WO1999032710A1 - Bleaching of chemical pulp with peracid - Google Patents
Bleaching of chemical pulp with peracid Download PDFInfo
- Publication number
- WO1999032710A1 WO1999032710A1 PCT/FI1998/000993 FI9800993W WO9932710A1 WO 1999032710 A1 WO1999032710 A1 WO 1999032710A1 FI 9800993 W FI9800993 W FI 9800993W WO 9932710 A1 WO9932710 A1 WO 9932710A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bleaching
- pulp
- post
- peracid
- carried out
- Prior art date
Links
Classifications
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/32—Bleaching agents
-
- 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
- D21C9/166—Bleaching ; Apparatus therefor with per compounds with peracids
Definitions
- the present invention relates to a method for the bleaching of chemical pulp, wherein the pulp is treated in a plurality of different steps and a solution containing a peracid is used in at least one of the steps.
- the invention additionally relates to the use of a peracid-containing bleaching solution in a process step according to the invention.
- a raw pulp obtained by digesting cellulose-containing materials with suitable digestion chemicals is subjected to a treatment wherein the lignin is removed and a bleaching which involves the use of oxidative chemicals is carried out.
- the purpose of conventional bleaching of chemical pulp is to bring to completion the removal of lignin from a raw pulp obtained from a digestion procedure.
- This bleaching can be carried out by using chlorine or chlorine dioxide and thereafter alkaline extraction steps in which the lignin is dissolved out of the pulp.
- the bleaching of a chemical pulp is increasingly often carried out by bleaching methods using no elementary chlorine or chlorine compounds.
- the first-mentioned bleaching is called ECF (elementary chlorine free) bleaching and the latter TCF (totally chlorine free) bleaching.
- ECF elementary chlorine free
- TCF totally chlorine free
- the chemical pulp is bleached in several successive steps.
- the bleaching is often started with an oxygen delignification, whereafter further bleaching can be carried out by various methods.
- delignification can be continued, for example, by using ozone, peracetic acid or hydrogen peroxide in acid or alkaline conditions.
- ECF bleaching chlorine dioxide steps and thereafter alkaline extraction steps are used.
- Peracetic acid can be prepared most simply by mixing vinegar and hydrogen peroxide, whereupon a so-called equilibrium solution is obtained which contains, in addition to peracetic acid, also unreacted initial substances. Also a pure peracetic acid solution can be prepared from this reaction solution by distillation. There are also known other methods for preparing peracetic acid.
- Peracetic acid is a highly selective bleaching chemical by the use of which good strength properties of the pulp can be maintained. When peracetic acid is used, the optimum pH is approx. 4-7. At a lower pH peracetic acid is a highly selective delignifying chemical. At a higher pH its bleaching action is greater but its selectivity decreases.
- Agents suitable for post-bleaching include peracetic acid and dithionite.
- the use of hydrogen peroxide is limited by the fact that in order to function properly it would require alkaline conditions.
- dithionite and peracetic acid are highly suited for post-bleaching.
- Dithionite is used commonly in the bleaching of mechanical pulps, but normally it is not used in the bleaching of chemical pulp. The sulfur present in it may also cause problems.
- Post-bleaching with peracetic acid is a very effective method of increasing brightness. The consumption of chemicals for bleached pulps is low, and in addition the reaction is rapid even at low consistency. Furthermore, the optimum pH range for bleaching is precisely suitable for post-bleaching.
- the peracetic acid post-bleaching of chemical pulps involves the problem that, within the pH range optimal for the bleaching result, selectivity is no longer at its best.
- selectivity is no longer at its best.
- the use of peracetic acid damages the fibers, causing the breaking down of carbohydrates and the lowering of pulp strength. This also causes dissolving of organic matter out of the pulp, a factor which may disturb the running of the paper machine.
- the bleaching method according to the invention which solves the problems mentioned above, is characterized in that a peracid is used in the post-bleaching which is the last step of the bleaching process and takes place in the presence of one or more earth-alkali metal compounds.
- An post-bleaching such as this can advantageously be carried out as a separate step at the paper mill to which the pulp has been transferred from a bleach plant.
- the earth-alkali metals such as magnesium and calcium, used simultaneously with a peracid in the method according to the invention stabilize carbohydrates so that the reducing of the pulp strength is prevented. In other words, the strength of the pulp remains good and the dissolving of organic matter is in- significant.
- the brightness and whiteness of the pulp are also higher than without the use of earth-alkali metals. This decreases, for example, the need for using optical brighteners in the paper machine. When this method is used, the pH of the stock to be turned into paper, and the brightness and whiteness of the pulp are more even, in which case the runnability of the paper machine is considerably improved.
- magnesium protects the viscosity of the pulp.
- delignification which is carried out on a pulp having a high kappa number. This delignification step is followed by a separate bleaching during which the brightness is raised to its final level.
- transition metals such as Fe and Mn are released from the pulp, and magnesium prevents their detrimental effects.
- the addition of magnesium is used for improving the ratio of magnesium to transition metal, which improves especially the running of the subsequent alkaline peroxide step.
- the invention concerns post- bleaching which is carried out on an already delignified pulp having a low kappa number (preferably below 4) and being free of transition metals, the purpose being to raise the brightness and whiteness of the pulp to the desired level.
- the peracetic acid turns colorless the chromophoric groups in the pulp, mainly in carbohydrates.
- the question is of the reactions of peracetic acid with residual lignin in the pulp.
- the peracetic acid dose is considerably smaller.
- a very small peracetic acid dose 0.1-7 kg/tp, preferably 0.5-3 kg/tp, is sufficient, larger doses being even detrimental.
- the peracid used in the method is preferably peracetic acid.
- Other usable peracids include performic acid, perpropionic acid or some longer-chain percarboxylic acid.
- the peracid may be a so- called equilibrium solution, i.e. a reaction mixture containing the said acid, a peracid and hydrogen peroxide, or a pure peracid solution can be used.
- the method by which the peracid solution is prepared does not restrict the use of the method; the peracid may be prepared, for example, by distilling an equilibrium solution or from an anhydride and hydrogen peroxide.
- the peracid may also be a monopersulfuric acid (Caro's acid) or a mixture of Caro's acid and a percarboxylic acid, e.g. peracetic acid.
- Persulfates may also be used, either as such or as a mixture with any of the above-mentioned peracids.
- the earth-alkali metal used in the post-bleaching according to the invention may be in particular calcium or magnesium. These may be added to the bleaching solution in the form of sulfate. acetate, carbonate, oxide or any other compound. It is possible to use in the method either magnesium or calcium alone or both of them together at any ratio. Calcium has over magnesium the advantage that calcium will not precipitate extract-based and resin-based substances which may be present at the wet end of the paper machine.
- the post-bleaching according to the invention may be preceded by any known bleaching reaction known from bleaching sequences.
- the post-bleaching is especially advantageous for use after chlorine dioxide or peroxide bleaching.
- acidification possibly taking place after the bleaching does not restrict the application of the method; it can be used on both non-acidified and acidified stock.
- the said acidification may be carried out with, for example, S0 2 , sulfuric acid or any acid suitable for this purpose.
- the functioning of the invention is not affected by a possible wash of the pulp before or after the post-bleaching, or by the absence of a wash.
- the consistency of the pulp to be after-bleached may be 1-30 % and the temperature during the post- bleaching may be between 30 and 100 °C.
- the after-bleached pulp may be taken directly to the paper machine or be dried to produce baled pulp.
- the method is suited for use on sulfate and sulfite pulps made both from softwood and from hardwood, and on various organosolv pulps.
- the said prior art methods in which a peracid and magnesium are used or in which a peracid has been present in the last steps of the bleaching sequence are characterized in that they are carried out in the normal manner in the bleach plant of the pulp mill.
- the post-bleaching according to the invention in which the bleaching reaction is very rapid even at a low consistency, is not tied to the bleach plant and thus also does not require investment in equipment for the bleach plant.
- the invention primarily concerns an post-bleaching carried out after the bleaching sequence of the bleach plant, outside the actual bleaching, for example in the pulp flow pipe during the transfer of pulp, during pulp storage or in the paper machine. Instead of the bleach plant, the place at which the post-bleaching according to the invention is carried out is typically a storage tower for bleached pulp or the paper mill.
- the earth-alkali metal compounds used can be added to the bleaching solution in any suitable process step. They can be added to the circulating waters before the water arrives in the post-bleaching step, or they may, for example, come in the dilution waters from the paper machine, where they may be added in any form. It is also possible to use chelators simultaneously with earth-alkali metals.
- the invention comprises the use of a solution which contains a peracid and an earth-alkali metal for post-bleaching of delignified pulp at a paper mill.
- a birch sulfate pulp which had been bleached using a sequence consisting of an oxygen step, chelation, an oxygen + peroxide step, a chlorine dioxide step, a peroxide extraction, a chlorine dioxide step (-O-Q-Op-D-Ep-D) was subjected separately to an post-bleaching at 50 °C with a 30 min retention at a consistency of 5 % with a peracetic acid dose of 3 kg/tp at two different pH levels (approx. 6.5 and approx. 4.5) .
- the peracetic acid used had been distilled.
- Calcium was added to the pulp in the form of acetate, and magnesium in the form of sulfate.
- the figures in the table indicate the dose of the chemical concerned per one metric ton of pulp (kg of 100 % chemical/one metric ton of pulp) .
- Experiment number 0 stands for pulp which has not been after- bleached.
- a birch sulfate pulp which had been bleached by the sequence -O-Q-Op-D-Ep-D according to Example 1 was subjected to an post- bleaching at 50 °C with a 30 min retention at a consistency of 5 % with a peracetic acid dose of 3 kg/tp at different pH levels.
- the magnesium sulfite addition was 1 kg/tp.
- the peracetic acid used had been distilled.
- the brightness of the pulp before the post-bleaching was 90,3 % ISO and viscosity 930 dm 3 /kg.
- a TCF-bleached softwood sulfate pulp which had been bleached using oxygen, ozone and hydrogen peroxide was after-bleached at 70 °C with a 240 min retention at a consistency of 10 % by using two different peracetic acid doses.
- the conditions and results of the post-bleaching are shown in Table 3.
- the brightness of the pulp before the post-bleaching was 86.8 % ISO and viscosity 642 dmVkg, and the kappa number was 1.7.
- a TCF-bleached softwood sulfate pulp which had been bleached using oxygen, ozone and hydrogen peroxide was after-bleached at 70 °C with a 240 min retention at a viscosity of 10 % by using two different peracetic acid doses.
- the conditions and results of the post-bleaching are shown in Table 4.
- the brightness of the pulp before the post-bleaching was 87.6 % ISO and viscosity 623 dmVkg, and the kappa number was 1.8.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98961279A EP1040222B1 (en) | 1997-12-19 | 1998-12-18 | Bleaching of chemical pulp with peracid |
CA002315063A CA2315063C (en) | 1997-12-19 | 1998-12-18 | Bleaching of chemical pulp with peracid |
AU16743/99A AU1674399A (en) | 1997-12-19 | 1998-12-18 | Bleaching of chemical pulp with peracid |
BRPI9813747-6A BR9813747B1 (pt) | 1997-12-19 | 1998-12-18 | alvejamento de polpa quÍmica com perÁcido. |
DE69839097T DE69839097T2 (de) | 1997-12-19 | 1998-12-18 | Bleichen von zellstoff mittels persäure |
JP2000525621A JP4499280B2 (ja) | 1997-12-19 | 1998-12-18 | 過酸による化学パルプの漂白 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI974575 | 1997-12-19 | ||
FI974575A FI112958B (fi) | 1997-12-19 | 1997-12-19 | Menetelmä kemiallisen massan valkaisemiseksi sekä valkaisuliuoksen käyttö |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999032710A1 true WO1999032710A1 (en) | 1999-07-01 |
Family
ID=8550176
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1998/000993 WO1999032710A1 (en) | 1997-12-19 | 1998-12-18 | Bleaching of chemical pulp with peracid |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP1040222B1 (fi) |
JP (1) | JP4499280B2 (fi) |
AT (1) | ATE385526T1 (fi) |
AU (1) | AU1674399A (fi) |
BR (1) | BR9813747B1 (fi) |
CA (1) | CA2315063C (fi) |
DE (1) | DE69839097T2 (fi) |
ES (1) | ES2302362T3 (fi) |
FI (1) | FI112958B (fi) |
PT (1) | PT1040222E (fi) |
WO (1) | WO1999032710A1 (fi) |
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WO2000052258A1 (en) * | 1999-03-02 | 2000-09-08 | Kemira Chemicals Oy | Bleaching of pulp with peracid as final bleaching agent |
JP2001316997A (ja) * | 2000-02-28 | 2001-11-16 | Oji Paper Co Ltd | 中性紙 |
US6677477B2 (en) | 2001-04-04 | 2004-01-13 | Kemira Chemicals Oy | Process for the production of peracetic acid |
EP1389646A1 (en) * | 2002-07-19 | 2004-02-18 | Crosmill Ltd | Process for making paper |
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US7371356B2 (en) | 2002-03-14 | 2008-05-13 | Basf Aktiengesellschaft | Method for the production of precipitated calcium carbonate with a high degree of brightness |
US7481905B2 (en) | 2001-12-19 | 2009-01-27 | Kemira Oyj | Process for manufacturing board |
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US7910347B1 (en) | 2009-12-07 | 2011-03-22 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
US7914646B2 (en) | 2006-07-21 | 2011-03-29 | Nalco Company | Compositions and processes for paper production |
US7923233B1 (en) | 2009-12-07 | 2011-04-12 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
US7927854B1 (en) | 2009-12-07 | 2011-04-19 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
US7932072B1 (en) | 2009-12-07 | 2011-04-26 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
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US8268123B2 (en) | 2006-05-17 | 2012-09-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing bleached pulp |
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US8865436B2 (en) | 2012-03-30 | 2014-10-21 | E. I. Du Pont De Nemours And Company | Enzymes useful for peracid production |
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BR112014024207B1 (pt) | 2012-03-30 | 2022-04-05 | E.I. Du Pont De Nemours And Company | Processo para a produção de um ácido peroxicarboxílico, composição e sistema de geração e fornecimento de perácido |
JP7013246B2 (ja) * | 2015-09-30 | 2022-02-15 | イメリーズ ミネラルズ リミテッド | 水性パルプを漂白するための方法及びこれらの方法において使用するための組成物 |
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1997
- 1997-12-19 FI FI974575A patent/FI112958B/fi not_active IP Right Cessation
-
1998
- 1998-12-18 JP JP2000525621A patent/JP4499280B2/ja not_active Expired - Lifetime
- 1998-12-18 CA CA002315063A patent/CA2315063C/en not_active Expired - Fee Related
- 1998-12-18 DE DE69839097T patent/DE69839097T2/de not_active Expired - Lifetime
- 1998-12-18 ES ES98961279T patent/ES2302362T3/es not_active Expired - Lifetime
- 1998-12-18 PT PT98961279T patent/PT1040222E/pt unknown
- 1998-12-18 AU AU16743/99A patent/AU1674399A/en not_active Abandoned
- 1998-12-18 EP EP98961279A patent/EP1040222B1/en not_active Expired - Lifetime
- 1998-12-18 BR BRPI9813747-6A patent/BR9813747B1/pt not_active IP Right Cessation
- 1998-12-18 WO PCT/FI1998/000993 patent/WO1999032710A1/en active IP Right Grant
- 1998-12-18 AT AT98961279T patent/ATE385526T1/de active
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Also Published As
Publication number | Publication date |
---|---|
EP1040222A1 (en) | 2000-10-04 |
ES2302362T3 (es) | 2008-07-01 |
FI974575A (fi) | 1999-06-20 |
JP4499280B2 (ja) | 2010-07-07 |
DE69839097T2 (de) | 2009-01-29 |
ATE385526T1 (de) | 2008-02-15 |
BR9813747A (pt) | 2000-10-17 |
CA2315063A1 (en) | 1999-07-01 |
EP1040222B1 (en) | 2008-02-06 |
BR9813747B1 (pt) | 2009-01-13 |
FI112958B (fi) | 2004-02-13 |
PT1040222E (pt) | 2008-05-05 |
DE69839097D1 (de) | 2008-03-20 |
JP2001527168A (ja) | 2001-12-25 |
CA2315063C (en) | 2008-11-18 |
FI974575A0 (fi) | 1997-12-19 |
AU1674399A (en) | 1999-07-12 |
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