EP0426652B2 - Verfahren zum chlorfreien Bleichen von Zellstoffen - Google Patents

Verfahren zum chlorfreien Bleichen von Zellstoffen Download PDF

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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
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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
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German (de)
English (en)
French (fr)
Other versions
EP0426652A1 (de
EP0426652B1 (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.)
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Publication date
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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
Application granted granted Critical
Publication of EP0426652B1 publication Critical patent/EP0426652B1/de
Publication of EP0426652B2 publication Critical patent/EP0426652B2/de
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Expired - Lifetime legal-status Critical Current

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    • 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.

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  • 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
AT249489 1989-10-30
AT258889 1989-11-10
AT258889 1989-11-10
AT2494/89 1989-11-10
AT2588/89 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

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EP90890291A Expired - Lifetime EP0426652B2 (de) 1989-10-30 1990-10-30 Verfahren zum chlorfreien Bleichen von Zellstoffen

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US (1) US5346588A (pt)
EP (1) EP0426652B2 (pt)
JP (1) JP2995422B2 (pt)
AR (1) AR243946A1 (pt)
AT (1) ATE105599T1 (pt)
AU (1) AU636173B2 (pt)
BG (1) BG51052A3 (pt)
BR (1) BR9005476A (pt)
CA (1) CA2028788C (pt)
DE (1) DE59005677D1 (pt)
DK (1) DK0426652T3 (pt)
ES (1) ES2023623T3 (pt)
FI (1) FI102194B1 (pt)
GR (1) GR910300078T1 (pt)
HR (1) HRP930459B1 (pt)
HU (1) HU205175B (pt)
LV (1) LV10513B (pt)
NO (1) NO176975B (pt)
PH (1) PH30483A (pt)
PT (1) PT95718B (pt)
RO (1) RO107715B1 (pt)
SI (1) SI9012041B (pt)
TR (1) TR24891A (pt)
UA (1) UA27098A1 (pt)
YU (1) YU47233B (pt)

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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

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

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