CN1089578A - 处理生产用水的方法 - Google Patents

处理生产用水的方法 Download PDF

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CN1089578A
CN1089578A CN93116508A CN93116508A CN1089578A CN 1089578 A CN1089578 A CN 1089578A CN 93116508 A CN93116508 A CN 93116508A CN 93116508 A CN93116508 A CN 93116508A CN 1089578 A CN1089578 A CN 1089578A
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slurry
water
bleaching
productive use
metal ion
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乌尔夫·杰格德
佐尔法伊格·努登
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Valmet AB
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Sunds Defibrator Industries AB
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0021—Introduction of various effluents, e.g. waste waters, into the pulping, recovery and regeneration cycle (closed-cycle)
    • D21C11/0028—Effluents derived from the washing or bleaching plants
    • 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
    • D21C9/001—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
    • 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
    • D21C9/1026—Other features in bleaching processes
    • 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
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S162/00—Paper making and fiber liberation
    • Y10S162/08—Chlorine-containing liquid regeneration

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Physical Water Treatments (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

处理含金属离子的生产用水以及漂白含木质纤 维素的浆。使生产用水在pH值为7以上、50～ 120℃温度下与浆接触，因而全部或部分的减少生产 用水中的金属离子含量。

Description

本发明涉及一种处理含金属离子的生产用水的方法，并涉及含木质纤维素材料浆的漂白。
为了将由各种排出物对环境造成的影响如BOD、COD颜料等减至最小，通过封闭漂白工厂的废水系统来限制排放是人们很感兴趣的，这意味着必须将废水在过程中再循环，而不是排出。但作为封闭系统的结果是系统中金属离子的含量，例如猛、铜、铁等会上升到一个会给使用过氧化氢漂白、或用臭氧漂白造成麻烦的水平。
金属离子是通过木头原料进入系统中的，所以不能通过加工过程将所汇集的金属离子除去。但在浆中这些金属离子的含量是很低的，所以它们对当地环境和容器中都不会引起环境问题。
在将来，纸浆的漂白会在很大程度上以过氧化氢漂白和臭氧漂白为基础，为了得到高的Iso光泽（Iso-brightness），这类漂白要求未漂白过的浆和用水不含或基本不含某种金属离子，否则可观数量的所加入的过氢化氢就会分解为水和氧气和/或加入的臭氧会分解为氧，而同时不会产生任何漂白作用。
为了在漂白之前除去这些金属离子，浆必须先用化学物质例如酸或络合物例如EDTA或DTPA来处理，这些物质能有选择性地与不希望存在的金属离子化合，而能在漂白前将其洗除。由于生产原因，所产生的洗涤水必须从系统中排除，而与此同时环境却要求不可将洗涤水放出。
本发明提供了上述问题的解决方法，这样本发明的目的就是从富含金属的生产用水中除去金属离子，并使其能重新作为生产用水使用，因而使漂白工厂的废水形成封闭系统，从保护环境观点来看，也能符合要求。
下面结合图1来更详细地描述本发明。图1是本发明方法应用的流程图。
图2是在一个实施例中所表现出的锰含量对于反应时间函数的图。
将未漂白的浆通过导管1送入预处理工序2，在该工序中用酸或用EDTA或DTPA类的络合物来处理浆。这时金属如锰就从纤维材料中溶解出来，将此处的浆导入第一洗涤工序3，例如以加压洗涤或洗涤过滤的形式，将含临界金属离子的废水从导管4排出。将不含临界金属离子的浆导入用过氧化氢或臭氧漂白的漂白工序5。在此之后将浆导入第二洗涤工序6，在工序6将自第一洗涤工序3的废水经过导管4再次与浆料接触，令浆料再次与原来的金属离子化合。来自第二洗涤工序的废水从导管7中排出并通过导管8来排出洗涤过的浆料。基本不含金属离子的废水，在重点要求低含量金属的地方例如在完全不用氯气的漂白工厂中可用来作为洗涤水，这种废水也可在生产的其它工序中使用。为达到与如COD等有关的改进的洗涤效果，在漂白后的洗涤工序6中采用另外的洗涤液9也是令人感兴趣的。
因此，浆料将把金属输动到漂白工厂之外，而且也因而避免了在封闭式排放系统时，漂白工厂的积累行为。
本发明富含金属的浆可以按常规方法直接用于造纸或首先净化去除金属离子，例如在低pH值下用含络合物的洗涤水来处理，或自毁（destruct）。
业已发现，在第二洗涤工序能良好地去除金属离子的适当条件如下：pH值大于7，适当地大于10.5，较好的pH为11或更高，特别好的是pH值在11.5～12，温度应在50～120℃，最好70～100℃。在生产用水与浆料之间的接触时间可以很短，在最佳条件下时间可短于1秒，但通常时间略长到1～6秒是较好的，更长的反应时间0.1～60分钟也可采用，但不会明显地影响结果。所以超过1～5分钟的时间一般就没有什么意义了。反应时间通常由所使用的洗涤设备来确定，在第二洗涤工序6中用加压洗涤和洗滤器可使停留时间变得很短。
一种可选择的方法是只将部分浆流用于从来自第一洗涤步骤的废水中分离金属离子，当然也可用一种不需进行漂白的未漂白过的浆料或废浆料流来分离金属离子。
也可以进一步考虑把本发明的金属分离法用于其它类型金属分离方法的一个补充。
实施例1
用过氧化氢漂白的浆处理不含木质素的水溶液，当处理是在pH为12而不是10-11进行时，溶液中锰含量明显减少，处理是在80℃进行10分钟。
液体1
最初含量（mg/l）    6.5
在pH为10时处理    6.4
在pH为11时处理    6.5
在pH为12时处理    1.2
实施例2
在用过氧化氢漂白的浆处理后，在一个实验室制的漂白设备排放物中测定锰的含量，处理是在不同的pH值下进行，在pH值为12以及甚至在pH为11的两种情况下都观察到了锰含量的明显降低。
液体2    液体2    液体3
最初含量(mg/l)    3.3    3.5    3.6
在pH为10时处理    -    -    3.4
在pH为11时处理    0.7和/个别地为0.4    2.7    0.3
在pH为12时处理    -    1.3    0.03
实施例3
在用过氧化氢漂白过的浆处理之后，在一个实验室制的漂白设备的排放物中测定锰的含量处理是在不同的pH和温度下进行，结果表明反应时间超过2分钟不会明显影响结果。结果亦表明pH值的增加比温度的增加更重要。
pH11/80℃    pH12/80℃    pH11/90℃
最初含量(mg/l)    3.5    3.5    3.5
反应时间2分钟    2.3    1.9    2.6
反应时间10分钟    2.6    1.3    2.5
反应时间60分钟    -    -    2.3
实施例4
对不同木质素含量的浆料在实验室制漂白设备中进行过氧化氢漂白，测量排放物中锰的含量。在80℃进行10分钟处理，浆中以Kappa数计的木质素含量对所得到的锰含量没有决定性的影响。
浆料1    浆料2
(Kappa数5)    (Kappa数9)
最初的含量(mg/l)    3.6    3.6
pH为10的处理    3.4    -
pH为11的处理    0.1    1.1
pH为12的处理    0.03    <0.01
实施例5
在用过氧化氢漂白的浆料在不同pH值下处理的不含木质素的水溶液中，测量了在经不同反应时间后锰的含量，结果示于图2。它表明当在80℃、pH为11.8～11.9，反应时间不到约2秒钟，锰含量的减少就可达到99%;结果也表明反应时间超过约2秒钟也不会进一步降低锰的含量。
当然，本发明不是仅仅限于这些实施例，在本发明构思的范围内可作出变化。

Claims (6)

1、一种在用过氧化氢或臭氧漂白浆之前处理含有金属离子的生产用水的方法，这些金属离子是从含木质纤维素的物质中洗涤出来的，其特征在于将生产用水在pH值7以上和在50～120℃的温度下与不准备用过氧化氢或臭氧漂白的浆接触，从而全部或部分地除去生产用水中所含的金属离子。
2、如权利要求1所述的方法，其特征在于使生产用水与浆在pH为11或更高的情况下接触。
3、如权利要求1或2所述的方法，其特征在于使生产用水与浆在pH为11～12情况下接触。
4、如权利要求1～3所述的方法，其特征在于生产用水是经络合物处理浆料后的洗涤废水。
5、如权利要求1～4的任一项所述的方法，其特征在于是在用过氧化氢或臭氧漂白之前在洗涤浆料时分离出金属离子，在所述漂白之后金属离子被全部或至少部分地返回到部分的浆流中。
6、如权利要求1～4的任一项所述的方法，其特征在于用于从生产用水中分离金属离子的浆是由漂白过的浆、未漂白过的浆或废料浆所组成。
CN93116508A 1992-08-28 1993-08-19 处理生产用水的方法 Pending CN1089578A (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE9202464A SE500052C2 (sv) 1992-08-28 1992-08-28 Behandling av processvatten från blekning av massa innehållande metalljoner
SE9202464-5 1992-08-28
SE9301160A SE9301160L (sv) 1992-08-28 1993-04-07 Förfarande för behandling av processvatten
SE9301160-9 1993-04-07

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CN1089578A true CN1089578A (zh) 1994-07-20

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EP (1) EP0656966B1 (zh)
JP (1) JPH08500645A (zh)
CN (1) CN1089578A (zh)
AT (1) ATE151825T1 (zh)
AU (1) AU665461B2 (zh)
BR (1) BR9306963A (zh)
CA (1) CA2139566A1 (zh)
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ES (1) ES2100563T3 (zh)
FI (1) FI950882A0 (zh)
NZ (1) NZ255613A (zh)
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WO (1) WO1994005850A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1079848C (zh) * 1995-12-22 2002-02-27 连津格股份公司 纤维素模塑体和它的制造方法

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SE500113C2 (sv) 1992-07-09 1994-04-18 Kamyr Ab Sätt vid blekning av massa för omhändertagande av utlösta metaller
SE501985C2 (sv) * 1993-11-05 1995-07-03 Sunds Defibrator Ind Ab Förfarande för avskiljning av metalljoner från massa i samband med blekning av massan
SE504789C2 (sv) * 1994-02-21 1997-04-28 Kemira Kemi Ab Förfarande för tungmetalleliminering från bakvattensystem inom pappers- och pappersmassaindustrien
SE9503004L (sv) * 1995-08-30 1997-03-01 Sunds Defibrator Ind Ab Blekning av massa
WO1998011295A1 (fr) * 1996-09-11 1998-03-19 Solvay Interox (Societe Anonyme) Procede de blanchiment de pate a papier
US6228215B1 (en) * 1998-04-06 2001-05-08 Hoffman Enviornmental Systems, Inc. Method for countercurrent treatment of slurries
CN106192517B (zh) * 2016-07-08 2018-01-16 华南理工大学 一种减少氧脱木素过程中草酸根形成的方法

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SE466061B (sv) * 1990-04-23 1991-12-09 Eka Nobel Ab Blekning av kemisk massa genom behandling med foerst ett komplexbildande aemne och sedan ett peroxidinnehaallande aemne
US5352332A (en) * 1991-01-28 1994-10-04 Maples Gerald E Process for recycling bleach plant filtrate
SE500783C2 (sv) * 1992-05-05 1994-09-05 Eka Nobel Ab Sätt att rena vedhartsinnehållande process- eller avloppsvatten
SE500113C2 (sv) * 1992-07-09 1994-04-18 Kamyr Ab Sätt vid blekning av massa för omhändertagande av utlösta metaller
US5401362A (en) * 1993-03-24 1995-03-28 Kamyr, Inc. Control of metals and dissolved organics in the bleach plant
SE9301161L (sv) * 1993-04-07 1994-10-08 Sunds Defibrator Ind Ab Förfarande för behandling av processvatten
US5554259A (en) * 1993-10-01 1996-09-10 Union Camp Patent Holdings, Inc. Reduction of salt scale precipitation by control of process stream Ph and salt concentration

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1079848C (zh) * 1995-12-22 2002-02-27 连津格股份公司 纤维素模塑体和它的制造方法

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FI950882A (fi) 1995-02-27
SE9301160L (sv) 1994-03-01
AU4987993A (en) 1994-03-29
US5741398A (en) 1998-04-21
BR9306963A (pt) 1999-01-12
NZ255613A (en) 1995-10-26
CA2139566A1 (en) 1994-03-17
DE69309938T2 (de) 1997-11-06
ATE151825T1 (de) 1997-05-15
JPH08500645A (ja) 1996-01-23
SE9301160D0 (sv) 1993-04-07
FI950882A0 (fi) 1995-02-27
AU665461B2 (en) 1996-01-04
WO1994005850A1 (en) 1994-03-17
EP0656966A1 (en) 1995-06-14
EP0656966B1 (en) 1997-04-16
ES2100563T3 (es) 1997-06-16

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