸盐混合物时,pH应降低至少一个或至少两个单位。
在第二方面,本发明公开了通过根据本发明的方法生产的组合物。
在第三方面,本发明公开了所述组合物在纸或纸板生产中的用途。包含硅酸盐-MFC的组合物可例如添加至纸或纸板配料以强化由此生产的纸或纸板的强度。所述组合物还可与阳离子型聚合物一起添加至纸或纸板配料以提供高效的留着体系。
所述组合物还可用于水泥生产或用于复合材料的生产,以进一步用于例如粘合剂、涂料、膜、油漆(颜料)、清洁剂和包装的用途。其他可能的最终用途包括作为脱墨方法中或纸浆漂白(滩涂,beaching)中的添加剂
具体实施方式
根据本发明,将纤维素纤维原纤化以形成微原纤化纤维素,该原纤化在碱金属硅酸盐的存在下进行。
在本专利申请的上下文中,微原纤化纤维素(MFC)应意指至少一个维度小于100nm的纳米尺度的纤维素颗粒纤维或原纤维。MFC包括部分或完全原纤化的纤维素或木质纤维素纤维。释放的原纤维的直径小于100nm,而实际的原纤维直径或粒度分布和/或纵横比(长度/宽度)取决于来源和制造方法。
最小的原纤维被称为基础原纤维(初级原纤维)并且直径约为2-4nm(参见例如Chinga-Carrasco,G.,Cellulose fibres,nanofibrils and microfibrils,:Themorphological sequence of MFC components from a plant physiology and fibretechnology point of view,Nanoscale research letters 2011,6:417),而常见的是聚集形式的基础原纤维(其也被定义为微原纤维)(Fengel,D.,Ultrastructural behaviorof cell wall polysaccharides,Tappi J.,March 1970,Vol 53,No.3.)是在制造MFC时获得的主要产品,例如通过使用延长的精磨过程或压降分解过程制造。取决于来源和制造方法,原纤维的长度可在约1至大于10微米内变化。粗MFC级可含有相当大部分的原纤化纤维,即来自管胞(纤维素纤维)的突出原纤维,以及一定量的从管胞(纤维素纤维)释放的原纤维。
MFC有不同的首字母缩略词,例如纤维素微原纤维、原纤化纤维素、纳米原纤化纤维素、原纤维聚集体、纳米级纤维素原纤维、纤维素纳米纤维、纤维素纳米原纤维、纤维素微纤维、纤维素原纤维、微原纤状纤维素、微原纤维聚集体和纤维素微原纤维聚集体。MFC的特征还可在于各种物理或物理化学性质,例如大的表面积或其在分散在水中时在低固体(1-5重量%)下形成凝胶状材料的能力。优选将纤维素纤维原纤化至这样的程度,所形成的MFC的最终比表面积为约1至300m2/g,比如1至200m2/g,或更优选50至200m2/g,当用BET方法为冷冻干燥的材料测定时。
存在制造MFC的各种方法,例如单次或多次精磨,预水解然后是精磨或高剪切分解或原纤维的释放。通常需要一个或若干个预处理步骤,以使MFC制造既节能又可持续。因此,待供应的纸浆的纤维素纤维可进行酶法或化学预处理,例如以降低半纤维素或木质素的量。纤维素纤维可在原纤化之前进行化学改性,其中纤维素分子含有除了在原始纤维素中所发现的之外(或更多)的官能团。这些基团尤其包括羧甲基(CM)、醛和/或羧基(通过N-氧基介导的氧化获得的纤维素,例如“TEMPO”)或季铵(阳离子纤维素)。在以上述方法之一中进行改性或氧化后,更容易将纤维分解成MFC或纳米原纤维尺寸的原纤维。
纳米原纤状纤维素可含有一些半纤维素;量取决于植物来源。经预处理的纤维例如水解的、预溶胀的或氧化的纤维素原材料的机械分解用合适的设备进行,例如精磨机,研磨机,均化器,胶体排出装置(colloider),摩擦研磨机,超声波超声仪,流化器如微流化器、宏观流化器或流化剂型均化器。取决于MFC制造方法,产品还可含有细粒或纳米结晶纤维素或例如在木质纤维或造纸过程中存在的其他化学品。该产品还可含有各种量的未被有效地原纤化的微米尺寸的纤维颗粒。
MFC由木质纤维素纤维制备,包括硬木或软木纤维两者。其还可由微生物来源、农业纤维如麦草浆、竹子、甘蔗渣或其他非木质纤维来源制成。其优选由纸浆制成,包括来自原始纤维的纸浆,例如,机械、化学和/或热机械纸浆。其还可由损纸或再生纸制成。
上述MFC的定义包括但不限于在纤维素纳米原纤维(CMF)上新提出的TAPPI标准W13021,其定义了含有多个基础原纤维的纤维素纳米纤维材料,其具有结晶和无定形区域两者。
根据本发明的一个实施方式,使包含纤维素纤维和碱金属硅酸盐的悬浮体原纤化。碱金属硅酸盐可在原纤化之前或在原纤化期间添加至包含纤维素纤维的悬浮体。碱金属硅酸盐可作为具有至少5重量%或至少10或至少15重量%的固含量的溶液添加至纤维悬浮体。纤维素纤维可为硬木(宽叶木)和/或软木(针叶木)纤维。原纤化可通过使用例如均质器,优选以1–4重量%的稠度实现,在超精磨机中,优选以1–10重量%的稠度实现或通过在捣碎器(compactor,压实机)、撕碎机(shredder)、精磨机、纤维分离机、螺杆、制浆机、泵、或高剪切混合装置中的机械处理,以在5–30重量%之间的优选的稠度实现。
在一个实施方式中,在原纤化之前或在原纤化期间,将温度升高至高于30℃,或高于50℃或优选高于75℃。
任选地,所述方法还包括在原纤化步骤之前的预处理步骤,该预处理步骤可包括酶预处理或机械预处理。
实施例1
进行系列试验,其中将根据本发明生产的含MFC的组合物(样品2–6)的抗脱水性与参照MFC组合物(样品1和样品7)进行比较。参照样品1为由100重量%牛皮纸(kraf)纤维制得的MFC,不添加水玻璃。参照样品7为由牛皮纸纤维制得的MFC和水玻璃的混合物,其中已经在精磨后将MFC和水玻璃混合(后混合,post-mixing)。参照样品2–6为根据本发明的组合物,其中牛皮纸纤维已经在水玻璃的存在下原纤化。
使用牛皮纸纤维(松木)的纤维悬浮体进行实验,所述纤维悬浮体通过在3重量%稠度下以30000转数(英国标准湿式分解机(崩解机))进行分解(崩解)而被预处理。
在添加硅酸钠之前,将纤维悬浮体的pH调节至约9.5。在原纤化之前,将水玻璃(硅酸钠)添加至样品2–6。所添加的水玻璃为硅酸钠(干cont.50,17重量%,Bé48-50,密度1.40-1.52kg/dm3,SiO2,Na2O摩尔比2-2.1)。在原纤化之前和在原纤化之后的工艺条件示于表1中。所添加的水玻璃的量基于原纤化之前悬浮体中纤维的总量计算(20意味着20重量%的干的纤维量)。“pH,初始”是指在添加硅酸钠之后但在原纤化之前的pH。在样品6中,通过在原纤化之前添加硫酸而将pH调节至3.9。
通过流体化(流化)对纤维悬浮体进行原纤化。流体化通过使悬浮体通过400/200微米腔室2次,然后通过200/100微米腔室(Microfluidizer,微流化器)一次而进行。在试验之前或之后,不进行温度调节。
表1
为了研究抗脱水性,通过配备有0.65μmDVPP过滤器的真空过滤装置分别对参照MFC样品1、本发明的MFC-水玻璃样品(样品2–6)和参照样品7(后混合)进行脱水。在原纤化之前,使用RO水将样品稀释至0.1重量%稠度。使用杆式混合器进行混合(30sec)随后磁力搅拌至少2分钟。将稀释的悬浮体倒入真空过滤漏斗中。在启动真空抽吸的同时开启计时器。监测可见的水层从原纤维垫(膜)的顶部消失所需的时间(=脱水时间)。参照和本发明的样品的结果示于表2中。
表2
结果明确显示,由于根据本发明的共-原纤化,抗脱水性显著降低。
实施例2
进行另一系列试验以研究本发明组合物的水留着值(WRV)。
根据表3,将参照MFC样品1、本发明的样品4和后混合参照样品7(全部都如实施例1中那样制备,但流体化浓度为3%)与漂白的未曾干燥的桦木牛皮纸浆(未精磨)混合,其中TP 1指的是样品1与牛皮纸浆的混合物,TP 4指的是样品4与牛皮纸浆的混合物以及TP 7指的是样品7与牛皮纸浆的混合物。
表3
使用配备有0.65μm DVPP过滤器的真空过滤装置形成用于离心的纸浆垫。使具有约7–15重量%干含量的饼状物(滤饼)经历进行离心并且根据SCAN-C 62:00测定水留着值。结果示于表3中。
图1显示了对于不同的测试点的水留着值如何随提高的MFC含量变化。对于包含100重量%MFC的样品的WRV使用来自图1中所示图表的趋势线外推计算得出(表4)。
TP | WRV[%)] |
1 | 646.02 |
4 | 409.50 |
7 | 492.00 |
表4
如图1中和表4中可以看出的,根据本发明(TP 4)制得的组合物的水留着值显著地低于参照(TP4和TP7)的水留着值,尤其是在较高的MFC含量下。
Claims (13)
1.制造组合物的方法,该方法包括使纤维悬浮体中的纤维原纤化以形成微原纤化纤维素,
其中在纤维原纤化之前或在原纤化期间将碱金属硅酸盐添加至纤维悬浮体,使纤维与碱金属硅酸盐混合,并且碱金属硅酸盐以1-80重量%的量存在,基于纤维的总固含量计,
其中初始pH范围为1-5,初始pH是指在原纤化方法开始时的pH。
2.根据权利要求1所述的方法,其中碱金属硅酸盐为硅酸钠。
3.根据权利要求1-2中任一项所述的方法,其中待与碱金属硅酸盐混合和原纤化的纤维的SR值在15-80之间。
4.根据权利要求3所述的方法,其中待与碱金属硅酸盐混合和原纤化的纤维的SR值在25-70之间。
5.根据权利要求1-2中任一项所述的方法,其还包括将形成的组合物脱水至至少3重量%的固含量的步骤。
6.根据权利要求5所述的方法,其中所述固含量为至少5重量%。
7.根据权利要求6所述的方法,其中所述固含量为至少10重量%。
8.根据权利要求1-2中任一项所述的方法,其中在原纤化期间存在颜料。
9.根据权利要求1-2中任一项所述的方法,其中在原纤化之后将酸性介质添加至组合物。
10.根据权利要求1-9中的任一项所述的方法所生产的组合物。
11.根据权利要求10所述的组合物在纸或纸板生产中的用途。
12.根据权利要求10所述的组合物在水泥生产中的用途。
13.根据权利要求10所述的组合物在复合材料中的用途。
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- 2019-02-18 JP JP2020545119A patent/JP7356993B2/ja active Active
- 2019-02-18 CN CN201980016299.0A patent/CN111788347B/zh active Active
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US11643776B2 (en) | 2023-05-09 |
WO2019166912A1 (en) | 2019-09-06 |
CN111788347A (zh) | 2020-10-16 |
SE1850231A1 (en) | 2019-09-03 |
JP2021515114A (ja) | 2021-06-17 |
EP3759275A1 (en) | 2021-01-06 |
JP7356993B2 (ja) | 2023-10-05 |
SE543549C2 (en) | 2021-03-23 |
BR112020017828A2 (pt) | 2020-12-29 |
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