WO1995021290A1 - Blanchiment de pate a papier - Google Patents

Blanchiment de pate a papier Download PDF

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Publication number
WO1995021290A1
WO1995021290A1 PCT/GB1995/000246 GB9500246W WO9521290A1 WO 1995021290 A1 WO1995021290 A1 WO 1995021290A1 GB 9500246 W GB9500246 W GB 9500246W WO 9521290 A1 WO9521290 A1 WO 9521290A1
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WO
WIPO (PCT)
Prior art keywords
pulp
bleaching
hydrogen peroxide
activator
acyl
Prior art date
Application number
PCT/GB1995/000246
Other languages
English (en)
Inventor
Vincent Brian Croud
Original Assignee
Warwick International Group Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from PCT/GB1994/000228 external-priority patent/WO1994018297A1/fr
Priority claimed from GB9415909A external-priority patent/GB9415909D0/en
Application filed by Warwick International Group Limited filed Critical Warwick International Group Limited
Priority to AU15842/95A priority Critical patent/AU1584295A/en
Publication of WO1995021290A1 publication Critical patent/WO1995021290A1/fr

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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

Definitions

  • the present invention relates to a process for bleaching of cellulosic pulps, especially for use in paper making, in which an activator is used during a peroxide bleaching step carried out at a pH which is acidic or slightly alkaline.
  • the process is usually part of multi- step process, especially a chlorine free pulp bleaching process.
  • the use of chlorine and even chlorine dioxide in bleaching processes for pulps causes environmental problems due to production' of polychlorinated organic compounds in the paper and the waste.
  • Pulp bleached with totally chlorine free sequences ( ⁇ CF) is being manufactured and sold by many pulp mills. In TCF bleaching, the pulp is first delignified as much as possible with existing cooking and oxygen pre-delignification facilities.
  • the pulp is th'.n treated in several bleaching stages, optionally preceded by a sequestering stage to remove heavy metals from the pulp. Heavy metals otherwise tend to increase the rate of decomposition of peroxygen bleaching moieties.
  • the multi-step bleaching processes may include steps carried out under acidic and/or alkaline processes. Although the mechanical properties of the paper from pulps produced by TCF processes are satisfactory, the final brightness is often inadequate, and the paper "has poor brightness reversion properties so that it tends to yellow after a time.
  • EP-A-0,543 , 174 suggests the use of sodium cyanate in an alkaline peroxide step.
  • US-A-3, 687,803 suggests the inclusion of an activator which is a benzoyl chloride, though the pH is usually 8.5 or higher.
  • US-A-3 , 193 ,445 describes a two-stage procedure in which pulp is treated with hydrogen peroxide under alkaline conditions to at least partially deplete the peroxide, after which acetic anhydride is added directly to the product of the first stage to continue the bleaching.
  • carboxylic acids are added to alkaline hydrogen peroxide.
  • EP-A-0456032 a pulp bleaching process is described in which pulp is bleached with a peroxide and a bleach activator such as TAED, under alkaline conditions. The highest bleaching effect is said to be obtained at pH 9-10.
  • oxygen gas or peroxides are added to an aqueous alkaline slurry of cellulose pulp. The treatment is conducted in the presence of an amine acylation product.
  • the alkali is preferably added on a bone-dry pulp weight basis 0.5-3% as Na z O, preferably sodium hydroxide is used.
  • JP-A-(1989)-104893 long chain alkanoyloxy-benzene sulphonate activators are used to enhance the activity of various alkaline bleaches including peracetic acid and hydrogen peroxide.
  • GB-A-1,117,336 describes an apparatus and process for making peracetic acid on the site where the solution is req ed as a bleaching agent by reaction of acetic antr .ride and hydrogen peroxide in the presence of a basic catalyst.
  • the Milox pulping process involves the cooking of woodchips with hydrogen peroxide in the presence of formic acid or acetic acid. In the process it is believed that the corresponding percarboxylic acid is formed and acts as the active oxidising agent. It has been suggested to use the Milox process steps also to treat pulp produced by other pulping processes (such as Kraft) as a delignification stage prior to subsequent bleaching stages. In WO-A-86/05529 it is suggested to produce the peracid by reaction of aldehyde with molecular oxygen.
  • Troughton et al from Solvay Interox, in a paper presented to The International Non-Chlorine Bleaching Conference, March 6-10, 1994 Amelia Island, Florida, USA, describe multi-stage bleaching processes for TCF kraft pulps, including an initial sequestration stage, followed by multiple peroxide bleaching stages and optional peracid bleaching stages.
  • the peracids used are permono sulphuric acid or Caro's acid and percarboxylic acid.
  • Troughton et al propose distilling peracetic acid to minimise waste of unreacted acetic acid and hydrogen peroxide. • ncentrating the peracid in this way, however increases handling difficulties.
  • the pH of the pulp during a peracid bleaching stage should be low, because of the rapid rate of decomposition of the peracid around the pKa of the peracid. It is also indicated that the initial rate of delignification by the peracid is increased at higher pH, but the competing decomposition reaction (forming oxygen gas) means that around half of the peracid may be lost to this side reaction.
  • the desirability of having a peracid stage between two alkaline peroxide stages is explained as allowing residual lignin resistant to alkaline peroxide from the first alkaline peroxide bleaching step to be attacked to generate phenolic hydroxyl groups, which can subsequently be attacked in the following alkaline peroxide stage.
  • the bleach solution may be prepared at a concentration for immediate bleaching or as a concentrate for dilution, under acidic conditions.
  • the new process according to the-present invention for bleaching cellulosic pulps comprises the steps: a) forming an aqueous solution containing hydrogen peroxide or an inorganic persalt and a bleach activator compound which is an acyl donor to form an oxidising compound which is a stronger oxidising agent than hydrogen peroxide, the step being carried out at a pH in the range 1 to p ⁇ a '; b) contacting the pulp with the stronger oxidising agent at a starting pH in the range 1 to pK a ' where pK a ' is the pK a of the percarboxylic acid corresponding to the acyl group of the activator, in which the bleach activator compound is selected from N-acyl and O-acyl derivatives, and wherein when the activator compound is an anhydride it is a solid material .
  • the invention also includes a process for bleaching cellulosic pulps comprising the steps:
  • the present invention is particularly advantageous because it has been found to produce pulps having good brightness reversion properties without the usual increase in fibre damage.
  • the activator is a compound of the formula I
  • the leaving group L is preferably a compound the conjugate acid of which has a pKa in the range 4 to 13, preferably 7 to 11, most preferably 8 to 11. It is preferred that R is an aliphatic group preferably a C. .18 alkyl group, or an aryl group.
  • the alk(en)yl groups may be straight, branched or cyclic.
  • L and R may be joined to form a cyclic compound, usually a lactone or a lacta .
  • These cyclic groups may include heteroatoms, for instance oxygen or optionally substituted nitrogen atoms, carboxyl groups as well as -CH 2 - groups or substituted derivatives thereof. They may be saturated or unsaturated.
  • the compound of the formula I can be any N-acyl or O-acyl acyl-donor compound, which has been described as a bleach activator for use in laundry detergents.
  • the compound of the formula I may be an anhydride, but is preferably an ester or, even more preferably, an amide derivative.
  • Amide derivatives include acyl imidazolides and N,N-di acylamides.
  • N-acyl derivatives are: a) l,5-diacetyl-2, 4-dioxohexahydro-l,3,5-triazine (DADHT) ; b) N-alkyl-N-suphonyl carbonamides, for example the compounds N-methyl-N-mesyl acetamide, N-methyl-N-mesyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, andN-methyl- N-mesy1-p-methoxybenzamide; c) N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl aleic acid hydrazide; d) 0,N,N-trisubstituted hydroxylamines, such as O-benzoyl- N,N-succinyl hydroxylamine
  • k 0,N,N-trisubstituted alkanolamines, such as 0,N,N- triacetyl ethanolamine.
  • Cyanamides such as those disclosed in DE-A-3,304,848.
  • N-acyl lactams such as N-benzoyl-caprolactam
  • the compound r y be an ester, for instance n) sugar esters, such as pentaacetylglucose, o) esters of imidic acids such as ethyl benzimidate, p) triacylcyanurates, such as triacetylcyanurate and tribenzoylcyanurate, q) esters giving relatively surface active oxidising products for instance of C 8 .
  • L comprises an aryl group having a sulphonic acid group (optionally salified) substituted in the ring to confer water solubility on a benzyl group, especially nonanoyloxy- benzenesulphonate sodium salt (NOBS) , isononanoyloxy- benzenesulphonate sodium salt (ISONOBS) and benzoyloxy- benzenesulphonate sodium salt (BOBS) r) phenyl esters of C 14 .
  • NOBS nonanoyloxy- benzenesulphonate sodium salt
  • ISONOBS isononanoyloxy- benzenesulphonate sodium salt
  • BOBS benzoyloxy- benzenesulphonate sodium salt
  • the activator is an anhydride it is preferably a solid material, and is preferably an intra-molecular anhydride, or a polyacid polyanhydride.
  • Such anhydride compounds are more storage stable than liquid anhydrides, such as acetic anhydride.
  • Anhydride derivatives which may be used as activator include v) intramolecular anhydrides of dibasic carboxylic acids, for instance succinic, maleic, adipic, phthalic or 5- norbornene-2,3-dicarboxylic anhydride, w) intermolecular anhydrides, including mixed anhydrides, of mono- poly-basic carboxylic acids, such as diacetic anhydride of isophthalic or perphthalic acid x) isatoic anhydride or related compounds such as described in WO-A-8907640 having the generic formula II wherein is a divalent organic group such that Q and N together with the carbonyl groups and oxygen atom of the anhydride group form one or more cyclic structures and R is H, alkyl, aryl, halogen or a carbonyl group of a carboxyl containing function; or benzoxazin-4-ones as described in WO-A-8907639, that is compounds of the formula
  • 0/ is selected from the same groups as Q and R is H, alkyl, aryl, alkaryl, aralkyl, alkoxyl, haloalkyl, amino, aminoalkyl, carboxylic group or a carbonyl- containing funcrion; preferably 2-methyl-(4H) 3,1- benzoxazin-4-one (2MB4) or 2-phenyl-(4H) 3, l-benzoxazin-4- one (2PB4) ; y) polymeric anhydrides such as poly(adipic) anhydride or other compounds described in WO-A-9306203.
  • a mixture of activators may be utilised.
  • a mixture of activators which will provide different oxidising compounds such compounds preferably having different hydrophilicities.
  • a mixture of activators which will provide a relatively hydrophobic oxidising compound and a relatively hydrophilic oxidising compound are described in our earlier patent publication EP-A-0299599.
  • the two activators will different R groups and may have the same or different leaving groups .
  • one of the groups R may be a methyl group, so as to form peracetic acid.
  • the other of the groups R may comprise a higher alkyl group, for instance a C 6 . 12 -alkyl, optionally branched alkyl.
  • the process of the present invention may be carried out in the presence of a bleach catalyst.
  • Suitable bleach catalysts are for instance, manganese complex based catalysts or polyoxometalates, as recently promoted by Kemira, as well as organic catalysts such as enzymes and sulphonamines.
  • step a) may be carried out before step b) .
  • the hydrogen peroxide or inorganic persalt and the bleach activator may be allowed to re'act in aqueous conditions for at least 5 minutes preferably 10 minutes, up to one or two days, preferably one day, before the aqueous reaction product of step a) is added to the aqueous pulp.
  • hydrogen peroxide or persalt and the bleach activator compound may be added direct to the pulp, either simultaneously or one after the other, optionally with a period of time between separate additions.
  • the reaction is preferably carried out at a temperature, in the range 10-60°C, most preferably in the range 20-40°C.
  • the concentration of hydrogen peroxide in step a) reaction mixture is preferably in the range 0.1% to 60%, usually in the range 0.2 or 0.5% to 30 or 10% w/v.
  • Inorganic persalt which is less preferred, can be used in a concentration to give the same amount of available oxygen in a given volume of solution as the specified preferred concentrations of hydrogen peroxide.
  • the bleach activator is preferably present in step a) and step b) in an amount to provide 0.1 to 5.0 mole equivalents, preferably 0.2 to
  • the pH is suitably in the range 2 to (pK a ' - 0.05), more preferably (pK a '-3) to (pK a '-0.2).
  • the pH in the step b) is at or below pK a ' and is preferably in the range (pK a '-5) - (pK a '-0.1) most preferably in the range (pK a ' ⁇ 2) to (pK a ' - 0.5).
  • the solution of step a) may be diluted before step b) if the steps are carried out in that order.
  • the pK a of some of the peracids corresponding to the acyl group of the activator are as follows: Peracetic:8.2; Performic:7.1; Perbenzoic:7.64 perbutanoic:8.2; perpropanoic:8.1. Use of a pH too far below pK a ' should be avoided because the rate of bleaching is too slow.
  • the mixture of peroxide and activator may be made up in either order, that is by formation of a peroxide solution followed by addition of activator or vice versa.
  • the activator is a solid best results have been obtained by predissolution of the activator in water if necessary at elevated temperature followed by mixing with peroxide solution, then adjusting pH.
  • the process is suitable for use as one stage in a multi-stage process, especially for providing totally chlorine free pulp. It may also be of use where the total process is free of elemental chlorine (or molecular chlorine or chlorine gas) , that is where the process includes a chlorine dioxide bleaching step. Such a step may be carried out before or after the steps of the present invention.
  • the present invention is particularly suitable for use following steps in which the pulp has been at least partially delignified. Such previous delignification and/or bleaching stages may be carried out, for instance, by peroxide under alkaline conditions or acidic conditions, oxygen and/or ozone treatment steps or peracid acid treatment steps, as well as any of the other delignification steps.
  • the pulp may be any type of pulp including mechanical, but is preferably chemical pulp.
  • the process of the present invention has been found to be of particular value where the process involves a subsequent alkaline peroxide bleaching stage. Since the process of the present invention is carried out at higher pH's than conventional peracid bleaching stages, the amount of alkaline chemical required to be added subsequently to achieve the desired alkaline pH is reduced and may be dispensed with altogether in some cases.
  • a subsequent alkaline bleaching step is usually carried out by contacting the pulp treated by the process of the present invention with hydrogen peroxide or another bleach, preferably an oxygen bleach, under alkaline conditions, preferably at a pH in the range 9 to 12, and optionally in the presence of an activator and/or sequestrant.
  • the alkaline bleaching step may be carried out after an intermediate rinsing step for instance where such a rinse step removes dissolved components which would otherwise react with reagents for subsequent steps, thereby deactivating them before they can interact with the pulp.
  • Such interstage rinses may also remove transition metals liberated during the acidic bleaching step of the present invention which could cause decomposition of the bleach in a subsequent alkaline bleaching stage.
  • a subsequent alkaline bleaching stage may be carried out without an intermediate rinsing step.
  • the pulp may be thickened prior to the subsequent alkaline peroxide or other alkaline bleaching step.
  • the present inventors have discovered that the bleaching step of the present invention is of particular value as the penultimate step of the overall bleaching process.
  • the present invention thus preferably comprises a single alkaline peroxide bleaching step following the novel activated bleach step.
  • novel process of the present invention may also be used to bleach or otherwise treat recycled pulp, including recycled deinked pulp, or as a combination deinking/bleaching step.
  • the pulp contacted with the stronger oxidising agent in step b) of the present invention should be relatively free of potentially interfering heavy metal or transition metal ions. Such ions might otherwise catalyse premature decomposition of oxidising species.
  • step b) of the present invention is carried out at a relatively late stage of multi-stage bleaching process, it may be unnecessary to take measures to remove transition metals from the pulp, especially where there has been a previous acid step in the pulping or delignification/bleaching steps. If, however, the pulp retains relatively high quantities of heavy metal ions, these can be removed in a previous step in which the pulp is contacted with a suitable organic sequestrant. For such steps it may be preferably to remove the sequestered heavy metal with the supernatant liquor.
  • Suitable sequestrants for remaining in the system are usually phosphonic acid or carboxylic acid derivatives, selected having regard to the pH and the metal ions to be sequestered. Examples are ethylene diamine tetraacetic acid (EDTA) and diethylene triamene pentacetic acid (DTPA) or poly(methylene phosphonic acid) derivatives such as ethylene diamine tetra methylenephosphonic acid (EDTMP) .
  • EDTA ethylene diamine tetraacetic acid
  • DTPA diethylene triamene pentacetic acid
  • poly(methylene phosphonic acid) derivatives such as ethylene diamine tetra methylenephosphonic acid (EDTMP) .
  • the process of the present invention is of particular utility where the incoming pulp has a brightness of less than 85% ISO (that is has a value of less than 85% when tested by International standard test method at 457 nm using a Carlzeiss Eirepho) .
  • the brightness of the incoming pulp is preferably in the range 83-85%.
  • the process of the present invention is preferably carried out a temperature of at least 40°C, preferably less than 95°C, more preferably in the . ange 60-80°C.
  • the step is generally carried out for a period of time sufficient to reduce the kappa number of the pulp (as determined by International standard test method number ISO 302) of at least 10%, preferably at least 20%.
  • the reaction is generally carried out over a period in the range 10 min to 6 hours, preferably at least 20 minutes up to three hours, for instance 30 minutes to 120 minutes.
  • the present invention is desirable for several reasons and has many advantages over the prior art. Although the reaction may be carried out in a holding tank, the components for the bleaching step may also be prior mixed immediately before addition to the bleaching tower, thus requiring no additional reaction vessel or holding tank.
  • the use of a mixture of activators may allow penetration of bleaching agents into relatively hydrophobic sites in the pulp not previously possible with peracetic acid alone, whilst retaining the desirable performance of a relatively hydrophilic oxidising species such as peracetic acid.
  • a relatively hydrophilic oxidising species such as peracetic acid.
  • the amount of activator added can be adjusted to adjust the extent of bleaching, for different sources of wood, or to give different degrees of bleaching, the present invention being more flexible and adaptable than the use of preformed peracids.
  • the concentration of actives and the rate of release of strong oxidising species can be controlled by changing the temperature in the bleach tower, altering the pH or altering the peroxide to activator ratio.
  • concentration of actives can only be changed by dilution.
  • dilution causes decomposition of the peracids by moving the equilibrium back to peroxide and acid.
  • optimising conditions in the process of the present invention essentially all the activator present may be productively consumed. Optionally this may be by recycling unreacted activator to form part of the starting materials for the bleaching step. Since the use of an activator allows the solutions created and the bleaching process itself to be carried out at relatively dilute concentrations, this minimizes handling problems otherwise encountered with prior art processes using peracetic acid.
  • the process of the invention provides treatment pulp, in which the product paper has better resistance to yellowing than prior art processes which do not use an activator. Furthermore the final brightness obtained using the process of the present invention is improved without any increase in the amount of fibre damage.
  • the invention is illustrated further in the following examples. Pulps
  • Pulp 1 a soft wood kraft pulp subjected to initial peroxide bleaching steps to give a brightness of 82.5%, kappa number 5.1 and viscosity of 780 dm /kg.
  • Pulp 2 a hard wood kraft pulp bleached by previous peroxide bleaching steps to give brightness 83.0%, kappa number 6/1 and viscosity 670 dm /kg.
  • Pulp 3 a second soft wood kraft pulp subjected to previous steps of peroxide bleach to give a brightness of 85.1%, kappa number 2.1% and viscosity 610 dm /kg Chelation Stage
  • Optimisation of a chelation stage carried out prior to the bleaching stage under test was carried out to select the optimal chelating agent (either diethylene triamine penta acetic acid (DTPA) or diethylenetriamine penta(methylene phosphonic acid) (DTPMP)) , the dosage, the time and the pH at which chelation takes place.
  • the chelation was carried out at concentrations of chelating agent in the range 0.1 to 0.3 % on pulp for DTPA and 0.05 to 0.8% on pulp for DTPMP.
  • the pH was 4.5 or 6 or DTPA or 6 for DTPMP.
  • the consistency of the pulp was 2% and the temperature was 7 * 0°C, the reaction time being 60 minutes. Following the chelation step the pulp slurry was concentrated and washed.
  • a solution containing hydrogen peroxide and tetracetylethylene diamine (TAED) was made up by first dissolving an appropriate amount of TAED into water at 70-80°C, then adding an appropriate amount of aqueous hydrogen peroxide and adjusting pH as necessary. It was used immediately in an amount so as to give the dosage mentioned in the tables below.
  • the pulp having been subjected to the previous chelation stage was adjusted to the desired pH (in the range 2 to 8) and temperature (60 or 80°C) and then a suitable quantity of the solution of TAED/peroxide was added to the pulp together with any other ingredients as specified in the tables. The mixture was allowed to react with intermittent stirring. The properties of pulp after reaction times of thirty minutes up to 360 minutes were determined. For some processes a subsequent alkaline bleaching step was conducted. The pulp from the novel bleaching step of this invention was then subjected to a number of tests. The following tests were used: Pulp Testing
  • the brightness of the pulp was determined as the brightness of a split sheet at a wavelength of 457nm.
  • the apparatus used was a Carl Zeiss Elrepho
  • Pulp viscosity was determined according to the standard SCAN-CM 15:88. 4.
  • the light scattering coefficient of the pulp was determined according to the standards ISO 5269/1 and SCAN C 27:76. The light absorption coefficient was calculated on the basis of this determination. 5.
  • the post-color value PC,a was determined at 100°C and 100% relative humidity after one hour TAPPI standard T260 om-85. 6.
  • the post-color value PC,b was determined at 105°C after 24 hours.
  • the post-color value PC,c was determined after irrad; ;ion in a Xenotester for three hours.
  • the pr./sical properties of the paper sheets made from pulp were determined according to the standards ISO 5264/2, ISO 5269/1, ISO 5267/1, ISO 5270 and SCAN C 27:76. Brightnesses before and after were determined at 457nm with an
  • the conditions selected for the chelation stage as suitable for all three pulps was found to utilise DTPMP at a concentration of 0.2% and at a pH of 6.
  • Figures 1 to 4 the results of paper making properties on the pulps made using experiment 7.5 ( Figures 1 and 2) and
  • Pulp brightness reversion is improved by TAED under humid and dry conditions (PC,a and PC,b) (Table 6).
  • PC,a and PC,b Humid and dry conditions
  • the benefits of TAED remain even when the pulp is further bleached in a conventional alkaline peroxide stage (tests 7.5 and 7.6 and Table 5).
  • TAED has no adverse effect on the physical properties of paper made from the pulp ( Figures 1 to 4) .
  • the improved colour reversion is obtained without trading-off against strength.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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Abstract

On fait réagir des activateurs de blanchiment avec une source de peroxygène dans une solution aqueuse d'un pH acide pour former un oxydant plus fort que la source initiale de peroxygène lorsqu'il est utilisé comme matière de départ. La solution résultante sert à la délignification et/ou au blanchiment des pâtes cellulosiques. Ledit activateur est de préférence solide à la température ambiante. La réaction entre les activateurs et le peroxygène peut se faire en présence de la pâte pour donner un maximum d'efficacité à l'oxydant.
PCT/GB1995/000246 1994-02-07 1995-02-07 Blanchiment de pate a papier WO1995021290A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU15842/95A AU1584295A (en) 1994-02-07 1995-02-07 Pulp bleaching

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/GB1994/000228 WO1994018297A1 (fr) 1993-02-08 1994-02-07 Agents d'oxydation
ATPCT/GB94/00228 1994-02-07
GB9415909.2 1994-08-05
GB9415909A GB9415909D0 (en) 1994-08-05 1994-08-05 Pulp delignification and bleaching

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000077297A1 (fr) * 1999-06-15 2000-12-21 Kemira Chemicals Oy Activateur de blanchiment et son procede d'utilisation
WO2003061550A2 (fr) * 2002-01-26 2003-07-31 Call, Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
WO2007025417A1 (fr) * 2005-09-02 2007-03-08 South China Uni. Of Tech. Procede de blanchiment de la pate
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing

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DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
EP0456032A1 (fr) * 1990-04-25 1991-11-13 Hoechst Japan Limited Procédé de blanchiment de pâtes
EP0534772A2 (fr) * 1991-09-27 1993-03-31 WARWICK INTERNATIONAL GROUP LIMITED(Company No. 2754514) Compositons oxidantes
WO1994018298A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation
WO1994018297A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation
WO1994018299A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation

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DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
EP0456032A1 (fr) * 1990-04-25 1991-11-13 Hoechst Japan Limited Procédé de blanchiment de pâtes
EP0534772A2 (fr) * 1991-09-27 1993-03-31 WARWICK INTERNATIONAL GROUP LIMITED(Company No. 2754514) Compositons oxidantes
WO1994018298A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation
WO1994018297A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation
WO1994018299A1 (fr) * 1993-02-08 1994-08-18 Warwick International Group Limited Agents d'oxydation

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WO2000077297A1 (fr) * 1999-06-15 2000-12-21 Kemira Chemicals Oy Activateur de blanchiment et son procede d'utilisation
WO2003061550A2 (fr) * 2002-01-26 2003-07-31 Call, Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
WO2003061550A3 (fr) * 2002-01-26 2004-09-10 Call Krimhild Nouvelles activites catalytiques d'oxydo-reductases pour l'oxydation et/ou le blanchiment
WO2007025417A1 (fr) * 2005-09-02 2007-03-08 South China Uni. Of Tech. Procede de blanchiment de la pate
CN100500990C (zh) * 2005-09-02 2009-06-17 华南理工大学 纸浆清洁漂白方法
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