EP1607519B1 - Aktivator zum Zellstoffbleichen - Google Patents
Aktivator zum Zellstoffbleichen Download PDFInfo
- Publication number
- EP1607519B1 EP1607519B1 EP04253546A EP04253546A EP1607519B1 EP 1607519 B1 EP1607519 B1 EP 1607519B1 EP 04253546 A EP04253546 A EP 04253546A EP 04253546 A EP04253546 A EP 04253546A EP 1607519 B1 EP1607519 B1 EP 1607519B1
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- EP
- European Patent Office
- Prior art keywords
- anhydride
- process according
- range
- solution
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000012190 activator Substances 0.000 title description 14
- 238000004076 pulp bleaching Methods 0.000 title description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000004061 bleaching Methods 0.000 claims abstract description 31
- -1 carboxylic acid anhydride compound Chemical class 0.000 claims abstract description 31
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 121
- 239000000203 mixture Substances 0.000 claims description 68
- 150000004965 peroxy acids Chemical class 0.000 claims description 36
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 17
- 239000002738 chelating agent Substances 0.000 claims description 14
- ODBPOHVSVJZQRX-UHFFFAOYSA-M sodium;[2-[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methyl-hydroxyphosphinate Chemical compound [Na+].OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)([O-])=O ODBPOHVSVJZQRX-UHFFFAOYSA-M 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000013505 freshwater Substances 0.000 claims description 4
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 description 49
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 36
- 239000007844 bleaching agent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- DZKRDHLYQRTDBU-UPHRSURJSA-N (z)-but-2-enediperoxoic acid Chemical compound OOC(=O)\C=C/C(=O)OO DZKRDHLYQRTDBU-UPHRSURJSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
Images
Classifications
-
- 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
- This invention relates to a process for generating a dilute solution of percarboxylic acid which is subsequently used to bleach wood or non wood pulp. More specifically, in this process the bleaching solution is formed by reaction of hydrogen peroxide with a carboxylic acid anhydride compound which behaves as a bleach activator.
- Wood and non wood pulp are valuable raw materials in the paper industry and it is desirable that a high degree of whiteness is obtainable.
- Oxygen based bleaching is used for pulp bleaching because of its environmental benefits and oxidising power. Hydrogen peroxide is increasingly being used in oxygen based pulp bleaching.
- Hydrogen peroxide however, suffers from some performance disadvantages which become particularly important when an existing pulp bleaching sequence is being converted to operate with hydrogen peroxide.
- One major problem is the fact that the degree of whiteness may be reduced compared with the use of chlorine based bleaches which significantly reduces the value of the pulp.
- bleaching solution In order to overcome these problems work has gone into developing an alternative bleaching solution. It is proposed in various patent applications to react at least part of the hydrogen peroxide with a bleach activator thereby generating a peroxyacid based oxygen bleaching species in situ. Bleach activators contain a good leaving group such that on mixing with hydrogen peroxide, reaction takes place to give peracid species which are more effective bleaching agents than hydrogen peroxide itself.
- EP-A-0670929 describes a method for bleaching lignocellulose containing pulp in which equilibrium peracid is generated by reacting acetic acid and hydrogen peroxide. It also suggests that in situ peracid can be generated by reaction of acelic anhydride with hydrogen peroxide directly in the bleaching stage although the equilibrium peracid is preferred and is what is used in the examples of this application. EP-A-0670928 describes an identical method. However, whilst equilibrium peracid improves the bleaching it also introduces problems of handling and dosing, peracid in the pulp plant.
- EP456032 and GB2304126 describe the use of tetraacetylethylenediamine (TAED) as the bleach activator. Whilst this produces a very effective bleaching solution, generation of such a solution in certain circumstances may not prove to be economical for all mills. It would therefore be desirable to develop a process by which peracid can be generated in a good yield by reacting hydrogen peroxide with a more cost effective bleach activator, thus ensuring that it is more cost effective than the method of the prior art which uses TAED.
- a bleach activator suitable for solving this problem is acetic anhydride. Whilst the use of acetic anhydride as a bleach activator to produce peracetic acid is well documented, surprisingly better performance can be delivered using peracetic acid generated from acetic anhydride as compared to preformed peracetic acid.
- US3,227,655 discloses a process of preparing a stable concentrated aqueous solution of a bleaching agent containing monoperacetic acid for bleaching fibre materials. Hydrogen peroxide and acetic anhydride are reacted together in an aqueous medium in the presence of ammonium hydroxide.
- the water used in step a) is of a temperature between 5°C-100°C, preferably between 10°C-50°C and more preferably between 15°C-30°C. At cooler temperatures the generation of the percarboxylic acid may be inhibited whilst at higher temperatures, although the generation would be rapid, it is anticipated that degradation of the percarboxylic acid species would be promoted.
- Chelating agent is added to the water in step a) prior to the addition of further components and is advantageous as it ensures that any trace metals which may be present in the supply are removed. Such trace metals could potentially promote the decomposition of hydrogen peroxide.
- a mixing step is preferably included to maximise the chelation of the trace metals.
- the chelating agent is an aqueous phosphonic acid based chelating agent.
- suitable phosphonic acid based chelating agents are polyamino methylene phosphonic acids such as based on ethylene diamine or diethylenetriamine.
- Commercially available compounds of this type include Dequest SPE9505, Dequest 20605.
- the chelating agent is Dequest SPE 9505 and/or Dequest 2066.
- An aqueous phosphonic acid based chelating agent has been found to work best under the conditions of the method of the present invention.
- the amount of chelating agent, eg phosphonic acid based agent, added to the water is 0.1-0.4wt%, more preferably 0.125-0.3%wt and most preferably 0.15-0.25%wt.
- the amount of hydrogen peroxide added in step b), based on a 50% solution is a value in the range 0.5-6wt%, more preferably in the range 1.5-4.0wt% and most preferably in the range 1.75-2.5wt%.
- the alkali is added in step c) in an amount to raise the pH of the solution from a value in the range 6-7 to a value in the range 10.5-11.5. It is important that this alkali addition occurs prior to step (d). This is because rendering the hydrogen peroxide solution of step b) alkaline promotes the formation of perhydroxyl ion with which the carboxylic acid anhydride compound preferentially reacts instead of water. If step c) was not included, the carboxylic acid anhydride compound would hydrolyse thus reducing the amount of percarboxylic acid eventually formed.
- Suitable alkalis include potassium hydroxide, calcium hydroxide, magnesium hydroxide and sodium hydroxide.
- the alkali is sodium hydroxide.
- Sodium hydroxide is available as a 30w/w% or 50w/w% solution. Suitable amounts were determined by monitoring the pH.
- the amount of sodium hydroxide added based on a 50% solution is a value in the range 0.2-3wt%, more preferably in the range 0.4-1.5wt% and most preferably in the range 0.5-1wt%.
- step d there is a further mixing step (step d)).
- the duration of this step is preferably at least one minute. This is important to optimise the extent of formation of the perhydroxyl ion in the subsequent steps. At present, a specific method for directly analysing whether complete formation of the perhydroxyl ion has taken place is not available. However, it is possible to obtain an indication of the extent of perhydroxyl ion formation by analysing the percentage conversion of the carboxylic acid anhydride compound to percarboxylic acid. A low percentage conversion rate may indicate incomplete formation of the perhydroxyl ion. If sufficient time is not allowed for this mixing step and the carboxylic acid anhydride compound is added prematurely then it would preferentially undergo a hydrolysis reaction with water resulting in a low percarboxylic acid generation.
- the carboxylic acid anhydride compound is added (step e)).
- the carboxylic acid anhydride compound added in step e) is selected from one or more of the group consisting of acetic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, malonic anhydride, benzoic anhydride and propanoic anhydride.
- the amount of carboxylic acid anhydride compound added is in the range 0.02 - 0.6mol%, more preferably in the range 0.05 - 0.3mol% and most preferably in the range 0.075 - 0.15mol% and this addition is followed by a further important mixing step (step f)).
- This mixing step should be allowed to occur for at least 10 minutes. This is to maximise generation of the percarboxylic acid species. It is, however, possible to accelerate the generation of the percarboxylic acid species by using amounts of alkali at the higher end of the ranges mentioned above prior to the carboxylic acid anhydride addition.
- the carboxylic acid anhydride compound comprises acetic anhydride.
- Acetic anhydride has a flash point of 54°C and as such is classified as flammable.
- a compound is classified as flammable where it has a flashpoint in the range of 21 °C-55°C.
- DSEAR Dangerous Substances and Explosive Atmosphere Regulations
- Flammability rating also has an impact on zone classification on manufacturing plants.
- the applicants have investigated increasing the flash point of acetic anhydride by mixing with a further carboxylic acid anhydride with a higher flashpoint. For example, maleic anhydride has a flash point of 102°C.
- the flashpoint of acetic anhydride is modified by addition of a carboxylic acid anhydride with a higher flashpoint to form a mixture which has a flash point of 55.1 °C or higher such that it is not classified as flammable.
- a mixture which has a flash point of 60°C or higher is formed.
- the amount of carboxylic acid anhydride with a higher flashpoint added is such that the resulting mixture has a ratio of acetic anhydride to carboxylic acid anhydride with a higher flashpoint greater than 50:50 but less than or equal to 80:20.
- the carboxylic acid anhydride with a higher flashpoint is maleic anhydride.
- a 50:50 mixture of acetic anhydride: maleic anhydride is not commercially practical as, upon cooling, the maleic anhydride precipitates out of the solution.
- the ratio of acetic anydride to maleic anhydride is 80:20.
- the mixture consists of the acetic anhydride and further carboxylic acid anhydride with a higher flashpoint only.
- the mixture of acetic anhydride and carboxylic acid anhydride with a higher flashpoint can then be used as the carboxylic acid anhydride compound in the method for bleaching cellulosic fibres of the invention.
- the molar ratio of carboxylic acid anhydride compound to hydrogen peroxide added is preferably in the range 1:1 to 1:10, preferably 1:1.5 to 1:6, more preferably 1:2 to 1:4. Most preferably the molar ratio is about 1:3. In terms of the number of moles added, it is preferable that more hydrogen peroxide is required than carboxylic acid anhydride compound in order to drive the reaction to form perhydroxyl ion.
- the resultant dilute percarboxylic acid solution formed in step f) will have a pH of approximately 5. Depending on the mill conditions, it may be necessary to increase the solution pH to suit the bleaching conditions required in the final step of the process, step g).
- the resultant solution contains percarboxylic acid in a concentration range of 0.1-10%, more preferably 0.25-5% and most preferably 0.5-2%.
- the final step (step g)) of the process is to contact the dilute percarboxylic acid solution with a cellulosic fibre suspension e.g formed from pulp.
- the pulp may be any sort of pulp, including chemical and mechanical pulp and mixture thereof, including recycled material. Wood and non wood fibres can be bleached using this process.
- the product may be used directly to form paper or board or may be fully or partially dewatered to form a pulp intermediate for eventual paper or board manufacture.
- each of the formulations were prepared according to the method of the present invention. More specifically, fresh water at a temperature in the range from 15-30°C was treated with 0.2wt% of Dequest 2066. 2wt% of a 50% hydrogen peroxide solution was added to the stabilised water supply the pH of the resulting hydrogen peroxide solution was adjusted to a pH in the range from 10.5 to 11.5 by the addition 0.75wt% of a 50% solution of sodium hydroxide. The mixture was then mixed for a period of 1 minute to allow complete formation of the perhydroxyl ion. The bleach activator was added to this mixed solution in the amounts shown above respectively and the solution was mixed to allow complete formation of peracetic acid to give a dilute solution of peracetic acid.
- the peracid release profile for each of formulations 1-5 was determined by taking measurements between 2 and 145 minutes. The solution temperatures were maintained at 25°C. pH profiles were also attained during the process. The results of the peracid release profile are shown in Table 1 and Figure 1 . The pH profiles attained are illustrated in Table 2 and Figure 2 .
- the bleaching ability of the acetic anhydride derived peracetic acid solution was compared with the bleaching ability of a preformed peracetic acid. More specifically, bleaching formulation 4 was compared to a preformed commercially available peracetic acid (supplied by Aldrich), hereinafter referred to as formulation 6.
- brown stock delignification and recycled bleaching studies were performed using brown stock and 80:20 Newsprint: MOW pulps respectively.
- the studies were performed using a 0.1 %, 0.25% and 0.5% charge of peracetic acid (based on 100% peracetic acid) respectively at a temperature of 70°C and with a retention time of 120 minutes.
- Formulation 4 was used at a pH in the range 8-8.5 and formulation 6 was used at a pH of 5 which represents the normal conditions under which it is used.
- the data shows that a superior bleaching performance is achieved using acetic anhydride derived peracetic acid as compared to preformed peracetic acid.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
Claims (21)
- Verfahren zum Bleichen vom Cellulosefasern, umfassend die Schritte:(a) Behandeln einer Frischwasser-Zuführung mit Chelatbildner, um eine stabilisierte Wasserzuführung zu ergeben;(b) Zugabe von Wasserstoffperoxid zu der stabilisierten Wasserzuführung, um eine Wasserstoffperoxid-Lösung zu bilden;(c) Einstellen des pH der Wasserstoffperoxid-Lösung durch Zugabe von Alkali;(d) Mischen der aus Schritt (c) erhaltenen, pH-eingestellten Lösung, um eine vollständige Bildung von Perhydroxylion zu ermöglichen;(e) Zugabe einer Carbonsäureanhydrid-Verbindung zu der aus Schritt (d) erhaltenen Lösung;(f) Mischen der aus Schritt (e) erhaltenen Lösung, um eine vollständige Bildung von Percarbonsäure zu ermöglichen, um eine verdünnte Lösung von Percarbonsäure zu ergeben; und(g) Kontaktieren der Lösung der Persäure mit einer Suspension von Cellulosefasern.
- Verfahren nach Anspruch 1, bei welchem die Frischwasser-Zuführung eine Temperatur im Bereich von 15 bis 30°C aufweist.
- Verfahren nach Anspruch 1, bei dem der Chelatbildner auf wässriger Phosphonsäure basiert.
- Verfahren nach Anspruch 3, bei dem der auf Phosphonsäure basierende Chelatbildner Dequest SPE9505 und/oder Dequest 2066 ist.
- Verfahren nach Anspruch 1, bei dem die zugegebene Menge an Chelatbildner im Bereich von 0,1 bis 0,4 Gew.-% liegt.
- Verfahren nach Anspruch 1, bei dem die zugegebene Menge an Chelatbildner im Bereich von 0,125 bis 0,3 Gew.-% liegt.
- Verfahren nach Anspruch 1, bei dem die zugegebene Menge an Chelatbildner im Bereich von 0,15 bis 0,25 Gew.-% liegt.
- Verfahren nach irgendeinem der vorhergehenden Ansprüche, bei dem die zugegebene Menge an Wasserstoffperoxid auf Basis einer 50% Lösung im Bereich von 0,5 bis 6 Gew.-%, bevorzugter im Bereich von 1,5 bis 4,0 Gew.-% und am meisten bevorzugt im Bereich von 1,75 bis 2,5 Gew.-% liegt.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem das Alkali Natriumhydroxid ist.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die zugegebene Menge an Alkali im Bereich von 0,2 bis 3 Gew.-%, bevorzugt im Bereich von 0,4 bis 1,5 Gew.-% und bevorzugter im Bereich von 0,5 bis 1,0 Gew.-% liegt.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem der pH auf einen Wert im Bereich von 10,5 bis 11,5 eingestellt wird.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Dauer des Mischschritts (d) mindestens 1 min beträgt.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die zugegebene Menge an Carbonsäureanhydrid-Verbindung im Bereich von 0,02 bis 0,6 Mol-%, bevorzugt im Bereich von 0,05 bis 0,3 Mol-% und bevorzugter im Bereich von 0,075 bis 0,15 Mol-% liegt.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Dauer des Mischschritts (f) mindestens 10 min beträgt.
- Verfahren nach irgendeinem vorhergehenden Anspruch, welches ferner einen zusätzlichen pH-Einstellschritt umfasst, bevor die Lösung mit der Cellulosefaserlösung kontaktiert wird.
- Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem das Carbonsäureanhydrid ausgewählt ist aus einem oder mehreren der Gruppe bestehend aus Essigsäureanhydrid, Maleinsäureanhydrid, Bernsteinsäureanhydrid, Malonsäureanhydrid, Benzoesäureanhydrid und Propansäureanhydrid.
- Verfahren nach Anspruch 16, bei dem die Carbonsäureanhydrid-Verbindung Essigsäureanhydrid umfasst.
- Verfahren nach Anspruch 17, bei dem die Carbonsäureanhydrid-Verbindung zusätzlich ein weiteres Carbonsäureanhydrid mit einem höheren Flammpunkt umfasst und das Essigsäureanhydrid mit dem weiteren Carbonsäureanhydrid mit einem höheren Flammpunkt vorgemischt worden ist, um eine Mischung Essigsäureanhydrid/Carbonsäureanhydrid mit einem modifizierten Flammpunkt von 55,1°C oder darüber zu bilden.
- Verfahren nach Anspruch 18, bei dem das Verhältnis von Essigsäureanhydrid zu Maleinsäureanhydrid in der Mischung Essigsäureanhydrid/Carbonsäureanhydrid mit einem modifizierten Flammpunkt größer als 50:50 ist.
- Verfahren nach Anspruch 18, bei dem das Verhältnis von Essigsäureanhydrid zu Maleinsäureanhydrid mit einem höheren Flammpunkt in der Mischung Essigsäureanhydrid/Carbonsäureanhydrid mit einem modifizierten Flammpunkt 80:20 ist.
- Verfahren nach irgendeinem der Ansprüche 19 bis 21, bei dem das Carbonsäureanhydrid mit einem höheren Flammpunkt Maleinsäureanhydrid ist.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES04253546T ES2300713T3 (es) | 2004-06-14 | 2004-06-14 | Activador para el blanqueado de pasta de papel. |
PL04253546T PL1607519T3 (pl) | 2004-06-14 | 2004-06-14 | Aktywator bielenia ścieru |
AT04253546T ATE386837T1 (de) | 2004-06-14 | 2004-06-14 | Aktivator zum zellstoffbleichen |
PT04253546T PT1607519E (pt) | 2004-06-14 | 2004-06-14 | Activador para branqueamento de pasta |
EP04253546A EP1607519B1 (de) | 2004-06-14 | 2004-06-14 | Aktivator zum Zellstoffbleichen |
DE602004011911T DE602004011911T9 (de) | 2004-06-14 | 2004-06-14 | Aktivator zum Zellstoffbleichen |
CA002569467A CA2569467A1 (en) | 2004-06-14 | 2005-06-10 | Activator for pulp bleaching |
PCT/GB2005/002312 WO2005121443A1 (en) | 2004-06-14 | 2005-06-10 | Activator for pulp bleaching |
US11/570,140 US20070246177A1 (en) | 2004-06-14 | 2005-06-10 | Activator for Pulp Bleaching |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04253546A EP1607519B1 (de) | 2004-06-14 | 2004-06-14 | Aktivator zum Zellstoffbleichen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1607519A1 EP1607519A1 (de) | 2005-12-21 |
EP1607519B1 true EP1607519B1 (de) | 2008-02-20 |
Family
ID=34930404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04253546A Expired - Lifetime EP1607519B1 (de) | 2004-06-14 | 2004-06-14 | Aktivator zum Zellstoffbleichen |
Country Status (9)
Country | Link |
---|---|
US (1) | US20070246177A1 (de) |
EP (1) | EP1607519B1 (de) |
AT (1) | ATE386837T1 (de) |
CA (1) | CA2569467A1 (de) |
DE (1) | DE602004011911T9 (de) |
ES (1) | ES2300713T3 (de) |
PL (1) | PL1607519T3 (de) |
PT (1) | PT1607519E (de) |
WO (1) | WO2005121443A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8268122B2 (en) * | 2005-12-02 | 2012-09-18 | Akzo Nobel N.V. | Process of producing high-yield pulp |
DE102006028018A1 (de) * | 2006-06-14 | 2007-12-20 | Henkel Kgaa | Aufhell-und/oder Färbemittel mit Estern und/oder Anhydriden |
CA3178055A1 (en) * | 2020-06-16 | 2021-12-23 | Leif Robertsen | Method for pitch control during bleaching |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2377038A (en) * | 1941-09-15 | 1945-05-29 | Du Pont | Manufacture of peracids |
US3227655A (en) * | 1957-11-25 | 1966-01-04 | Fmc Corp | Process for preparation of a bleaching agent |
US4294575A (en) * | 1979-01-02 | 1981-10-13 | Monsanto Company | Peroxide stabilization |
FR2457339A1 (fr) * | 1979-05-25 | 1980-12-19 | Interox | Procede pour la delignification et le blanchiment de pates cellulosiques chimiques et semi-chimiques |
JPH04108192A (ja) * | 1990-04-25 | 1992-04-09 | Hoechst Japan Ltd | パルプの漂白法 |
ES2096441T3 (es) | 1992-11-27 | 1997-03-01 | Eka Chemicals Ab | Procedimiento para deslignificar pasta que contiene lignocelulosa. |
CA2149649C (en) * | 1992-11-27 | 2000-09-19 | Magnus Linsten | Process for bleaching of lignocellulose-containing pulp |
GB2304126A (en) * | 1995-08-10 | 1997-03-12 | Warwick Int Group | Pulp treatment process |
-
2004
- 2004-06-14 EP EP04253546A patent/EP1607519B1/de not_active Expired - Lifetime
- 2004-06-14 PL PL04253546T patent/PL1607519T3/pl unknown
- 2004-06-14 AT AT04253546T patent/ATE386837T1/de active
- 2004-06-14 DE DE602004011911T patent/DE602004011911T9/de active Active
- 2004-06-14 ES ES04253546T patent/ES2300713T3/es not_active Expired - Lifetime
- 2004-06-14 PT PT04253546T patent/PT1607519E/pt unknown
-
2005
- 2005-06-10 CA CA002569467A patent/CA2569467A1/en not_active Abandoned
- 2005-06-10 WO PCT/GB2005/002312 patent/WO2005121443A1/en active Application Filing
- 2005-06-10 US US11/570,140 patent/US20070246177A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
DE602004011911D1 (de) | 2008-04-03 |
PL1607519T3 (pl) | 2008-07-31 |
DE602004011911T9 (de) | 2009-01-02 |
US20070246177A1 (en) | 2007-10-25 |
CA2569467A1 (en) | 2005-12-22 |
DE602004011911T2 (de) | 2008-08-28 |
WO2005121443A1 (en) | 2005-12-22 |
ATE386837T1 (de) | 2008-03-15 |
PT1607519E (pt) | 2008-04-16 |
EP1607519A1 (de) | 2005-12-21 |
ES2300713T3 (es) | 2008-06-16 |
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