CA2435813C - Bleaching of pulp with chlorine dioxide after alkaline bleaching - Google Patents

Bleaching of pulp with chlorine dioxide after alkaline bleaching Download PDF

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Publication number
CA2435813C
CA2435813C CA2435813A CA2435813A CA2435813C CA 2435813 C CA2435813 C CA 2435813C CA 2435813 A CA2435813 A CA 2435813A CA 2435813 A CA2435813 A CA 2435813A CA 2435813 C CA2435813 C CA 2435813C
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Canada
Prior art keywords
pulp
chlorine dioxide
bleaching
stage
acid
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Expired - Fee Related
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CA2435813A
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French (fr)
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CA2435813A1 (en
Inventor
Ann-Sofi Nasholm
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Valmet Technologies Oy
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Metso Paper Oy
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Publication of CA2435813C publication Critical patent/CA2435813C/en
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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
    • D21C9/12Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
    • D21C9/144Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 and other bleaching agents in a multistage process

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

Abstract

The present invention relates to a method for end-bleaching of pulp containing metal ions after a sequence comprising alkaline bleaching stages only and optionally treatment with complex forming agent, wherein the end-bleaching comprises two chlorine dioxide stages at a pulp concentration of 8-20 % and pH 2.5-4.5 wherein the pulp after the first chlorine dioxide stage is washed and dewatered to a concentration of 12-50 % for removal of the out-dissolved metal ions and that alkali thereupon is added to the pulp for fast alkali extraction and increase of pH to 8-14, whereupon the pulp is provided with acid and chlorine dioxide and introduced into the second chlorine dioxide stage.

Description

BLEACHING OF PULP WITH CHLORINE DIOXIDE
AFTER ALKALINE BLEACHING
TECHNICAL FIELD
The present invention relates to a method for efficient and economical end-bleaching with chlorine dioxide wherein the method relates to a method for end bleaching of pulp containing metal ions after a sequence comprising alkaline bleaching stages only and optionally treatment with complex forming agent, wherein the end-bleaching comprises two LO chlorine dioxide steps with intermediate wash and alkali extraction where the chlorine dioxide stages are performed at a pulp concentration of 8-20t and pH 2.5-4.5 wherein the pulp after the first chlorine dioxide steps is washed and dewatered to a concentration of 12-50% for removal of out-dissolved metal ions and that alkali thereupon is added to the pulp for extraction and fast increase of pH to 8-14, whereupon the pulp is provided with acid and chlorine dioxide and is introduced into the second chlorine dioxide step.

BACKGROUND OF THE TECHNOLOGY
It is common that end bleaching of chemical pulp is performed with chlorine dioxide, see for instance SE 466 062.
In most of the cases it is performed in two steps with an extraction stage (E), that is an alkalisation of the pulp, and/or with a wash between the stages. If there is no separate extraction stage alkali may be added in order to raise the pH, during the dilution at the end of the first chlorine dioxide tower before the pulp is washed. A short alkalisation/neutralisation step (n) results in that chlorine dioxide bleaching in the following chlorine dioxide stage will be more efficient (see for instance Papermaking Science and Technology, Book 6A, Chemical Pulping, Editor J. Gullichsen and H. Paulapuro, page A642). When alkali is added to the chlorine dioxide bleached pulp lignin is out-dissolved which would, if not out-washed before the following chlorine dioxide stage, consume bleaching chemicals or result in a lower end-brightness. Therefore two-stage chlorine dioxide bleaching is presently performed with intermediate neutralisation stage according to the Dn-Wash-D.
Further, SE 98000797-4 describes a bleaching method for cooked and oxygen delignified pulp where you make use of a commencing acid bleaching stage which is followed by a washing stage at an even lower pH than in the bleaching stage from which washing stage a filtrate is taken out. The purpose here is to bring metals, which forms difficultly dissolvable compounds, into solution so that they may be removed in the washing stage. Accordingly the degree of closing for the following bleaching may be increased.

PROBLEMS WITH THE PRESENT TECHNOLOGY
Concurrently with the bleach plants being closed even harder and pre-bleaching is preferably performed in alkaline stages (for instance 0, 00, (OP), (PO), (EO), (EOP) ) and complex forming agent stage (Q) the overcarry of metals with the pulp to the end-bleaching increases, as they have not been washed out in any acid stage. This results in that the risk for precipitations increases if the pulp is taken into an acid stage for end bleaching which it does in a chlorine dioxide stage, D-stage. If the manufacture of pulp is performed in alkaline bleaching stages and complex forming agent stage and the end-bleaching in D-stage the metals are out-dissolved in the surrounding liquid in the acid D-stage. When the pulp thereupon is alkalised the conditions in the pulp suspension becomes favourable for precipitations, above all for calcium compounds. An example of one such calcium compound is calcium oxalate, which may form a china-resembling precipitation, which may be very difficult to remove from process equipment.
A change in pH in a pulp suspension where the pulp concentration is approximately 10-15% gives a gradual change of pH, which.may result in that the pH interval for precipitations (-- pH 4-9) is reached. If the pulp could have a high dry substance content, ds>25t before the pH adjustment and dilution, a quick and stepwise change of pH from acid conditions to alkaline conditions could be performed and critical conditions for precipitation would therewith be avoided.

SUMMARY OF THE INVENTION
The present invention solves the above problems through providing a method which minimises the risk for precipitations during two-step chlorine dioxide bleaching with intermediate short alkali extraction, in which the alkalisation of the pulp suspension is performed after a dewatering step, including wash of the pulp, wherein the out-dissolved metals are separated in the wash-/dewatering equipment. The wash/dewatering execution is preferably performed in a wash/dewatering press. That is the sequence will be after an alkaline pre-bleaching: D-dewatering (including wash)-nD. A
further advantage with the invention is that a less amount of alkali is consumed, as a smaller liquid amount is to be alkalised at high pulp concentration. Further pH gradients may be avoided as the dilution with alkaline filtrate is performed when the pulp essentially has a higher consistency, preferably high consistency.
According to one aspect of the present invention, there is provided a method for end bleaching of pulp containing metal ions after a sequence of alkaline bleaching stages comprising: treating the pulp in a first chlorine dioxide stage; washing and dewatering said pulp to a consistency of 25-50% for removal of out-dissolved metal ions; adding alkali to said pulp for extraction and an increase of pH to 8-14; providing said pulp with acid and chlorine dioxide;
and treating the resulting pulp in a second chlorine dioxide stage.

The present invention relates to a method for end-bleaching of pulp containing metal ions after a sequence comprising alkaline bleaching stages only and optionally treatment with complex forming agent, wherein the end-bleaching comprises two chlorine dioxide stages at a pulp concentration of 8-20% and pH 2.5-4.5, with intermediate wash and alkali extraction, wherein the pulp after the first chlorine dioxide stage is washed and dewatered to a concentration of 12-50%
for removal of out-dissolved metal ions, and that alkali thereupon is added to the pulp for extraction and fast increase of pH to 8-14, whereupon the pulp 3a is provided with acid and chlorine dioxide and introduced into the second chlorine dioxide stage.

DETAILED DESCRIPTION OF THE INVENTION
The expression "pulp" is intended to embrace in the present description preferably chemical pulp, which may be soft wood pulp or hard wood pulp or mixtures thereof. The chemical pulp is achieved through the fibre freeing being performed in a chemical way; for instance it may be bleached pulp from both soft wood (softwood) and pulp from hard wood (hardwood).
The expression "acid" is intended to embrace in the present description an acid which may be selected from the group consisting of sulphuric acid, hydrochloric acid, nitric acid, sulphur dioxide, acetic acid or carbonic acid or a combination of these.
Other chemicals which may be used in connection with chlorine dioxide bleaching is ozone, hydrogen peroxide, hypo chlorite or alkali. If the pulp has high consistency ozone may be preferred.
According to a preferred embodiment of the present invention the pulp is de-watered after the first chlorine dioxide stage to a concentration of 25-50%, preferably 30-40%.

According to a preferred embodiment of the present invention the chlorine dioxide stages are performed at a pulp concentration of 8-15%, preferably 10-12%.
Chlorine dioxide, which is used, is preferably in the form of a water solution. Further the bleaching is preferably performed in an acid environment, pH 2.5 to 4.5.
According to a preferred embodiment of the present inven-tion the fast increase of pH in the method, during the alkali extraction, is performed to a pH 8-14, preferably 9-12, most preferred pH 9-11.
According to a preferred embodiment of the present inven-tion the in-going pulp has medium consistency (normally 8 to 20% pulp concentration; so called MC-pulp) and the de-watered pulp after the first end-bleaching stage with chlorine dioxide, high consistency (normally 25 to 50% pulp concentration; so called HC-pulp).
According to a preferred embodiment of the present inven-tion the pulp is diluted and dewatered, including wash of the pulp, after the first chlorine dioxide stage wherein an acid outflow with high metal content is obtained from.the pulp whereupon the pulp is diluted with alkalised filtrate so that pH is increased to >8, preferably from pH 8 to 14, before the pulp is provided with chlorine dioxide and acid for the second chlorine dioxide stage.
According to a preferred embodiment of the present inven-tion the acid- and chlorine dioxide addition is performed before the second chlorine dioxide stage 15 seconds to 5 minutes, preferably 30 seconds to 2 minutes after the alkali addition.
According to a preferred embodiment of the present invention the treatment with complex forming agent has been performed in a pH interval from 4.5 to 10, preferably from 4.5 to 7 before the end-bleaching.
According to a preferred embodiment of the present invention the concentration of the pulp is performed in an apparatus for washing and dewatering in the method, for instance by using a wash-press or a press, preferably a wash-press or a dewatering press. In order to convey (transport) the pulp between the reactors further a pump preferably is used or a corresponding apparatus.
We will now in more details describe the present invention by use of figures and example and these shall only be regarded as illuminating and not in any way limiting for the invention as it is set out in the appended set of claims.
DESCRIPTIONS OF FIGURE
Figure 1 shows a principal sketch where the method according to the invention is illuminated in the form of a system for end bleaching by using chlorine dioxide wherein said method may be performed.

EXAMPLE
As can be seen in figure 1 the method for end bleaching according to the present invention may be performed through the following:
Pulp which has been bleached in alkaline bleaching stages and which has been treated with complex forming agent is transported to a first chlorine dioxide (C1O2) reactor whereupon the pulp is diluted and washed. (The initial pulp may have a pH of 8-12). This washing may be performed by using a concentration apparatus as set out in the description before, preferably by using a wash-press or a dewatering-press. A metal rich drainage is removed during the washing of the pulp. At this moment the pulp has essentially a higher consistency, preferably high consistency. The pulp is then quickly diluted to the earlier consistency with dilution liquid, which contains sodium hydroxide (NaOH), wherein a fast alkali extraction is achieved. Acid for regulation of pH and C1O2 is added in connection with the introduction into the second reactor, which is included in the end-bleaching phase for the pulp.
The invention is of course not limited to the showed embodiment but may be varied within the frame of the spirit of the invention.

Claims (10)

CLAIMS:
1. A method for end bleaching of pulp containing metal ions after a sequence of alkaline bleaching stages comprising:

.cndot. treating the pulp in a first chlorine dioxide stage;

.cndot. washing and dewatering said pulp to a consistency of 25-50%
for removal of out-dissolved metal ions;

.cndot. adding alkali to said pulp for extraction and an increase of pH to 8-14;

.cndot. providing said pulp with acid and chlorine dioxide; and .cndot. treating the resulting pulp in a second chlorine dioxide stage.
2. The method according to claim 1, wherein said pulp is dewatered to a consistency of 30-40% after said first chlorine dioxide stage.
3. The method according to claim 1 or 2, wherein said increase of pH is performed to pH 9-12.
4. The method according to claim 1 or 2, wherein said increase of pH is performed to pH 9-11.
5. The method according to claim 1 or 2, wherein said pulp is chemical pulp.
6. The method according to any one of claims 1 to 5, wherein said acid and chlorine dioxide addition is performed from 15 seconds to 5 minutes after the alkali addition.
7. The method according to any one of claims 1 to 5, wherein said acid and chlorine dioxide addition is performed from 30 seconds to 2 minutes after the alkali addition.
8. The method according to any one of claims 1 to 7, wherein said pulp is treated with complex forming agent prior to said first chlorine dioxide stage.
9. The method according to claim 8, wherein said treatment with said complex forming agent is performed in a pH interval of from 4.5 to 10.
10. The method according to claim 8, wherein said treatment with said complex agent is performed in a pH interval of from 4.5 to 7.
CA2435813A 2001-03-20 2002-02-19 Bleaching of pulp with chlorine dioxide after alkaline bleaching Expired - Fee Related CA2435813C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0100977-8 2001-03-20
SE0100977A SE518692C2 (en) 2001-03-20 2001-03-20 Bleaching of pulp with chlorine dioxide
PCT/SE2002/000287 WO2002075046A1 (en) 2001-03-20 2002-02-19 Bleaching of pulp with chlorine dioxide

Publications (2)

Publication Number Publication Date
CA2435813A1 CA2435813A1 (en) 2002-09-26
CA2435813C true CA2435813C (en) 2010-04-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA2435813A Expired - Fee Related CA2435813C (en) 2001-03-20 2002-02-19 Bleaching of pulp with chlorine dioxide after alkaline bleaching

Country Status (6)

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US (1) US20040112556A1 (en)
AT (1) AT412482B (en)
CA (1) CA2435813C (en)
FI (1) FI120652B (en)
SE (1) SE518692C2 (en)
WO (1) WO2002075046A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7976677B2 (en) 2006-12-18 2011-07-12 International Paper Company Process of bleaching hardwood pulps in a D1 or D2 stage in a presence of a weak base
US7976676B2 (en) 2006-12-18 2011-07-12 International Paper Company Process of bleaching softwood pulps in a D1 or D2 stage in a presence of a weak base
SE532370C2 (en) * 2008-02-28 2009-12-29 Metso Paper Inc Method of bleaching a pulp
EP3262490A4 (en) * 2015-02-23 2018-10-17 Somniq, Inc. Empathetic user interface, systems, and methods for interfacing with empathetic computing device

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4238281A (en) * 1979-04-30 1980-12-09 Canadian International Paper Company Simplified bleaching process
SE466062B (en) * 1990-04-30 1991-12-09 Sunds Defibrator Ind Ab CHEMISTRY OF CHEMICAL MASS
US5938892A (en) * 1991-01-28 1999-08-17 Champion International Corporation Process for recycling bleach plant filtrate
US6706143B1 (en) * 1996-03-19 2004-03-16 International Paper Company Minimizing chlorinated organics in pulp bleaching processes
US6475338B1 (en) * 1996-06-05 2002-11-05 Andritz Inc. Method of minimizing transition metal ions during chemical pulping in a digester by adding chelating agent to the digester

Also Published As

Publication number Publication date
CA2435813A1 (en) 2002-09-26
WO2002075046A1 (en) 2002-09-26
FI120652B (en) 2010-01-15
FI20031338A (en) 2003-09-18
US20040112556A1 (en) 2004-06-17
SE0100977L (en) 2002-09-21
AT412482B (en) 2005-03-25
SE518692C2 (en) 2002-11-05
SE0100977D0 (en) 2001-03-20
ATA90412002A (en) 2004-08-15

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