CN101171386B - 二氧化氯处理组合物和方法 - Google Patents

二氧化氯处理组合物和方法 Download PDF

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CN101171386B
CN101171386B CN2005800496985A CN200580049698A CN101171386B CN 101171386 B CN101171386 B CN 101171386B CN 2005800496985 A CN2005800496985 A CN 2005800496985A CN 200580049698 A CN200580049698 A CN 200580049698A CN 101171386 B CN101171386 B CN 101171386B
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chlorine dioxide
peroxidase
pulp
laccase
haloperoxidase
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徐辉
金·布卢姆菲尔德
亨里克·伦德
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Novozymes North America Inc
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    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • 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
    • D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
    • D21H11/04—Kraft or sulfate pulp
    • D—TEXTILES; PAPER
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    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
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    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/18—Pulping cellulose-containing materials with halogens or halogen-generating compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • 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
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites

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Abstract

本发明涉及通过使纸浆与二氧化氯、过氧化物酶和/或漆酶反应用于二氧化氯脱木质化和/或漂白过程的方法和组合物。

Description

二氧化氯处理组合物和方法
发明领域
本发明涉及用于改进二氧化氯处理工艺，如纸浆脱木质化(pulpdelignification)和漂白工艺的方法和组合物。
发明背景
二氧化氯是纸浆及造纸工业(pulp and paper industry)中最广泛使用的脱木质化剂/漂白剂之一，其提供了高质量、低成本的脱木质化和漂白方法。二氧化氯处理优于氯漂白方法之处在于，它实际上消除了排入环境的所有二英(dioxin)，并因此有助于纸浆及造纸生产(pulp and paper manufactures)采用环境友好的方法并满足环境要求。因此，二氧化氯处理的使用正在增加并且大多数纸浆及造纸厂目前具有至少一个二氧化氯脱木质化或漂白阶段。二氧化氯处理也已用于处理废水、污泥(sludge)和其它工业生产液流(process streams)。
在二氧化氯处理方法中，一些二氧化氯转变成氯酸盐和亚氯酸盐，这降低了二氧化氯处理的效率。已提出了多种方法以通过减少氯酸盐和亚氯酸盐的形成去改进二氧化氯处理方法的效率。例如，Seger et al.，Chiang，Tappi J.，1992，75(7)：174-180公开了两步高-pH和低-pH方法，认为该方法在较高的pH减少了氯酸盐的形成并且亚氯酸盐在低pH步骤中变得易起反应。Joncourt etal.，International Symp.Wood Pulping Chemistry，Montreal，Jun.9-12，1997公开了铁从亚氯酸盐中再生二氧化氯的用途。Jiang等美国专利号6,235,154公开了用甲醛通过从亚氯酸盐中再生二氧化氯来改进二氧化氯脱木质化或漂白的方法。
需要新的组合物和方法来改进二氧化氯处理的效率和有效性，所述二氧化氯处理包括二氧化氯脱木质化和漂白方法。
发明概述
本发明涉及通过使纸浆与二氧化氯和过氧化物酶和/或漆酶反应用于二氧化氯脱木质化和/或漂白工艺的方法和组合物。依据本发明，将过氧化物酶和/或漆酶加入二氧化氯脱木质化和/或漂白步骤中。虽然不受限于任一操作理论，认为将过氧化物酶和/或漆酶加入二氧化氯处理组合物导致二氧化氯从亚氯酸盐再生，从而在纸浆的漂白过程中导致改进的脱木质化和/或增白(brightening)。
本发明涉及用于废水、污泥或任何其它工业生产液流的二氧化氯处理的方法和组合物。依据本发明，将过氧化物酶和/或漆酶加入二氧化氯处理步骤以改进二氧化氯处理方法。
发明详述
“过氧化物酶”指过氧化物酶(E.C.1.11.1.7)和/或卤素过氧化物酶(haloperoxidase)，例如，优选氯化物过氧化物酶(chloride peroxidase)(E.C.1.11.1.10)。优选，过氧化物酶是酸稳定的过氧化物酶。
可以从任何适宜的来源获得过氧化物酶，例如，来自植物(例如大豆过氧化物酶或辣根过氧化物酶(soy bean or horseradish peroxidase))，和来自微生物(真菌和细菌，例如，例如可从鬼伞属(coprinus)菌株例如灰盖鬼伞(coprinuscinerius)或长根鬼伞(coprinus macrorhizus)或芽孢杆菌属(Bacillus)菌株如短小芽孢杆菌(Bacillus pumilu)中获得过氧化物酶)。一些优选的真菌来源包括属于半知菌亚门(Deuteromycotina)，丝孢菌类(class Hyphomycetes)的菌株，例如镰孢属(Fusarium)、腐质霉属(Humicola)、木霉属(Tricoderma)、漆斑菌属(Myrothecium)、轮枝孢属(Verticillum)、Arthromyces、卡尔黑霉属(Caldariomyces)、单格孢属(Ulocladium)、Embellisia、枝孢属(Cladosporium)或Dreschlera，具体为尖镰孢(Fusarium oxysporum)(DSM 2672)、特异腐质霉(Humicola insolens)、里氏木霉(Trichoderma resii)、疣孢漆斑菌(Myrotheciumverrucana)(IFO 6113)、黄萎轮枝孢(Verticillum alboatrum)、大丽花轮枝孢(Verticillum dahlie)、Arthromyces ramosus(FERM P-7754)、烟色卡尔黑霉(Caldariomyces fumago)、纸单格孢(Ulocladium chartarum)、Embellisia alli或Dreschlera halodes。其它优选的真菌来源包括属于担子菌亚门(Basidiomycotina)、担子菌纲(Basidiomycetes)的菌株，例如鬼伞属、平革菌属(Phanerochaete)、革盖菌属(Coriolus)或栓菌属(Trametes)，特别是Coprinuscinereusf.microsporus(IFO 8371)、长根鬼伞、黄孢平革菌(Phanerochaetechrysosporium(例如NA-12))或采绒革盖菌(Coriolus versicolor(例如PR428-A))。其它优选的真菌来源包括属于接合菌亚门(Zygomycotina)，classMycoraceae的菌株，例如根霉菌属(Rhizopus)或毛酶属(Mucor)，具体为冻土毛霉(Mucor hiemalis)。
一些优选的细菌过氧化物酶来源包括放线菌目(Actinomycetales)的菌株，例如类球形链霉菌(Streptomyces spheroides)(ATTC 23965)、热紫链霉菌(Streptomyces thermoviolaceus)(IFO 12382)或者轮丝链轮丝菌轮丝种(Streptoverticillum verticillium ssp.verticillium)。其它优选的细菌来源包括短小芽孢杆菌(ATCC 12905)、嗜热脂肪芽孢杆菌(Bacillus stearothermophilus)、类球红细菌(Rhodobacter sphaeroides)、Rhodomonas palustri、乳链球菌(Streptococcus lactis)、吡咯菌素假单孢菌(Pseudomonas purrocinia)(ATCC15958)或荧光假单孢菌(Pseudomonas fluorescens)(NRRL B-11)。
可从任何适宜的来源获得卤过氧化物酶。卤过氧化物酶例如已经从各种生物体分离，包括哺乳动物、海洋动物、植物、藻类、地衣、真菌和细菌(参见Biochimica et Biophysica Acta 1161，1993，pp.249-256)。适宜的氯过氧化物酶(choloroperoxidases)包括从真菌不等弯孢(Curvularia inaequalis)获得的氯过氧化物酶(参见SWISS-PROT：P49053)，从小疣弯孢(Curvularia verruculosa)获得的氯过氧化物酶(参见WO97/04102)和Svendsen等美国专利号6,372,465中公开的氯过氧化物酶。
可从任何适宜的来源，例如从选自下组的属获得漆酶(EC1.10.3.2)：曲霉属(Aspergillus)、葡萄孢属(Botrytis)、金钱菌属(Collybia)、层孔菌属(Fomes)、香菇属(Lentinus)、毁丝霉属(Myceliophthora)、脉孢菌属(Neurospora)、侧耳属(Pleurotus)、柄孢壳属(Podospora)、多孔菌属(Polyporus)、柱顶孢属(Scytalidium)、栓菌属以及丝核菌属(Rhizoctonia)。在更优选的实施方案中，漆酶从选自下组的菌种获得：Humicola brevis var.thermoidea、Humicolabrevispora、Humicola grisea var.thermoidea、特异腐质霉和Humicolalanuginosa(也称为疏棉状嗜热丝孢菌(Thermomyces lanuginosus))、嗜热毁丝霉(Myceliophthora thermophila)、Myceliophthora vellerea、Polyporus pinsitus、嗜热柱顶孢(Scytalidium thermophila)、Scytalidium indonesiacum和嗜热色串孢(Torula thermophila)。漆酶可以从柱顶孢属的其它菌种获得，例如Scytalidiumacidophilum、Scytalidium album、Scytalidium aurantiacum、Scytalidiumcircinatum、Scytalidium flaveobrunneum、透明柱顶孢(Scytalidium hyalinum)、木生柱顶孢(Scytalidium lignicola)和Scytalidium uredinicolum、立枯丝核菌(Rhizoctonia solani)和灰盖鬼伞。漆酶可以从多孔菌属的其它菌种获得，例如环纹多孔菌(Polyporus zonatus)、Polyporus alveolaris、Polyporus arcularius、Polyporus australiensis、Polyporus badius、二型多孔菌(Polyporus biformis)、冬生多孔菌(Polyporus brumalis)、Polyporus ciliatus)、Polyporus colensoi、Polyporus eucalyptorum、Polyporus meridionalis、黑柄多孔菌(Polyporusvarius)、Polyporus palustris、喜根多孔菌(Polyporus rhizophilus)、Polyporusrugulosus、鳞多孔菌(Polyporus squamosus)、块茎形多孔菌(Polyporus tuberaster)和Polyporus tumulosus。
“二氧化氯处理”指任何二氧化氯处理过程，例如，用于纸浆及造纸厂中的二氧化氯处理阶段以及废水和/或污泥，例如植物废水或普通的家庭污水(sewage)或废水的二氧化氯处理。
通常，将二氧化氯处理应用于纸浆及造纸厂中脱木质化和漂白过程中。可处理任何适宜的纸浆，虽然优选纸浆是木质纤维素纸浆。在二氧化氯处理前、处理过程中或处理后，可将纸浆用其它的脱木质化剂和/或漂白剂处理，例如，例如氧脱木质化(oxygen delignification)、过氧化物处理以及酶处理过程。
可通过任何适宜的方法产生处理方法中使用的二氧化氯。然而，因为二氧化氯作为气体是不稳定的，并且只能保存为溶液，它通常在现场(on-site)，例如在纸浆厂(pulp mills)产生。但是，一旦在溶液中，二氧化氯相当稳定。
如本领域所知的，通常将二氧化氯以有效处理纸浆或工艺用水(processwaters)(例如废水)的量加入。
通常在约40至80℃的温度进行纸浆的二氧化氯处理约15-120分钟的时间。二氧化氯的有效性部分地倚赖于pH，并且在约2至4的pH最大化。因为纸浆液流(pulp streams)和其它工艺用水的pH通常是碱性更强的，可将酸加入处理水(treatment water)以降低pH。在一些方法中，可通过使用过量的二氧化氯来控制工艺用水的pH。
将过氧化物酶和/或漆酶以有效改进二氧化氯处理方法的量直接施用于二氧化氯工业生产液流中，如下文所示例的。过氧化物酶和/或漆酶可作为二氧化氯溶液的部分、用于制备工业用水的滤出液的一部分(例如脱木质化或漂白液)应用于循环的工艺用水中和/或通过单独的添加来应用。
以有效改进二氧化氯处理方法的量，例如，如通过改进的纸浆脱木质化和/或改进的纸浆漂白所测量的量，施用过氧化物酶和/或漆酶。过氧化物酶的有效量的实例是0.005mg-10g/L工艺用水，更优选0.01-1000mg/L工艺用水，以及最优选0.05-500mg/L工艺用水。对于纸浆应用，过氧化物酶的此有效量可包括0.01g-20kg/吨纸浆，更优选0.1g-5kg/吨纸浆，并最优选1g-2kg/吨纸浆。漆酶的有效量的实例是0.005mg-10g/L工艺用水，更优选0.01-1000mg/L工艺用水，以及最优选0.05-500mg/L工艺用水。对于纸浆应用，漆酶的此有效量可包括0.01g-20kg/吨，更优选0.1g-5kg/吨，并最优选1g-2kg/吨。基于过氧化物酶和漆酶与纸浆处理或废水/污泥处理的过程条件，例如最适pH、最适温度、酸稳定性的相容性，优选选择过氧化物酶以及漆酶。
尽管已参考具体的实施方案在本文中描述了本发明，但可以理解，这些实施方案仅仅是本发明原理和应用的示例性说明。因此，可以理解，可对示例性的实施方案进行多种修饰并可设计其它的方案而不偏离如所附权利要求所限定的本发明的精神和范围。
实施例
实施例1
将160mg的NaClO2溶解于100ml的DI水中。将NaClO2溶液的10ml等分试样加入不同的试管中。将20uL的醋酸加入每个试管，并将pH调至约3.5。接着将100uL的酶加入溶液。在环境温度温育30分钟后，将溶液用DI水稀释3倍。通过在360nm的UV吸光度(absorbency)检测ClO2形成。显然在此试验所用的条件下，所有的酶在某种程度上都能产生ClO2。
表1酶促二氧化氯产生
 No. 样品 在360nm的吸光度
 1 对照     0.155
 2 来自灰盖鬼伞的过氧化物酶(Novozymes)     0.764
 3 来自小疣弯孢的卤过氧化物酶(Novozymes)     0.168
 4 来自Trametes villosa的漆酶(Novozymes)     0.802
 5 来自灰盖鬼伞的漆酶(Novozymes)     0.190
 6 来自嗜热毁丝霉的漆酶(Novozymes)     0.197
 7 来自烟色卡尔黑霉的氯过氧化物酶(Sigma，C-0278)     0.393
实施例2
将5g(o.d.干燥的)未漂白的牛皮纸浆(kraft pulp)加入每个烧杯，并稀释至约5％的稠度(consistency)。用2N H2SO4将纸浆调节到不同的pH。将10mL11.3/L的NaClO2加入每个烧杯。将500uL过氧化物酶(灰盖鬼伞过氧化物酶，Novozymes)加入溶液并将烧杯在60°温育1小时。漂白后，用DI水冲洗纸浆并制成手抄纸(handsheet)，并测试白度(brightness)。依据Tappi标准(T452)测试白度。显然，在所有的pH范围内过氧化物酶改进了纸浆的白度。
    pH 样品     白度
    3 对照     50.4
    3 过氧化物酶     51.4
    4 对照     46.8
    4 过氧化物酶     47.3
    5 对照     43.3
    5 过氧化物酶     44.2
    6 对照     42.8
    6 过氧化物酶     45.0

Claims (9)

1.使纸浆脱木质化和/或漂白的方法，该方法使纸浆、二氧化氯和卤过氧化物酶反应。
2.权利要求1的方法，其中所述卤过氧化物酶是氯化物过氧化物酶。
3.权利要求2的方法，其中所述氯化物过氧化物酶是不等弯孢过氧化物酶或小疣弯孢过氧化物酶。
4.处理废水和/或污泥的方法，其包括使废水和/或污泥、二氧化氯和卤过氧化物酶反应。
5.权利要求4的方法，其中所述卤过氧化物酶是氯化物过氧化物酶。
6.权利要求5的方法，其中所述氯化物过氧化物酶是不等弯孢过氧化物酶或小疣弯孢过氧化物酶。
7.使纸浆脱木质化和/或漂白的方法，其包括使纸浆、二氧化氯和漆酶及卤过氧化物酶反应。
8.权利要求7的方法，其中漆酶是栓菌属、鬼伞属或者毁丝霉属漆酶。
9.根据权利要求7的方法，其中所述卤过氧化物酶是氯化物过氧化物酶。
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