EP0426652B2 - Verfahren zum chlorfreien Bleichen von Zellstoffen - Google Patents

Verfahren zum chlorfreien Bleichen von Zellstoffen Download PDF

Info

Publication number
EP0426652B2
EP0426652B2 EP90890291A EP90890291A EP0426652B2 EP 0426652 B2 EP0426652 B2 EP 0426652B2 EP 90890291 A EP90890291 A EP 90890291A EP 90890291 A EP90890291 A EP 90890291A EP 0426652 B2 EP0426652 B2 EP 0426652B2
Authority
EP
European Patent Office
Prior art keywords
ozone
pulp
process according
containing gas
kappa
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.)
Expired - Lifetime
Application number
EP90890291A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0426652B1 (de
EP0426652A1 (de
Inventor
Wilfried Rückl
Walter Dr. Dipl.-Ing. Peter
Friedrich Kurz
Alfred Schrittwieser
Manfred Schneeweisz
Herbert Sixta
Gerhard Götzinger
Anton Höglinger
Peter Hendel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25598564&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0426652(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from AT0249489A external-priority patent/AT404740B/de
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of EP0426652A1 publication Critical patent/EP0426652A1/de
Publication of EP0426652B1 publication Critical patent/EP0426652B1/de
Application granted granted Critical
Publication of EP0426652B2 publication Critical patent/EP0426652B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone

Definitions

  • the invention relates to a method for bleaching cellulose, in particular cellulose for the production of synthetic fibers, e.g. B. hardwood pulps, with initial cap values of 15-1, preferably 4-1, or of pulps for the production of paper, for example softwood pulps, with initial cap values up to 30, preferably up to 10, by means of ozone, in which a pulp suspension at a temperature of 15-80 ° C, preferably 40-70 ° C, and at a pH of 1-8, preferably 2-3, with an ozone-containing gas with vigorous stirring or mixing in contact, the ozone-containing gas 20-300g / m 3 , preferably 50-150 g / m 3 , contains ozone and at most 2% by mass, preferably 0.05-0.5% by mass, of ozone, based on dry cellulose, is used.
  • ozone in which a pulp suspension at a temperature of 15-80 ° C, preferably 40-70 ° C, and at a pH of 1-8, preferably
  • HC high consistency
  • LC low consistency
  • HC ozone bleaching is carried out at consistencies above 25%, generally at 35 - 40%.
  • a method of the type mentioned is known from US-A-4 080 249.
  • the stirring energy is according to claim 5, preferably at most 18 kWh / t of pulp suspension.
  • the size of the vesicles ozone-containing gas should not exceed 3 mm.
  • the invention has set itself the task of the method mentioned in the middle consistency area (MC) to apply, whereby of course good results should be achieved in comparison to the LC technique.
  • this object is achieved by a method of the type mentioned in the introduction in that that the pulp suspension has a consistency of 7-15 mass% and that the ozone-containing gas with a pressure of 5-15 bar, preferably 5 - 10 bar, is introduced into the pulp suspension.
  • the medium consistency range offers the advantage that the reaction vessels can be made smaller in comparison to the LC technology, but that on the other hand no expensive dewatering devices are necessary as with the HC technology.
  • a homogeneous and gentle, but nevertheless efficient reaction of the pulp with ozone takes place.
  • the required mixing energy is lower than with LC.
  • the reaction of the ozone with the pulp is more homogeneous than with HC.
  • the cellulose damage - measured by the viscosity and the DP distribution - even at very low kappa values - is significantly less than with HC and at least comparable to LC.
  • the specific ozone consumption (O 3 consumption per eliminated kappa point) is significantly lower than with LC.
  • Existing systems are relatively easy to convert: apart from pH-controlled acidification (which would also be required for LC and HC), only an investment in an MC pump and an MC mixer is required. Waste water recirculation and reuse of the reaction waste gases with a residual ozone content is possible, so that the process works in an environmentally friendly manner. Overall, the process (required mixing energy, amount of ozone used and necessary devices) makes the process very economical.
  • MC pulp can also be successfully treated directly with an ozone-containing gas can, provided that this is under pressure and at the same time is stirred or mixed vigorously. This makes it fall Dilute and dewater the pulp suspension as provided for in AT-A-380 496 (see Page 3, lines 19-20 and 35-36), gone.
  • the volume ratio gas liquid 1: 0.5 - 1: 8, preferably 1: 1 - 1: 6.
  • Cooled compressors preferably water ring pumps, are preferably used to compress the ozone-containing gas. used.
  • a high-shear mixer is preferably used for vigorous stirring or mixing.
  • High-shear mixers are known and are currently used for a wide variety of applications for example for the production of dispersions for paints (DE-A 24 06 430), for the production of PVC resin powder (US-A-3 775 359) and for the preparation of semi-solid emulsions (US-A-3 635 834). It's also beautiful known to use them for pulp suspensions (JP-A 6 309 9389).
  • a high-shear mixer has plates with bumps that are spaced apart are. This means that there is no grinding, but an intimate mixing.
  • alkaline extraction can be done using of oxygen or peroxide. This multiple implementation can be done in practice simply be ensured that part of the pulp is removed behind the reactor and the high-shear mixer is fed again, so that a cycle results
  • Oxygen can also be used in the peroxide stage.
  • the wastewater filtrate obtained in the treatment with ozone at least part of the pulp suspension is supplied before it comes into contact with the ozone-containing gas is brought, which together with the wastewater filtrate also required for the desired pH Acid, especially sulfuric acid, is supplied. Because the wastewater filtrate is acidic, this can Acid can be saved; at the same time the wastewater filtrate is put to sensible use, so that it does not have to be disposed of or discharged in an environmentally harmful way.
  • the molecular weight distribution of synthetic fiber pulps can be set.
  • the pH value, the amount of ozone used and temperature the viscosity, DP distribution and reactivity required for the further use of the cellulose, measured by the filter value.
  • FIGS. 1a and 1b show plants that are to be implemented of the method according to the invention are suitable.
  • pulp feed for ozone bleaching from one of the previous bleaching stages, such as oxygen and / or Peroxide bleach, referred to as subsequent alkaline extraction.
  • Acidic waste water filtrate 14 the at the end of the ozone bleaching stage, the pulp suspension is added to adjust the consistency and to use the residual acidity.
  • a pH-regulating acid addition 2 takes place pH value.
  • the pulp suspension is transferred to an MC mixer 4, which is preferably a high-shear mixer is encouraged.
  • Gas 7 containing ozone is compressed in a compressor 8 and introduced into the MC mixer 4 under pressure.
  • the MC mixer 4 there is an intimate, rapid mixing of the suspension and the ozone-containing gas 7.
  • reaction tube 5 The reaction is continued under pressure in a reactor which is designed as a reaction tube 5.
  • a return 9 (in the form of a tube and a pump) of the reaction mixture provided, if necessary, the pulp suspension several times the inventive method to subjugate.
  • FIG. 1a and 1b is the integration of the fumigated stock suspension in conventional bleaching towers 10 shown. According to the invention, this is not absolutely necessary. It is between the up and down tower distinguished.
  • Fig. 1a is the pressurized gas pulp suspension promoted with or without throttle 6 in the bleaching tower 10, where a subsequent reaction can still take place.
  • the pressure has been released and the exhaust gas is discharged via an exhaust gas disposal device 11 derived.
  • the relaxed pulp suspension is mixed with dilution water 12 and from the bleaching tower 10 discharged to the washing filter 13.
  • the resulting wastewater filtrate 14 is a Waste water recirculation 15 of the pulp feed 1 supplied.
  • the oxygen produced in the waste gas disposal 11 can be used in an oxygen bleaching stage and the excess oxygen is returned to the ozone generator after appropriate cleaning steps become. If the oxygen is not used in an oxygen bleaching stage, it can be used entirely according to the required cleaning steps are returned.
  • Waste water and exhaust gas recirculation can also be used, especially at high process temperatures some energy can be saved.
  • the residence time of the pulp suspension in the reaction tube 5 and in the bleach tube 10 is in any case less than 3 hours, usually less than 1 hour, preferably even less than 5 minutes.
  • beech synthetic pulp or spruce paper pulp is used a conventional, peroxide-enhanced oxygen extraction of an ozone bleach according to the invention subject.
  • EXAMPLE 1 After the peroxide-enhanced oxygen extraction (EOP stage), the pulp has the following characteristics: Kappa unwashed 2.1 Kappa washed 1.9 White 76% (Elrepho) viscosity 255 mP COD accompanying waste water 5 g / kg dry cellulose It is subjected to ozone bleaching with the following parameters: print 5.2 bar Consistency 10% temperature 47 ° C PH value 2.3 special O 3 insert 1.82 g O 3 / kg spec.O 3 consumption 1.69 g / kg Ozone concentration in fresh gas 76.8 mg / NI Ozone concentration in the exhaust gas 5.2 mg / NI reaction time 120 s Mixing time 20 s V g / V l 1 / 3.2 (at 5.2 bar) Speed of the high-shear mixer 1700 / min The bleached pulp has the following key figures: Kappa 0.9 delta kappa 1.85 O 3 consumption / delta kappa 0.91 White 83.5% delta white 7.
  • EXAMPLE 2 The pulp has the same characteristics as in Example 1 with the following exception: Kappa unwashed 2.9 It is subjected to ozone bleaching with the following parameters: print 5.0 bar Consistency 9.5% temperature 50 ° C pH 2.5 spec. Use of ozone 1.60 g / kg spec.
  • EXAMPLE 3 The pulp has the following key figures: Kappa 1.9 viscosity 255 mP Whiteness 76% It is subjected to ozone bleaching with the following parameters: print 5 bar Material density 10% temperature 50 ° C PH value 5.0 spec. O 3 insert 1.5 g / kg spec.
  • EXAMPLE 4 The same pulp as in Example 3 is subjected to ozone bleaching with the following parameters: print 5.0 bar Material density 10.7% temperature 23 ° C PH value 2.5 spec. O 3 insert 1.6 g / kg spec. O 3 consumption 1.2 g / kg reaction time 120 s Mixing time 120 s Ozone concentration in fresh gas 83.2 mg / NI Ozone concentration in the exhaust gas 21 mg / NI V g / V l 1: 2.6 (at 5 bar) Speed of the high-shear mixer 3200 / min The bleached pulp has the following key figures: Kappa 0.60 delta kappa 1.3 O 3 consumption / delta kappa 0.91 White 86.3% delta white 10.3% viscosity 228 mP delta viscosity 27 mP The differences in the material properties between Examples 3 and 4 are exclusively due to the changed pH value and the changed temperature. The pH value is therefore suitable for adjusting the viscosity.
  • Examples 5 and 6 relate to spruce paper sulfite pulps.
  • the raw material had the following key figures: Kappa (Tappi 236 os-76) 20.4 viscosity 1500 mPa s ⁇ 10 Whiteness (Elrepho) 49.7% Tear length (24 ° SR) 8900 m Tear length (41 ° SR) 9200 m WRA (24 ° SR) 1143 mNm / m WRA (41 ° SR) 1010 mNm / m Burst resistance (24 ° SR) 4.4 kg / cm 2 Burst resistance (41 ° SR) 4.2 kg / cm 2
  • the strength values correspond despite the exceptionally high degree of whiteness (> 90%) and the low Viscosity values that of standard bleached pulps. (The sequence is under "standard bleaching” C-PE-H-H understood. “C” means chlorine bleach and "H” hypochlorite bleach.)
  • the strength values of the three-stage bleached cellulose essentially correspond to that of five-stage bleached cellulose. This is an indication that when sequential use is less specific ozone levels will not affect the strength properties of the pulps, however nevertheless very high degrees of whiteness can be achieved.
  • a spruce kraft pulp was subjected to two different bleaching sequences according to the invention after conventional oxygen extraction.
  • the pulp had the following key figures: Kappa 16 White 37.7 Tear length 10.5 km (17 ° SR) 10.7 km (21 ° SR) WRA 1666 mNm / m (17 ° SR) 1620 mNm / m (21 ° SR) Relative initial strength 7.42 kPam 2 / g (17 ° SR) 7.13 kPam 2 / g (21 ° SR)
  • the cellulose had the following properties after each stage: parameter Z 1 -EO-Z 2 -P Z 1 -EOP-Z 2 -P according to Z 1 Kappa 12th 12th White 41 41 before Z 2 Kappa 7 6 White 62 65 according to Z 2 Kappa 4th 3.5 White 78 80 after P (fully bleached) White 85 87 Tearing length (km) 9.8 (15 ° SR) 9.7 (15 ° SR) 10.9 (23 ° SR) 10.6 (22 ° SR) Relative residual resistance (kPa m 2 / g) 7.0 (15 ° SR) 7.4 (15 ° SR) 7.5 (23 ° SR) 7.6 (22 ° SR) WRA (mNm / m) 1816 (15 ° SR) 1780 (15 ° SR) 1580 (23 ° SR) 1610 (22 ° SR)
  • the process conditions of the Z 1 stage, the EO stage and the Z 2 stage were identical to those of Example 7.
  • the reaction conditions of the D stage were as follows: Consistency 10 - 12% temperature 70 ° C Active chlorine 1 %
  • the cellulose had the following properties after each stage: parameter Z 1 -EO-Z 2 -D according to Z 1 Kappa 12th White 41 before Z 2 Kappa 7 White 62 according to Z 2 Kappa 4th White 78 after P (fully bleached) White 89 Tearing length (km) 9.8 (15 ° SR) 11.0 (24 ° SR) Relative initial strength (kPa m 2 / g) 7.2 (15 ° SR) 7.5 (24 ° SR) WRA (mNm / m) 1820 (15 ° SR) 1520 (22 ° SR)
  • Examples 7 and 8 show that there are no differences between the strength properties unbleached or bleached with chlorine pulp on the one hand and bleached without chlorine according to the invention On the other hand, pulp exist.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP90890291A 1989-10-30 1990-10-30 Verfahren zum chlorfreien Bleichen von Zellstoffen Expired - Lifetime EP0426652B2 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
AT0249489A AT404740B (de) 1989-10-30 1989-10-30 Verfahren zum chlorfreien bleichen von zellstoffen
AT2494/89 1989-10-30
AT249489 1989-10-30
AT258889 1989-11-10
AT2588/89 1989-11-10
AT258889 1989-11-10

Publications (3)

Publication Number Publication Date
EP0426652A1 EP0426652A1 (de) 1991-05-08
EP0426652B1 EP0426652B1 (de) 1994-05-11
EP0426652B2 true EP0426652B2 (de) 2001-11-14

Family

ID=25598564

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90890291A Expired - Lifetime EP0426652B2 (de) 1989-10-30 1990-10-30 Verfahren zum chlorfreien Bleichen von Zellstoffen

Country Status (25)

Country Link
US (1) US5346588A (hu)
EP (1) EP0426652B2 (hu)
JP (1) JP2995422B2 (hu)
AR (1) AR243946A1 (hu)
AT (1) ATE105599T1 (hu)
AU (1) AU636173B2 (hu)
BG (1) BG51052A3 (hu)
BR (1) BR9005476A (hu)
CA (1) CA2028788C (hu)
DE (1) DE59005677D1 (hu)
DK (1) DK0426652T3 (hu)
ES (1) ES2023623T3 (hu)
FI (1) FI102194B (hu)
GR (1) GR910300078T1 (hu)
HR (1) HRP930459B1 (hu)
HU (1) HU205175B (hu)
LV (1) LV10513B (hu)
NO (1) NO176975B (hu)
PH (1) PH30483A (hu)
PT (1) PT95718B (hu)
RO (1) RO107715B1 (hu)
SI (1) SI9012041B (hu)
TR (1) TR24891A (hu)
UA (1) UA27098A1 (hu)
YU (1) YU47233B (hu)

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5411634A (en) * 1991-04-30 1995-05-02 Kamyr, Inc. Medium consistency ozone bleaching
US5411633A (en) * 1991-04-30 1995-05-02 Kamyr, Inc. Medium consistency pulp ozone bleaching
NZ242792A (en) * 1991-05-24 1993-12-23 Union Camp Patent Holding Two-stage pulp bleaching reactor: pulp mixed with ozone in first stage.
NO912449L (no) * 1991-06-24 1992-12-28 Norske Stats Oljeselskap Flyttbar plattform til havs.
ZA924351B (en) * 1991-06-27 1993-03-31 Ahlstroem Oy Ozone bleaching process
FR2684697B1 (fr) * 1991-12-09 1996-05-03 Toulouse Inst Nat Polytech Procede de fabrication de pate a papier blanchie.
SE9200183L (sv) * 1992-01-23 1993-07-24 Kamyr Ab Avskiljningsanordning samt foerfarande
EP0581631A1 (en) * 1992-07-31 1994-02-02 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Selective treatment of pulp with ozone
CA2078276C (en) * 1992-09-15 2004-05-25 Derek Hornsey Recovery of oxygen-rich gas from ozone bleaching processes
SE500335C2 (sv) * 1992-10-26 1994-06-06 Sca Wifsta Oestrand Ab Blekning av sulfatmassa med peroxid-ozon-peroxid
US5364505A (en) * 1992-12-07 1994-11-15 Kamyr, Inc. Pressurized ozone pulp delignification reactor and a compressor for supplying ozone to the reactor
US6010594A (en) * 1993-03-03 2000-01-04 Ahlstrom Machinery Corporation Method of bleaching pulp with chlorine-free chemicals wherein a complexing agent is added immediately after an ozone bleach stage
FI93232C (fi) * 1993-03-03 1995-03-10 Ahlstroem Oy Menetelmä massan valkaisemiseksi kloorivapailla kemikaaleilla
SE501253E8 (sv) * 1993-06-08 1994-12-19 Klorfri blekning av kemisk pappersmassa
CA2170733A1 (en) * 1993-09-03 1995-03-09 Spencer W. Eachus Medium consistency ozone brightening of high consistency ozone bleached pulp
AU7243594A (en) * 1993-09-15 1995-04-03 Kamyr Inc. Eop stage for chlorine free bleaching
US5529660A (en) * 1994-04-15 1996-06-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Calude Method of reducing fluorescence in deinked pulp by treating pulp with ozone and a bleaching agent
US5770011A (en) * 1995-11-17 1998-06-23 International Paper Company Neutral monoperoxysulfate bleaching process
AT402827B (de) * 1995-12-22 1997-09-25 Chemiefaser Lenzing Ag Celluloseformkörper und verfahren zu seiner herstellung
US6045588A (en) 1997-04-29 2000-04-04 Whirlpool Corporation Non-aqueous washing apparatus and method
DE19816925B4 (de) 1998-04-16 2009-12-10 SOCIéTé BIC Handgerät zum Übertragen eines Filmes von einem Trägerband auf ein Substrat
US6773547B2 (en) * 1998-05-08 2004-08-10 American Air Liquide, Inc. Process for the bleaching of low consistency pulp using high partial pressure ozone
US6579412B2 (en) * 1998-05-08 2003-06-17 L'air Liquide - Societe' Anonyme A' Directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude Process for ozone bleaching of low consistency pulp
FI981808A (fi) * 1998-08-24 2000-02-25 Crs Reactor Engineering Uk Ltd Menetelmä massan valkaisemiseksi
US20050173082A1 (en) * 1998-08-24 2005-08-11 Arbozon Oy Ltd. Bleaching of medium consistency pulp with ozone without high shear mixing
DE10158449C1 (de) * 2001-11-30 2003-12-24 Wedeco Umwelttechnologie Gmbh Verfahren und Vorrichtung zum Verdichten von ozonhaltigem Gas für eine Ozon-Zellstoffbleiche
US7300468B2 (en) 2003-10-31 2007-11-27 Whirlpool Patents Company Multifunctioning method utilizing a two phase non-aqueous extraction process
US7513004B2 (en) 2003-10-31 2009-04-07 Whirlpool Corporation Method for fluid recovery in a semi-aqueous wash process
US7739891B2 (en) 2003-10-31 2010-06-22 Whirlpool Corporation Fabric laundering apparatus adapted for using a select rinse fluid
US7695524B2 (en) 2003-10-31 2010-04-13 Whirlpool Corporation Non-aqueous washing machine and methods
EP1740757A1 (en) 2004-04-29 2007-01-10 Unilever N.V. Dry cleaning method
US7966684B2 (en) 2005-05-23 2011-06-28 Whirlpool Corporation Methods and apparatus to accelerate the drying of aqueous working fluids
US20080177089A1 (en) 2007-01-19 2008-07-24 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
JP5698348B2 (ja) 2010-05-18 2015-04-08 ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ 蛍光増白剤およびそれを含む組成物
US8262743B2 (en) 2010-05-18 2012-09-11 Milliken & Company Optical brighteners and compositions comprising the same
US8470760B2 (en) 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents
US8476216B2 (en) 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
WO2010151906A2 (en) 2010-10-22 2010-12-29 Milliken & Company Bis-azo colorants for use as bluing agents
MX2013005276A (es) 2010-11-12 2013-06-03 Procter & Gamble Colorantes azoicos de tiofeno y composiciones para el cuidado de ropa que contienen estos colorantes.
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
JP2014500350A (ja) 2010-11-12 2014-01-09 ミリケン・アンド・カンパニー チオフェンアゾ色素およびこれを含有する洗濯ケア組成物
WO2012112741A1 (en) 2011-02-16 2012-08-23 The Procter & Gamble Company Compositions and methods of bleaching
EP2678101A1 (en) 2011-02-25 2014-01-01 Milliken & Company Capsules and compositions comprising the same
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
FR3007044B1 (fr) * 2013-06-13 2016-01-15 Air Liquide Procede de traitement des pates papetieres chimiques par traitement a l'ozone en presence d'ions magnesium
US9777250B2 (en) 2015-10-13 2017-10-03 Milliken & Company Whitening agents for cellulosic substrates
US9976035B2 (en) 2015-10-13 2018-05-22 Milliken & Company Whitening agents for cellulosic substrates
US9902923B2 (en) 2015-10-13 2018-02-27 The Procter & Gamble Company Polyglycerol dye whitening agents for cellulosic substrates
US10155868B2 (en) 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US9745544B2 (en) 2015-10-13 2017-08-29 The Procter & Gamble Company Whitening agents for cellulosic substrates
US9719056B1 (en) 2016-01-29 2017-08-01 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20180072970A1 (en) 2016-09-13 2018-03-15 The Procter & Gamble Company Stable violet-blue to blue imidazolium compounds
US20200123319A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US20200123472A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US11299591B2 (en) 2018-10-18 2022-04-12 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11518963B2 (en) 2018-10-18 2022-12-06 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US11732218B2 (en) 2018-10-18 2023-08-22 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
US20200123475A1 (en) 2018-10-18 2020-04-23 Milliken & Company Polyethyleneimine compounds containing n-halamine and derivatives thereof
US20210269747A1 (en) 2020-03-02 2021-09-02 Milliken & Company Composition Comprising Hueing Agent
US11718814B2 (en) 2020-03-02 2023-08-08 Milliken & Company Composition comprising hueing agent
US11344492B2 (en) 2020-09-14 2022-05-31 Milliken & Company Oxidative hair cream composition containing polymeric colorant
US20220079862A1 (en) 2020-09-14 2022-03-17 Milliken & Company Hair care composition containing polymeric colorant
WO2022197295A1 (en) 2021-03-17 2022-09-22 Milliken & Company Polymeric colorants with reduced staining

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4119486A (en) * 1975-08-14 1978-10-10 Westvaco Corporation Process for bleaching wood pulp with ozone in the presence of a cationic surfactant
US4080249A (en) * 1976-06-02 1978-03-21 International Paper Company Delignification and bleaching of a lignocellulosic pulp slurry with ozone
CA1090510A (en) * 1976-06-02 1980-12-02 Arthur W. Kempf Delignification and bleaching of a lignocellulosic pulp slurry with ozone
US4216054A (en) * 1977-09-26 1980-08-05 Weyerhaeuser Company Low-consistency ozone delignification
US4372812A (en) * 1978-04-07 1983-02-08 International Paper Company Chlorine free process for bleaching lignocellulosic pulp
US4229252A (en) * 1979-01-11 1980-10-21 Weyerhaeuser Company Additives for ozone bleaching
US4310384A (en) * 1979-01-11 1982-01-12 Weyerhaeuser Company Reducing chemical transfer between treatment stages
US4283251A (en) * 1980-01-24 1981-08-11 Scott Paper Company Ozone effluent bleaching
US4619733A (en) * 1983-11-30 1986-10-28 Kooi Boon Lam Pollution free pulping process using recycled wash effluent from multiple bleach stages to remove black liquor and recovering sodium hydroxide from the black liquor
AT380496B (de) * 1984-06-27 1986-05-26 Steyrermuehl Papier Verfahren und reaktor zur delignifizierung von zellstoff mit sauerstoff
US4902381A (en) * 1988-12-09 1990-02-20 Kamyr, Inc. Method of bleaching pulp with ozone-chlorine mixtures
FI89516B (fi) * 1989-05-10 1993-06-30 Ahlstroem Oy Foerfarande foer blekning av cellulosamassa med otson

Also Published As

Publication number Publication date
FI102194B1 (fi) 1998-10-30
LV10513A (lv) 1995-02-20
ES2023623A4 (es) 1992-02-01
EP0426652B1 (de) 1994-05-11
RO107715B1 (ro) 1993-12-30
JP2995422B2 (ja) 1999-12-27
DE59005677D1 (de) 1994-06-16
AU6455290A (en) 1991-05-02
PH30483A (en) 1997-05-28
HRP930459B1 (en) 1998-12-31
ES2023623T3 (es) 1994-08-01
LV10513B (en) 1995-10-20
SI9012041A (en) 1997-08-31
FI102194B (fi) 1998-10-30
CA2028788A1 (en) 1991-05-01
FI905327A0 (fi) 1990-10-29
AR243946A1 (es) 1993-09-30
YU204190A (sh) 1992-07-20
CA2028788C (en) 1997-04-15
ATE105599T1 (de) 1994-05-15
PT95718B (pt) 1997-11-28
HRP930459A2 (en) 1996-04-30
HU205175B (en) 1992-03-30
TR24891A (tr) 1992-07-01
NO904673D0 (no) 1990-10-29
BR9005476A (pt) 1991-09-17
EP0426652A1 (de) 1991-05-08
UA27098A1 (uk) 2000-02-28
YU47233B (sh) 1995-01-31
AU636173B2 (en) 1993-04-22
HU906923D0 (en) 1991-05-28
NO176975B (no) 1995-03-20
NO904673L (no) 1991-05-02
US5346588A (en) 1994-09-13
DK0426652T3 (da) 1994-06-13
BG51052A3 (en) 1993-01-15
GR910300078T1 (en) 1991-12-10
PT95718A (pt) 1991-09-13
SI9012041B (sl) 2000-06-30
HUT55847A (en) 1991-06-28
JPH03152286A (ja) 1991-06-28

Similar Documents

Publication Publication Date Title
EP0426652B2 (de) Verfahren zum chlorfreien Bleichen von Zellstoffen
DE3017712C2 (de) Verfahren zur alkalischen Extraktion von Fasermaterial enthaltenden Cellulosesuspensionen nach Behandlung mit Chlor oder Chlordioxid oder Mischungen davon
DE69206313T2 (de) Verfahren zum Bleichen von Lignocellulose enthaltendem Material.
DE2845025A1 (de) Verfahren zum behandeln von pulpe mit ozon
DE68924793T2 (de) Verfahren zum Bleichen von mechanischem Holzstoff.
DE3938198C2 (de) Verfahren zum Bleichen von Cellulosefasern enthaltendem Pulpen-Material
EP0087553B1 (de) Verfahren zur Herstellung von halbgebleichten Zellstoffen
DE2040763A1 (de) Verfahren zum Bleichen zellulosehaltiger Stoffe
DE69332725T2 (de) Rückgewinnung von sauerstoffreichem Gas aus Bleichverfahren mittels Ozon
DE4039099C2 (de) Verfahren zum Bleichen von Cellulosebrei
DE69503147T2 (de) Verfahren zur delignifizierung und zum bleichen von chemischen zellstoff
AT404740B (de) Verfahren zum chlorfreien bleichen von zellstoffen
DE2407542A1 (de) Verfahren zum bleichen von pulpe
AT395445B (de) Verfahren zum bleichen von cellulosehaeltigem material
DE2124324C3 (de) Verfahren zum Bleichen von Holzzellstoffen
EP0120132A1 (de) Verfahren zum Bleichen von Papierrohstoffen
DE4039294C2 (de) Verfahren zum Bleichen von Cellulosebrei
DE69420035T2 (de) Verfahren zum bleichen von zellstoff ohne verwendung von chlor enthaltenden chemikalien
DE3034042C2 (de) Verfahren zur Reduzierung des Harzgehalts bei der Herstellung von Zellulosepulpe aus Lignozellulose-Material
DE3923728A1 (de) Verfahren zur stabilisierung der viskositaet von zellstoffen
DE3148101C2 (de) Verfahren zur Reduzierung des Harzgehalts bei der Herstellung von Zellulosepulpe
WO2019170667A1 (de) Chemiezellstoff
EP0185858B1 (de) Verfahren zur Delignifizierung von Sulfatzellstoffen
DE60124081T2 (de) Verfahren zum bleichen von holzstoff und chemothermomechanischer pulpe
DE10357437A1 (de) Verfahren zum Beladen einer Faserstoffsuspension und Anordnung zur Durchführung des Verfahrens

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901218

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

ITCL It: translation for ep claims filed

Representative=s name: STUDIO BIANCHETTI

EL Fr: translation of claims filed
GBC Gb: translation of claims filed (gb section 78(7)/1977)
17Q First examination report despatched

Effective date: 19930324

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 105599

Country of ref document: AT

Date of ref document: 19940515

Kind code of ref document: T

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REF Corresponds to:

Ref document number: 59005677

Country of ref document: DE

Date of ref document: 19940616

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940531

ET Fr: translation filed
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2023623

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3012881

EAL Se: european patent in force in sweden

Ref document number: 90890291.9

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: INGERSOLL-RAND COMPANY

Effective date: 19950210

Opponent name: SUNDS DEFIBRATOR INDUSTRIES AKTIEBOLAG

Effective date: 19950209

NLR1 Nl: opposition has been filed with the epo

Opponent name: SUNDS DEFIBRATOR INDUSTRIES AKTIEBOLAG

Opponent name: INGERSOLL-RAND COMPANY

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: INGERSOLL-RAND COMPANY * 950209 SUNDS DEFIBRATOR I

Effective date: 19950210

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

NLR1 Nl: opposition has been filed with the epo

Opponent name: SUNDS DEFIBRATOR INDUSTRIES AKTIEBOLAG

Opponent name: INGERSOLL-RAND COMPANY

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19980902

Year of fee payment: 9

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990913

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19990915

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19990920

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19990922

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990923

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19990929

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19991020

Year of fee payment: 10

Ref country code: GR

Payment date: 19991020

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991030

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: INGERSOLL-RAND COMPANY * 19950209 VALMET FIBERTECH

Effective date: 19950210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001030

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001030

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001030

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001031

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001031

NLR1 Nl: opposition has been filed with the epo

Opponent name: VALMET FIBERTECH AKTIEBOLAG

Opponent name: INGERSOLL-RAND COMPANY

BERE Be: lapsed

Owner name: LENZING A.G.

Effective date: 20001031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010501

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20001030

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20010501

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20011114

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020225

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051030

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081022

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20081014

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20081014

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20001031

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100501

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091031