CN1117301A - 用乙酸作酸化剂的纸浆无氯漂白方法 - Google Patents

用乙酸作酸化剂的纸浆无氯漂白方法 Download PDF

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Publication number
CN1117301A
CN1117301A CN 94191058 CN94191058A CN1117301A CN 1117301 A CN1117301 A CN 1117301A CN 94191058 CN94191058 CN 94191058 CN 94191058 A CN94191058 A CN 94191058A CN 1117301 A CN1117301 A CN 1117301A
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pulp
peroxide
acid
chelating agent
paper pulp
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E·尼尔松
P·狄比林
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Chemrec AB
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Chemrec AB
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-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
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/16Bleaching ; Apparatus therefor with per compounds
    • D21C9/166Bleaching ; Apparatus therefor with per compounds with peracids
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-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
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/1005Pretreatment of the pulp, e.g. degassing the pulp
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-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
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/1026Other features in bleaching processes
    • D21C9/1042Use of chelating agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-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
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/16Bleaching ; Apparatus therefor with per compounds
    • D21C9/163Bleaching ; Apparatus therefor with per compounds with peroxides

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

本发明公开了一种在制备化学纸浆时不用氯而将纤维素纤维材料漂白的方法,其中将纸浆连续送料进入漂白流程,在至少一种酸存在下调节pH值于7以下并用螯合剂处理,然后经过包括过氧化物、至少一种有机过酸和过氧化物几个步骤的流程进行漂白,其特点是在对纸浆进行螯合剂处理时以乙酸作为酸化剂。

Description

用乙酸作酸化剂的 纸浆无氯漂白方法
本方法涉及在制备化学纸浆时不用氯而将纤维素纤维材料漂白的方法。本方法中将纸浆连续送料进入漂白流程,在至少一种酸存在下调节pH值于7以下并用螯合剂处理,然后经过包括过氧化物、一种或几种有机过酸和过氧化物几个步骤的流程进行漂白。
含氯漂白剂会形成氯化了的有机化合物,用含氯漂白剂漂白纸浆需要严格的环境要求,因此许多研究工作都旨在发现对环境无害的其它漂白剂。已有人提出先用螯合剂处理再用臭氧、过氧化物等不同流程漂白纸浆。如SE—A—9101300—3中所述。但是用臭氧的方法有许多缺点。臭氧对纤维素有分解作用,而且与漂白步骤相关的生产和贮备臭氧的设备庞大而昂贵。与SE—B—405130相对应的US—A—3,867,246描述了另一种不用氯的漂白流程,包括过氧化物、过乙酸和过氧化物步骤。在第一个过氧化物步骤前,用酸调节至较低pH值并用螯合剂进行处理,通常所用的酸是硫酸。但是同臭氧一样,过乙酸对纤维素有很强的分解作用。
本发明的目的是解决不用氯漂白纸浆方法中的问题。在一种酸存在下先用螯合剂(Q)进行处理,在PPaP漂白流程中将过乙酸和过氧化物结合使用,以使所得到的漂白纸浆具有可接受的粘度和强度特性并满足市场要求的85—90%ISO的白度。
本发明所涉及方法的特点是在用螯合剂处理期间纸浆用乙酸酸化。
进料的纸浆优选是用产生低卡伯值的蒸煮工艺制造出来的并经氧气去木质化的纸浆,其卡伯值约为12或小于12。粘度至少约为1000dm3/kg。
所用过氧化物优选为过氧化氢。
第一过氧化物步骤之后是第二漂白步骤,用过甲酸、过乙酸或过丙酸处理。优选使用过乙酸或至少两种上述过酸的混合物。
根据一个适宜的实施方案,乙酸添加量为使pH值低于6,优选低于5。
漂白流程中温度应为80℃或80℃以上,优选90℃。
每个过氧化物步骤适于在碱性溶液中进行。
过乙酸步骤优选在酸性溶液中进行。
乙酸、过乙酸或其它适用的过酸优选在现场制备。
在各处理步骤中纸浆浓度约为8—16%,优选9—11%。
以下实施例进一步说明本发明和其意想不到的效果。
实施例
用软木硫酸盐纸浆作了多次实验,纸浆用氧气去木质化并洗涤。去木质化纸浆的卡伯值为12.1,白度为33.7%ISO,粘度为1020dm3/kg。将纸浆以10%的浓度送入漂白流程,并在螯合剂EDTA处理过程中和所有漂白步骤中均保持此浓度。实施例1和2中用硫酸作Q步骤的酸化剂,根据本发明的实施例3和4用乙酸作酸化剂。
实施例1—4
    1.添加剂          漂白流程
    2.条件        QPPaP1      2       QPPaP3       4
       3.结果
 Q—步骤1.EDTA,kg/BDMTH2SO4,kg/BDMT乙酸,kg/BDMT2.初始pH值时间,分钟温度,℃P—步骤1.H2O2,kg/BDMTMgSO4,kg/BDMTNaOH,kg/BDMT2.时间,分钟温度,℃最终pH值3.消耗H2O2,kg/BDMT卡伯值粘度,dm3/kg白度,%ISO 2.06.2-4.76070353.0252409010.9185.191077.3 2.0-15.04.86070353.0252409011.0164.991177.0
    1.添加剂                   漂白流程
    2.条件           QPPaP1               2           QPPaP3           4
    3.结果
pa-步骤1.以总的H2O2计的过乙酸,kg/BDMT2.缓冲液pH值醋酸钠时间,分钟温度,℃3.以H2O2计消耗的过乙酸kg/BDMT卡伯值粘度,dm3/kg自度,%ISOP—步骤1.H2O2,kg/BDMTMgSO4,kg/BDMTNaOH,kg/BDMT2.时间,分钟温度,℃最终pH值3.消耗的H2O2,kg/BDMT卡伯值粘度,dm3/kg白度,%ISO 204.32409011.61.184284.44.03.07.01809010.31.50.880888.1 304.32409017.90.781487.44.03.07.01809010.41.30.577889.3 204.3240909.91.285284.44.03.07.01809010.60.91.183487.8 304.32409014.20.984186.84.03.07.01809010.51.10.782889.2
结果惊奇地发现按本发明方法进行预处理和漂白的纸浆与按实施例1和2的方法进行预处理和漂白的纸浆相比,具有明显改进的粘度,并随之获得改进的强度特性。在第二个漂白步骤中用等量的过乙酸(Pa),在实施例1和3中用20kg,在实施例2和4中用30kg;在Q步骤中用乙酸代替硫酸作为酸化剂,结果粘度分别提高26和50单位。
如前面所提及的,乙酸、过乙酸或其它适用的过酸优选在现场制备。例如,乙酸可以在制备纸浆时从黑液(black liquor)中以每吨纸浆50kg的量回收。再例如,过乙酸可以从回收的乙酸用已知的方法制备。因此,从经济的观点看,本发明方法具有很大优越性。

Claims (8)

1.一种在制备化学纸浆时不用氯而将纤维素纤维材料漂白的方法,其中将纸浆连续送料进入漂白流程,在至少一种酸存在下调节pH值于7以下并用螯合剂处理,然后经过包括过氧化物,一种或几种有机过酸和过氧化物几个步骤的流程进行漂白,其特点是在对纸浆进行螯合剂处理时以乙酸作为酸化剂。
2.权利要求1所要求的方法,其特点是所用过氧化物为过氧化氢。
3.权利要求1或2所要求的方法,其特点是所用的一种或几种有机过酸为过甲酸、过乙酸、过丙酸,优选使用过乙酸或至少两种上述过酸的混合物。
4.权利要求1—3中任一项所要求的方法,其特点是乙酸的添加量为使pH值低于6,优选低于5。
5.权利要求1—4中任一项所要求的方法,其特点是每个过氧化物步骤在碱性溶液中进行。
6.权利要求1—5中任一项所要求的方法,其特点是,在螯合剂处理过程中和漂白流程中纸浆浓度约为6—16%,优选9—11%。
7.权利要求1—6中任一项所要求的方法,其特点是进料的纸浆是经过氧气处理的,其卡伯值约为14或小于14,优选为12或小于12,最优选为10或小于10的纸浆。
8.不用氯的纸浆漂白过程中,用螯合剂处理化学纸浆时以乙酸作为酸化剂,其中纸浆连续进料送入漂白流程,在乙酸存在下调节pH值于7以下并用螯合剂处理,然后经过包括过氧化物、一种或几种有机过酸和过氧化物几个步骤的流程进行漂白。
CN 94191058 1993-01-29 1994-01-26 用乙酸作酸化剂的纸浆无氯漂白方法 Pending CN1117301A (zh)

Applications Claiming Priority (2)

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SE9300277A SE501325E (sv) 1993-01-29 1993-01-29 Förfarande för klorfri blekning av massa, varvid massan surgöres med ättiksyra vid behandlingen med komplexbildare
SE9300277-2 1993-01-29

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EP (1) EP0681624A1 (zh)
JP (1) JPH08505907A (zh)
CN (1) CN1117301A (zh)
AU (1) AU675291B2 (zh)
BR (1) BR9406193A (zh)
CA (1) CA2154076A1 (zh)
FI (1) FI111387B (zh)
NO (1) NO305763B1 (zh)
SE (1) SE501325E (zh)
WO (1) WO1994017239A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050642C (zh) * 1996-06-25 2000-03-22 华南理工大学 高浓纸浆过氧化氢漂白方法
CN115210417A (zh) * 2020-03-16 2022-10-18 雷纽赛尔公司 用于酸性金属去除和漂白的一个阶段方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103726382B (zh) * 2013-12-31 2016-08-17 安徽泾县千年古宣宣纸有限公司 一种纯草型宣纸及其无氯漂白生产工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2219505C3 (de) * 1972-04-21 1974-10-17 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Chlorfreie Mehrstufenbleiche von Zellstoff
DE2841013C2 (de) * 1978-09-21 1984-06-07 Degussa Ag, 6000 Frankfurt Verfahren zur Vollbleiche von Zellstoff
DE402335T1 (de) * 1989-06-06 1992-04-09 Eka Nobel Ab, Surte Verfahren zum bleichen von lignocellulose enthaltenden zellstoffen.
SE468355B (sv) * 1991-04-30 1992-12-21 Eka Nobel Ab Blekning av kemisk massa genom behandling med komplexbildare och ozon

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1050642C (zh) * 1996-06-25 2000-03-22 华南理工大学 高浓纸浆过氧化氢漂白方法
CN115210417A (zh) * 2020-03-16 2022-10-18 雷纽赛尔公司 用于酸性金属去除和漂白的一个阶段方法

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CA2154076A1 (en) 1994-08-04
WO1994017239A1 (en) 1994-08-04
SE501325E (sv) 1999-09-20
FI111387B (fi) 2003-07-15
NO952935L (no) 1995-09-13
JPH08505907A (ja) 1996-06-25
SE501325C2 (sv) 1995-01-16
SE9300277D0 (sv) 1993-01-29
FI953589A0 (fi) 1995-07-27
NO952935D0 (no) 1995-07-24
AU675291B2 (en) 1997-01-30
BR9406193A (pt) 1996-01-09
NO305763B1 (no) 1999-07-19
FI953589A (fi) 1995-07-27
AU5982094A (en) 1994-08-15
EP0681624A1 (en) 1995-11-15
SE9300277L (sv) 1994-07-30

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