CN1829840A - 非木本植物材料的化学机械脱硅 - Google Patents
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Abstract
本发明涉及一种利用化学和机械作用从非木本植物材料去除硅石的方法。富含硅石的表皮细胞通过预制浆和低稠度磨浆步骤进行机械分离，并接着随增稠步骤的滤液从纸浆中脱除。无定形的硅石通过使用打浆机中的碱稀释源进行化学分离，然后随着增稠步骤和脱水步骤的滤液从纸浆中脱除。此后，通过调节滤液的pH值及接下来的分离步骤从滤液中脱除硅石。然后脱硅的纤维材料可以用已知的工艺进行化学或机械制浆和漂白。从非木本植物材料中脱除出来的硅石可以作为其他应用的原料。
Description
发明领域
本发明涉及一种从非木本植物纤维原料中去除硅石的化学机械方法。
发明背景
在利用非木本植物纤维原料，如麦秸、亚麻和大麻制浆及造纸方面的兴趣正在增加。这些以及其他的非木本木质素纤维素材料可以发规将提高农产品利润的增值利用。
由于预计将来木纤维短缺，相信非木本植物将成为一种可维持的纤维原料以潜在地补充木纤维在造纸方面的应用。市场压力及法律要求可能促进包含非木本植物纤维的纸张的生产，如用再生纤维验证的例子。
最初的造纸技术是由非木本植物原料发展而来的，而用木材生产纸浆与纸张是相对近些年的发展。制浆过程一般可以分成两大类：化学制浆和机械制浆。化学制浆包含利用化学反应溶解木质素并用木质素纤维素原材料制成单独的纤维或纸浆。在机械制浆分类中，有许多种工艺包含不同的化学、机械和热处理的组合以促进纤维分散、去除初始纤维中的某些木质素和其他化学成分、或增加最终纤维的白度或造纸强度。由木材得到的化学机械纸浆(CMP)通过如下工艺制成，用制浆化学品如二氧化硫、亚硫酸钠、亚硫酸氢钠或次硫酸钠的稀溶液处理原材料，接着进行机械纤维分离。
与非木本植物化学制浆相关的一个问题是从用过的蒸煮废液(“黑液”)中回收蒸煮化学品很困难，这是由于与木材相比，大多数非木本植物纤维中含有相对高含量的硅石。在非木本植物纤维的碱煮过程中，硅石被溶解并随着黑液流随后从纤维上除去，黑液被输送到化学品回收系统以转换成新鲜的蒸煮液。载有硅石的黑液引起蒸发器、增稠器和回收锅炉的起皮与结垢，结果造成低效率的运行及因清除而增加的停工时间。不能从载硅石黑液中回收蒸煮化学品导致了运行成本和流出液处理系统负荷的增加。
可选择地是，机械制浆似乎更适合于具有较高硅石含量的原材料，特别是麦秸与稻秸，这是因为硅石的溶解程度不会象化学制浆那么大，在整个制浆与漂白过程中大部分硅石将保留在纤维上。机械制浆也只产生小量的流出液，因此减小了环境影响。然而，机械制浆通常造成较低质量的纸浆。大量的木质素残留在机械纸浆中，使其与同样的化学纸浆相比，更脆弱也更难以漂白到高白度。
在美国专利No.6,183,598中，公开了一种从黑液中回收碱和热能的方法。黑液是在非木本植物材料与包含氢氧化钠的碱煮液一起加热的化学过程的结果。黑液中包含大量的硅酸根离子。用石灰回收氢氧化纳经常因硅酸钙的形成而受阻，以至于很难或不可能回收石灰。这篇专利提出的解决方法是用二氧化碳处理黑液使硅石和木质素沉淀。然后脱除固体，将剩余的黑液蒸发和燃烧以产生热，碳酸钠熔融，从而形成二氧化碳。然后将所形成的二氧化碳再用于处理黑液。然而，随着木质素的沉积，也可能损失一些无机物，这将限制潜在的回收效率。由于沉积一些木质素造成热量损失，这种方法也是耗能的，另外这些木质素可以在回收锅炉中燃烧产生蒸汽。
在本领域中仍旧需要一些方法可以允许用非木本植物纤维制浆，同时允许高硅石含量纤维的化学回收。
发明概述
一方面，本发明包括一种在由非木本植物纤维制浆的工艺中的化学机械除硅方法，其包括如下步骤：
(a)在控制的温度、固体含量或稠度、和pH值条件下，对非木本植物纤维进行湿法预制浆；
(b)通过过滤或脱水，或过滤和脱水把悬浮固体和溶解的固体从预制浆材料的纤维部分脱除；
(c)在滤液中加酸，以促使溶解的硅石沉淀；和
(d)把硅石和其他固体从滤液中脱除，滤液重新用于预制浆步骤。
附图说明
现在，将参照简化的、图表式的、没有标度的附图用实施方式描述本发明。在附图中，图1是本发明的一个实施方式的图示说明。
本发明的详细说明
本发明提供了一种从非木本植物纤维原料中对物料脱硅的方法。在本发明的描述中，所有在本文中没有限定的术语都具有常规的本领域认可的意义。
如本文使用的术语“非木本植物纤维”是指不是源自木本植物的木质素纤维素材料。非木本植物纤维原料包括但不限于农业废弃物、一年生或多年生草类和每年收割的纤维作物。农业废弃物的例子包括麦秸、稻秸、大麦秸、燕麦秸、谷秸杆、甘蔗渣、油籽用亚麻杆、和油籽用大麻杆。一年生或多年生草类的例子包括芦苇淡黄色草、黑麦草、芦苇草、鞭子草、和羊矛。每年收割的纤维作物的例子包括纤维亚麻、纤维大麻和南非槿麻。
在一个实施方式中，本发明包括预制浆工艺，其后面可以跟着酸处理和漂白步骤。预制浆工艺的目的是分离并去除存在于非木本植物材料中的大量硅石。下面的说明书用麦秸对本方法进行说明，不过本领域技术人员将意识到此方法也同样适用于其他的非木本植物纤维。
概括地说，，预制浆步骤是在常规制浆工艺之前用于对物料进行准备并脱硅。确信后面可以生产出质量合格的纸浆，同时对环境的影响较少而且化学品与能量成本较低。上述工艺在同一单元操作中结合了化学和机械作用。机械作用分离了含有存在于麦秸中总硅石量大部分的麦秸部分(包括表皮和结节材料)，化学作用溶解掉分布于整个麦秸残余部分的硅石。在将碱溶液，例如在接下去的碱制浆步骤中产生的淡黑液添加到打浆机和磨浆机的稀释液中时发生化学作用。上述作用优选在控制的稠度、温度和pH值或碱度的条件下进行。
第一步是用机械制浆设备对麦秸的表皮层和结节材料进行机械分离。在一个优选实施方式中，机械作用可以通过两步进行，包括用打浆机减小从预切割阶段生成的粗粒子的尺寸并开始分离表皮层和结节材料，和用低稠度磨浆机完成尺寸减小和表皮层及结节材料的分离。麦秸可以在此机械制浆阶段之前用干法工艺进行切割和筛浆，如用盘式削片机、铡草机或筒式粉碎机进行切割，接着用如转鼓筛浆机、振荡筛浆机或滚筒型筛浆机进行筛浆步骤。在一个实施方式中，使用Tornado打浆机TM(Bolton-Emerson Americas Inc.)，在弱碱性(pH为7-11)条件下，以低稠度对麦秸进行制浆，例如约0.5％-6％固含量，之后对纸浆进行脱水或增稠。pH值使用淡黑液维持在预定范围内，上述黑液从下面所述的后续步骤中回收而来并用作机械制浆的稀释源。浑浊的白水、酸滤液、新鲜碱液或新鲜酸也可以用于调节pH值。
增稠作用既可以分离载有硅石的小颗粒又可以分离由于碱溶解而进入到滤液流中的可溶性硅石。本文使用的“小颗粒”，是指能通过150目筛网的材料。一旦滤液被去除，就可以降低其pH值以使可溶性硅石沉淀。然后沉淀出的硅石可以用重力沉淀、离心作用或过滤进行分离。然后滤液可以返回到体系重新用作机械制浆步骤的稀释液。
经预制浆和脱硅后的物料可以用已知的常规制浆和漂白技术进行处理。例如，适宜的技术被描述在美国专利No.6,302,997和6,258,207中。
图1所示的图表是一个脱硅预制浆过程。成捆的植物材料(10)被投入到此过程中。拆捆机(12)把整捆分割成易操作的小段，减小粒度(例如，用铡草机)或者不减小粒度(例如，用简单的机械楔子)以喂入到打浆机(14)中。在打浆机(14)中，减小粒度并基本上开始除去麦秸中富含硅石的部分。传送通过打浆机(14)的物料在旋风分离器(15)加工以在磨浆前除去大块的外来杂质如石块和金属。然后植物材料在磨浆机(16)中进行低稠度磨浆，在此表皮和结节部分的机械分离基本上完成。磨浆后，物料通过一个斜筛(sidehillscreen)(18)，在这里水与表皮和结节材料一起从纤维化悬浮体中脱除。分离出的表皮材料的尺寸能够随滤液通过斜筛。在一个压榨机(20)中进行进一步的脱水，压榨机可以是一个螺杆压榨机、皮带压滤机或类似的脱水设备。
打浆机中pH值和温度可以控制到去除硅石的最佳条件。优选条件是温度在50℃-90℃，pH值在7-12之间。本文所用的“硅石”既是指存在于表皮层和结节材料中的硅石，这些材料可以被机械分离并脱除，又是指可以在优选工艺条件下被溶解的硅石。
从斜筛和脱水压榨机得到的滤液都富含硅石。上述滤液送到一个滤液罐(22)并可以在此处与后续加工步骤中的白水进行混合。
然后可以调节富含硅石的滤液(24)的pH值以使可溶性硅酸根离子沉淀，接着在一个水力旋流离心机(26)系统中进行分离以除去悬浮的固体和沉淀的硅石。然后稀滤液(28)可以随着来自前述原料的补充水重新作为打浆机(14)和低稠度磨浆机的稀释液。
在这个循环中的余量水(30)可以直接排放到流出液处理系统进行进一步的处理。处理可以包括沉降或浮选以除去悬浮固体，有氧或厌氧处理以除去溶解的和胶状的有机物质，或上述处理方法的组合。
沉淀的硅石本身是一种有用或有价值的产品，可以被用于其他工业应用或工艺。这种回收和再利用硅石的能力可以提高非木纤维加工设备的经济效益。
本领域技术人员能够明显看出，在不背离本发明的范围的情况下，可以对上述特定公开作出各种更改、改变和变化。在不背离本发明的范围的情况下，上述发明的各种特征与元素可以以不同于已经描述或提出的组合的方式进行组合。
Claims (8)
1、一种非木本植物纤维脱硅方法，包括：
(a)在控制的温度、固体含量和pH值条件下，对非木本植物纤维进行湿法预制浆；
(b)通过过滤或脱水，或过滤和脱水把悬浮固体和溶解的固体从预制浆材料的纤维部分脱除；
(c)在滤液中加酸，以促使溶解的硅酸盐沉淀；和
(d)把硅石和其他固体从滤液中脱除，滤液重新用于预制浆步骤。
2、如权利要求1的方法，其中对得到的非木本植物纤维继续进行化学、机械或化学机械制浆，然后漂白。
3、如权利要求1的方法，其中沉淀的硅石被回收并使用。
4、如权利要求1的方法，其中纤维进行湿法预制浆的pH值约为7-11。
5、如权要求1的方法，其中纤维进行湿法预制浆的温度约为50℃-90℃。
6、如权利要求1的方法，其中纤维进行湿法预制浆到固含量约为0.5％-6.0％固体。
7、如权利要求1的方法，其中纤维包括麦秸。
8、如权利要求2的方法，其中纤维进行湿法预制浆时使用从后面的碱制浆过程回收的淡黑液。
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| FI122815B (fi) * | 2005-04-18 | 2012-07-13 | Cerefi Oy | Menetelmä lignoselluloosamateriaalien ja niistä saatujen jakeiden fraktioimiseksi |
| US20070000628A1 (en) * | 2005-06-30 | 2007-01-04 | Sealey James E Ii | Method for removal of metals from a bleach plant filtrate stream |
| KR100669109B1 (ko) * | 2006-08-04 | 2007-01-16 | 김해곤 | 감귤류박섬유를 함유한 종이 |
| DE102006057861A1 (de) * | 2006-12-08 | 2008-06-12 | Voith Patent Gmbh | Verfahren zur Behandlung von beim Eindicken von Papierfasersuspension anfallendem Filtrat |
| DE102007044952A1 (de) * | 2007-09-20 | 2009-04-02 | Voith Patent Gmbh | Verfahren zur Behandlung einer Papierfasersuspension |
| US20150122442A1 (en) * | 2012-04-03 | 2015-05-07 | Ovivo Luxembourg S.Å.R.L. | Process for removal of solid nonifibrous material from pulp |
| CN103046426A (zh) * | 2013-01-14 | 2013-04-17 | 岳阳林纸股份有限公司 | 一种以芦苇为原料的半化学浆的制浆方法 |
| CN103469664B (zh) * | 2013-08-26 | 2015-09-16 | 陕西科技大学 | 一种碱回收工段绿液絮凝除硅方法 |
| CN103526625B (zh) * | 2013-10-14 | 2016-03-23 | 于志强 | 生物酶化与煸法相结合的制浆方法及制浆的单根煸管装置 |
| WO2015139141A1 (en) * | 2014-03-21 | 2015-09-24 | Iogen Energy Corporation | Method for processing a cellulosic feedstock at high consistency |
| GB2530987B (en) | 2014-10-03 | 2017-06-21 | Nafici Env Res (Ner) Ltd | A method for processing straw |
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| US1588335A (en) * | 1920-02-12 | 1926-06-08 | Puttaert Jean Francois | Process of making pulp from hulls |
| US1757768A (en) * | 1925-09-02 | 1930-05-06 | Northwest Paper Company | Purified fiber |
| US1758655A (en) * | 1927-01-17 | 1930-05-13 | Cornstalk Products Company | Method of producing cellulosic material |
| US1879503A (en) * | 1931-08-22 | 1932-09-27 | Rinman Erik Ludvig | Method of relieving alkaline solutions, particularly waste liquors from the soda or sulphate pulp manufacture, of silica |
| GB576785A (en) * | 1942-03-11 | 1946-04-18 | Henry Dreyfus | Improvements in or relating to the manufacture of cellulose |
| US4199399A (en) * | 1976-04-19 | 1980-04-22 | Process Evaluation & Development Corp. | Method for preparing bagasse dissolving pulps and producing rayon having a degree of polymerization of at least 800 therefrom |
| US4331507A (en) * | 1979-12-10 | 1982-05-25 | Dorr-Oliver Incorporated | Desilication in alkaline pulp processes |
| DE3107447C2 (de) * | 1981-02-27 | 1985-08-29 | Kraftanlagen Ag, 6900 Heidelberg | Verfahren zum Entfernen von Kieselsäure aus Schwarzlauge |
| DE3208200A1 (de) * | 1982-03-06 | 1983-09-08 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur kontinuierlichen entfernung von kieselsaeure aus zellstoffablaugen |
| US4957599A (en) * | 1988-04-15 | 1990-09-18 | E. I. Du Pont De Nemours And Company | Alkaline extraction, peroxide bleaching of nonwoody lignocellulosic substrates |
| US5198074A (en) * | 1991-11-29 | 1993-03-30 | Companhia Industreas Brasileiras Portela | Process to produce a high quality paper product and an ethanol product from bamboo |
| US5374333A (en) * | 1992-07-30 | 1994-12-20 | Kamyr, Inc. | Method for minimizing pulp mill effluents |
| US5635024A (en) * | 1993-08-20 | 1997-06-03 | Bountiful Applied Research Corporation | Process for separating lignins and dissolved organic compounds from kraft spent liquor |
| FI104335B (sv) * | 1997-10-13 | 1999-12-31 | Poeyry Jaakko & Co Oy | Förfarande för återvinning av alkali och energi ur silikathaltig svartlut |
| ES2209420T3 (es) * | 1998-04-17 | 2004-06-16 | Alberta Research Council, Inc. | Metodo de produccion de pulpa lignocelulosica a partir de especies no leñosas. |
| US6302997B1 (en) * | 1999-08-30 | 2001-10-16 | North Carolina State University | Process for producing a pulp suitable for papermaking from nonwood fibrous materials |
| CN2552996Y (zh) * | 2002-05-09 | 2003-05-28 | 朱杰 | 干煸分离草浆机 |
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| EP1664421B1 (en) | 2011-12-07 |
| CA2526406A1 (en) | 2005-03-17 |
| CA2526406C (en) | 2012-06-26 |
| US20050051287A1 (en) | 2005-03-10 |
| CN100595375C (zh) | 2010-03-24 |
| EP1664421A4 (en) | 2009-01-14 |
| EP1664421A1 (en) | 2006-06-07 |
| US7364640B2 (en) | 2008-04-29 |
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