WO1995023891A1 - Impact of temperature and alkali charge on pulp brightness - Google Patents

Impact of temperature and alkali charge on pulp brightness Download PDF

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Publication number
WO1995023891A1
WO1995023891A1 PCT/US1995/002719 US9502719W WO9523891A1 WO 1995023891 A1 WO1995023891 A1 WO 1995023891A1 US 9502719 W US9502719 W US 9502719W WO 9523891 A1 WO9523891 A1 WO 9523891A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquor
cooking
digester
white liquor
temperature
Prior art date
Application number
PCT/US1995/002719
Other languages
English (en)
French (fr)
Inventor
Nam Hee Shin
Original Assignee
Beloit Technologies, Inc.
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 to DE69505503T priority Critical patent/DE69505503T2/de
Priority to PL95316144A priority patent/PL316144A1/xx
Priority to MX9603876A priority patent/MX9603876A/es
Priority to EP95912729A priority patent/EP0748412B1/de
Priority to BR9506974A priority patent/BR9506974A/pt
Priority to AU19789/95A priority patent/AU684623B2/en
Application filed by Beloit Technologies, Inc. filed Critical Beloit Technologies, Inc.
Priority to RU96121355A priority patent/RU2127342C1/ru
Priority to CA002184706A priority patent/CA2184706C/en
Priority to RO96-01743A priority patent/RO117929B1/ro
Publication of WO1995023891A1 publication Critical patent/WO1995023891A1/en
Priority to NO963520A priority patent/NO963520L/no
Priority to FI963448A priority patent/FI118348B/fi

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00Regeneration of pulp liquors or effluent waste waters
    • D21C11/0021Introduction of various effluents, e.g. waste waters, into the pulping, recovery and regeneration cycle (closed-cycle)
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00Pretreatment of the finely-divided materials before digesting
    • D21C1/06Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00Pulping cellulose-containing materials
    • D21C3/22Other features of pulping processes

Definitions

  • the present invention relates to a process for improving the final brightness of pulp. More particularly, the present invention relates to
  • Rapid Displacement Heating is a low energy batch cooking process for producing kraft pulp. Combining the inherent advantages of batch cooking with the energy efficiencies of a continuous digester, RDH reuses the spent black liquors that are displaced from a cooked digester to pretreat the wood chips in a consequent cook. Thus, both the chemicals and the heat in these spent liquors are recycled to a consequent cook.
  • the pretreatment of fresh wood chips in a consequent cook begins with lower temperature liquors (approximately 80 ⁇ 130°C), and is followed by high temperature liquors (approximately 130° to 165°C) which heat the digester to the highest possible temperature before raising the temperatures to the final cooking temperature ( 3 170°C) with steam.
  • RDH and other alkaline cooking processes produce pulp that is relatively dark in color. Greater contrast is usually needed for the many uses of pulp and paper, so pulp is usually bleached to a high brightness in order to make white pulp for writing and printing papers and paperboard. Pulp color arises from changes in the lignin component of the raw material which occur in the pulping process.
  • high cooking temperatures and low black liquor strength in the RDH process low bleachability problems have occurred following the use of conventional, ECF and TCF bleaching processes. High cooking temperatures and low black liquor strength seem to accelerate condensation reactions, resulting in the condensation of lignin with lignin and other wood extractives. As a result, the bleachability of pulp decreased.
  • the present invention provides a method for improving pulp brightness. Based on modifications to a batch cooking process utilizing rapid displacement heating, the method of the present invention combines the steps of adding white liquor solution (% active alkalinity (AA) or effective alkalinity (EA)) or NaOH to both the warm fill and initial hot fill stages and cooking wood chips at lower temperatures than previously used in a batch type operation to produce pulp that has improved bleachability.
  • white liquor solution % active alkalinity (AA) or effective alkalinity (EA)
  • NaOH sodium nitrate
  • AA active alkalinity
  • EA effective alkalinity
  • a total white liquor charge ranging from 15% AA ⁇ 35% AA is distributed over the warm, hot and cooking stages in a predetermined amount.
  • cool white liquor is also added to the black liquor that is released from the cool liquor accumulator. Essentially, white liquor is added to every stage of the batch cooking process prior to the actual cook.
  • FIG. 1 illustrates a schematic view of a digested and its associated equipment used in the current RDH cooking system.
  • FIGS. 2A, 2B and 2C each illustrate white liquor profiling or the addition of white liquor at various stages of the RDH cooking process.
  • plot A represents the addition of a small amount of white liquor at the beginning of the warm fill mode.
  • Plot B represents the cooking stage and illustrates the presence of white liquor in the digester during the actual cooking of the chips.
  • FIG. 2B illustrates the continuous addition of white liquor to the black liquor at each stage of the RDH cooking process, beginning with the warm fill and continuing through the end of the hot fill.
  • White liquor as shown, is also present in the digester during the actual cook.
  • FIG. 2C illustrates the continuous addition of white liquor at each RDH stage including the addition of white liquor to the washer filtrate from the displacement tank.
  • FIG. 3 illustrates a Stage 3 RDH system without white liquor addition during the warm and hot fill modes.
  • FIG. 4 illustrates a Stage 3 RDH system with the addition of white liquor during the warm and hot fill modes.
  • FIG. 5 illustrates a plot of D1-brightness versus total (D100 + D1) available chlorine charge for the best case and baseline case RDH pulps.
  • Plot A represents RDH pulp R3 (0.225 Kappa factor).
  • Plot B represents RDH pulp R4 (0.27 Kappa factor).
  • Plot C represents RDH pulp R7 (0.225 Kappa factor).
  • Plot D represents RDH pulp R8 (0.27 Kappa factor).
  • FIG. 5A illustrates a plot of D1-brightness versus D1-chlorine dioxide charge.
  • Plot A represents RDH pulp R3 (0.225 Kappa factor).
  • Plot B represents RDH pulp R4 (0.27 Kappa factor).
  • Plot C represents RDH pulp R7 (0.225 Kappa factor).
  • Plot D represents RDH pulp R8 (0.27 Kappa factor).
  • FIG. 5A illustrates a plot of D1-brightness versus D1-chlorine dioxide charge.
  • Plot A
  • Plot C represents RDH pulp R7 (0.225 Kappa factor).
  • Plot D represents RDH pulp R8 (0.27 Kappa factor).
  • FIG. 6 illustrates the D1 -brightness versus the total available chlorine charge in the D100- and D1-stages for all 0.225 Kappa factor bleaches.
  • Plot A represents RDH pulp R3.
  • Plot B represents RDH pulp R12.
  • Plot C represents RDH pulp R7.
  • FIG. 6A illustrates the D1-brightness versus the D1-stage chlorine dioxide charges.
  • Plot A represents RDH pulp R3 (0.225 Kappa factor).
  • Plot B represents RDH pulp R12 (0.225 Kappa factor).
  • Plot C represents RDH pulp R7 (0.225 Kappa factor).
  • FIG. 7 illustrates the D1 -brightness versus the total available chlorine charge in the D100- and D1-stages for all 0.27 Kappa factor bleaches.
  • Plot A represents RDH pulp R4.
  • Plot B represents RDH pulp R12.
  • Plot C represents RDH pulp R8.
  • FIG. 7A illustrates the D1-brightness versus the D1 -stage chlorine dioxide charges.
  • Plot A represents RDH pulp R4 (0.27 Kappa factor).
  • Plot B represents RDH pulp R12 (0.27 Kappa factor).
  • Plot C represents RDH pulp R8 (0.27 Kappa factor).
  • the present invention provides a method for improving pulp bleachability, which is based on modifications to the existing RDH Cooking System for the digestion of wood chips. More specifically, the method involves the addition of a white liquor charge commencing at the start of the RDH cooking cycle and continuing until the time to temperature stage of the process, at which time the actual cook begins. The method of the present invention is also predicated on the use of somewhat lower cooking temperatures for the actual cook as compared to cooking temperatures commonly used in the RDH pulping process.
  • a total white liquor charge ranging between approximately 15%AA ⁇ 35%AA is distributed over the warm black liquor, initial hot black liquor and cooking stages.
  • the cool pad or cool liquor accumulator also receives a white liquor charge.
  • the present invention utilizes lower cooking temperatures ranging between approximately 150°C ⁇ 167°C. As a result, pulp is produced which, upon bleaching with any combination of bleaching chemicals, is improved in final brightness.
  • FIG. 1 schematically illustrates the type of apparatus for RDH that is used for the digestion of pulp. It should be understood that this figure illustrates very general features of the cooking apparatus, and modifications and variations in this system are indeed made as will be discussed in greater detail below. Many instrumentalities such as gauges, pressure vents, pumps and valves have been eliminated from the figures disclosed herein for reasons of simplicity.
  • FIG. 1 is used to illustrate the existing RDH cooking process and to facilitate an understanding of the improvements to the process in accordance with the principles of the present invention.
  • a digester is illustrated at 10 of the type generally used in the chemical digestion of wood chips.
  • the digester 10 has a truncated bottom 12.
  • An inlet valve 14 controls the entry of various reactive liquors into digester 10.
  • the contents of digester 10 can be heated to a final cooking temperature by pumping cooking liquor through a heat exchanger or steam sparger which is connected to digester 10 by a
  • Hot black liquor (temperature between 150°-168°C) is then pumped from the hot liquor accumulator (C tank) 28 by means of a pump 30 which is controlled by a valve 32 into the bottom of the digester 10 utilizing valve 14.
  • black liquor is displaced from the digester 10 and returned to the warm liquor accumulator 24 and hot liquor accumulator 28 through lines 34 and 36, respectively.
  • hot white liquor stored in the hot white liquor accumulator 38 is pumped out by means of a pump 30 where it combines with the hot black liquor leaving the hot liquor accumulator 28, the combined liquors then passing through a valve 32 and into the base of the digester 10.
  • the inlet and outlet valves to the digester 10 are closed as the time to temperature stage commences. Steam is injected into the digester 10 and the temperature is increased to the cooking
  • the temperature of the digester is maintained at about this temperature until the wood chips are digested, depending on white liquor charge and H-factor.
  • washer filtrate (temperature approximately 70 ⁇ 85°C) stored in a displacement tank (D tank) 40 is pumped into the digester 10, utilizing pump 42 and valve 44. The contents are washed and the digester 10 is cooled. As the washer filtrate is added to the digester 10, the spent liquors are displaced and returned to the warm liquor accumulator 24 and the hot liquor accumulator 28 by lines 46 and 48, respectively. The displacement mode is concluded when all washer filtrate is used, which is based on the dilution factor of the washer. After displacement is completed, the digested pulp is then pumped out of the digester 10 to a discharge tank using pump 50.
  • the present invention overcomes these problems and improves pulp bleachability by modifying the cooking process for wood chips.
  • This improved RDH process utilizes a combination of higher alkalinity (or white liquor charge) and lower cooking temperatures. More specifically, white liquor is added during the warm and initial hot fill stages. This is in contrast to the existing RDH cooking process, wherein white liquor is added only during the middle of the hot fill mode. Further, when a cool pad is used in the present invention, white liquor is added to the cool black liquor leaving the cool liquor accumulator (or A tank).
  • white liquor is added during each stage to the black liquor.
  • white liquor profiling is illustrated in greater detail below in FIGS. 2A, 2B and 2C.
  • plot A illustrates the addition of a small amount of white liquor at the beginning of the warm fill mode when warm black liquor leaves the B tank or warm liquor accumulator and flows to the digester.
  • White liquor can also be added to the A tank or cool pad when used.
  • Plot B represents the cooking stage and illustrates the presence of white liquor in the digester during the actual cooking of the chips. Black liquor is also present during the cook.
  • FIG. 2B illustrates the continuous addition of white liquor to black liquor at each stage of the cooking process, beginning with the warm fill through the end of the hot fill mode.
  • FIG. 2C illustrates the continuous addition of white liquor throughout the various stages, including the addition of white liquor to the washer filtrate from the displacement tank.
  • FIG. 3 illustrates a Stage 3 RDH system where no white liquor is added during the warm and hot fill modes. Only warm black liquor is leaving the warm liquor accumulator (B tank) 24 to flow through line 56 during the warm fill mode and into line 20, which then empties into the digester 10. Although this RDH system contains two hot liquor accumulators 28 (C1 tank) and 58 (C2 tank),
  • hot black liquor leaves the hot liquor accumulators 28 and 58 by lines 60 and 62, respectively, and flows to the digester 10 through lines 64 and 20.
  • hot white liquor from the hot white liquor accumulator 38 mixes with the hot black liquor leaving hot liquor accumulator 58 by line 66. The mixture then flows through lines 64 and 20 and into the digester 10.
  • FIG. 4 illustrates a Stage 3 RDH System with the addition of white liquor during the warm and hot fill modes.
  • white liquor is added to the warm black liquor leaving the warm liquor accumulator 24 by line 70.
  • the warm fill flows through lines 56 and 20 into the digester 10.
  • Either cool or hot white liquor may be used during the warm fill mode.
  • hot white liquor from the hot white liquor accumulator 38 is mixed with black liquor leaving hot liquor accumulator 28 by line 72, and is further mixed with the black liquor exiting the second hot liquor accumulator 58 by lines 62 and 66.
  • the mixture of hot white and black liquors flows from the two hot liquor accumulators 28 and 58 through lines 64 and 20 into the digester 10.
  • concentration of dissolved organic compounds at initial hot fill operation can be adjusted by adding white liquor to the hot fill line.
  • concentration of dissolved organic compounds in the C1 black liquor and in the C2 black liquor decreases from 13.1% to 10.1% and 14.9% to 9.8%, respectively.
  • warm black liquor temperatures between approximately 70° and 150°C and its strength between 3 and 20 g/l AA
  • hot black liquor temperatures between approximately 100° and 168°C and its strength between 8 and 30 g/l AA
  • warm and hot black liquor can be modified using white liquor profiling. These liquors can also be modified by sodium hydroxide (NaOH) profiling.
  • NaOH sodium hydroxide
  • the addition of white liquor or NaOH controls the total dissolved solids (TDS) concentration and black liquor strength using any combination of black liquor, white liquor ancS NaOH.
  • the washer filtrate displacement stage in which the black liquor temperature is held between approximately 50° and 105°C and black liquor strength between 1 and 18 g/l AA, can be reinforced with any combination of white liquor or NaOH solution.
  • Tables 1, 1A, 2, 2A, 3 and 3A provide the pulping results and conditions for a number of cooks used in preparing the RDH pulps for subsequent bleaching studies.
  • a summary of the pulping results is provided in Table 3B.
  • RDH pulps (R3, R4, R7, R8 and R12) were bleached using an (O)(D100)(EO)(D) sequence. However, each of the five RDH pulps were first oxygen delignified in stirred reactors using the conditions shown below in Table 4.
  • FIGS. 7 and 7A show that the best do-able case RDH pulp (R12) gave intermediate brightness between the best case RDH pulp (R4) and the baseline case RDH pulp (R8).

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  • Paper (AREA)
  • Pens And Brushes (AREA)
  • Glass Compositions (AREA)
  • Secondary Cells (AREA)
  • Dental Preparations (AREA)
  • Primary Cells (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Peptides Or Proteins (AREA)
PCT/US1995/002719 1994-03-04 1995-03-02 Impact of temperature and alkali charge on pulp brightness WO1995023891A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
PL95316144A PL316144A1 (en) 1994-03-04 1995-03-02 Effect to temperature and alkalinity onto brightness of paper pulp
MX9603876A MX9603876A (es) 1994-03-04 1995-03-02 Procedimiento intermitente de digestion para producir pulpa deslignficada.
EP95912729A EP0748412B1 (de) 1994-03-04 1995-03-02 Auswirkung von temperatur und alkalibeladung auf den zellstoffweissgrad
BR9506974A BR9506974A (pt) 1994-03-04 1995-03-02 Aperfeiçoamento em um processo de digestão por batelada do tipo usando aquecimento de deslocamento rápido para produzir polpa deslignificada
AU19789/95A AU684623B2 (en) 1994-03-04 1995-03-02 Impact of temperature and alkali charge on pulp brightness
DE69505503T DE69505503T2 (de) 1994-03-04 1995-03-02 Auswirkung von temperatur und alkalibeladung auf den zellstoffweissgrad
RU96121355A RU2127342C1 (ru) 1994-03-04 1995-03-02 Периодический способ варки целлюлозы и способ получения целлюлозы
CA002184706A CA2184706C (en) 1994-03-04 1995-03-02 Impact of temperature and alkali charge on pulp brightness
RO96-01743A RO117929B1 (ro) 1994-03-04 1995-03-02 Procedeu discontinuu de dezintegrare, pentru obtinerea pastei celulozice
NO963520A NO963520L (no) 1994-03-04 1996-08-23 Virkning av temperatur og alkalipåfylling på masselyshet
FI963448A FI118348B (fi) 1994-03-04 1996-09-03 Lämpötilan ja alkalipanoksen vaikutus massan vaaleuteen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20649694A 1994-03-04 1994-03-04
US08/206,496 1994-03-04

Publications (1)

Publication Number Publication Date
WO1995023891A1 true WO1995023891A1 (en) 1995-09-08

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PCT/US1995/002719 WO1995023891A1 (en) 1994-03-04 1995-03-02 Impact of temperature and alkali charge on pulp brightness

Country Status (19)

Country Link
EP (1) EP0748412B1 (de)
JP (1) JP2876428B2 (de)
CN (1) CN1143398A (de)
AT (1) ATE172503T1 (de)
AU (1) AU684623B2 (de)
BR (1) BR9506974A (de)
CA (1) CA2184706C (de)
DE (1) DE69505503T2 (de)
ES (1) ES2126263T3 (de)
FI (1) FI118348B (de)
MX (1) MX9603876A (de)
NO (1) NO963520L (de)
NZ (1) NZ282616A (de)
PL (1) PL316144A1 (de)
RO (1) RO117929B1 (de)
RU (1) RU2127342C1 (de)
TW (1) TW270159B (de)
WO (1) WO1995023891A1 (de)
ZA (1) ZA951777B (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998032912A1 (en) * 1997-01-22 1998-07-30 Ahlstrom Machinery Oy Batch cooking with black liquor pretreatment
WO1998056980A1 (en) * 1997-06-11 1998-12-17 Beloit Technologies, Inc. Improved displacement batch digester cooking system
WO2001094691A1 (en) * 2000-06-06 2001-12-13 Metso Paper, Inc. Method for batch cooking
EP2089571A1 (de) * 2006-11-22 2009-08-19 Metso Fiber Karlstad AB Verfahren zur nutzung der wärmeenergie der schwarzlauge
US8535480B2 (en) 2010-05-06 2013-09-17 Bahia Specialty Cellulose Sa Method and system for pulp processing using cold caustic extraction with alkaline filtrate reuse

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103757961B (zh) * 2013-12-30 2016-01-20 汶瑞机械(山东)有限公司 一种间歇蒸煮装置及其布液方法
US9644317B2 (en) 2014-11-26 2017-05-09 International Paper Company Continuous digester and feeding system
FI129440B (fi) * 2020-01-15 2022-02-28 Chempolis Oy Keittolaitteisto ja -menetelmä lignoselluloosaa sisältävän biomassan käsittelemiseksi

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0135461A1 (de) * 1983-08-24 1985-03-27 Beloit Corporation Mehrstufiges Aufschlussverfahren in einem satzweise arbeitenden Kocher
US4578149A (en) * 1981-03-05 1986-03-25 Fagerlund Bertil K E Process for digesting cellulosic material with heat recovery
SU1498857A1 (ru) * 1987-07-17 1989-08-07 Сибирский научно-исследовательский институт целлюлозы и картона Способ щелочной варки целлюлозы в котлах периодического действи

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1687076A (en) * 1927-10-12 1928-10-09 Venning D Simons Process for cooking wood chips by the alkaline process of pulp manufacture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578149A (en) * 1981-03-05 1986-03-25 Fagerlund Bertil K E Process for digesting cellulosic material with heat recovery
EP0135461A1 (de) * 1983-08-24 1985-03-27 Beloit Corporation Mehrstufiges Aufschlussverfahren in einem satzweise arbeitenden Kocher
SU1498857A1 (ru) * 1987-07-17 1989-08-07 Сибирский научно-исследовательский институт целлюлозы и картона Способ щелочной варки целлюлозы в котлах периодического действи

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9021, Derwent World Patents Index; Class F09, AN 90-162384 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998032912A1 (en) * 1997-01-22 1998-07-30 Ahlstrom Machinery Oy Batch cooking with black liquor pretreatment
US6350348B1 (en) 1997-01-22 2002-02-26 Andritz-Ahlstrom Oy Batch cooking with black liquor pretreatment
WO1998056980A1 (en) * 1997-06-11 1998-12-17 Beloit Technologies, Inc. Improved displacement batch digester cooking system
US6139689A (en) * 1997-06-11 2000-10-31 Beloit Technologies, Inc. Apparatus for digesting pulp in a displacement batch digester that uses displacement liquor having a sufficient hydrostatic head
WO2001094691A1 (en) * 2000-06-06 2001-12-13 Metso Paper, Inc. Method for batch cooking
EP2089571A1 (de) * 2006-11-22 2009-08-19 Metso Fiber Karlstad AB Verfahren zur nutzung der wärmeenergie der schwarzlauge
EP2089571A4 (de) * 2006-11-22 2012-09-05 Metso Paper Sweden Ab Verfahren zur nutzung der wärmeenergie der schwarzlauge
US8535480B2 (en) 2010-05-06 2013-09-17 Bahia Specialty Cellulose Sa Method and system for pulp processing using cold caustic extraction with alkaline filtrate reuse
US8734612B2 (en) 2010-05-06 2014-05-27 Bahia Specialty Cellulose Method and system for high alpha dissolving pulp production

Also Published As

Publication number Publication date
NZ282616A (en) 1997-05-26
FI963448A0 (fi) 1996-09-03
ATE172503T1 (de) 1998-11-15
RU2127342C1 (ru) 1999-03-10
AU684623B2 (en) 1997-12-18
NO963520L (no) 1996-08-23
DE69505503T2 (de) 1999-10-21
MX9603876A (es) 1997-03-29
FI963448A (fi) 1996-09-03
AU1978995A (en) 1995-09-18
BR9506974A (pt) 1997-09-16
ZA951777B (en) 1995-12-11
DE69505503D1 (de) 1998-11-26
ES2126263T3 (es) 1999-03-16
CA2184706C (en) 2001-10-30
TW270159B (de) 1996-02-11
EP0748412A1 (de) 1996-12-18
CN1143398A (zh) 1997-02-19
RO117929B1 (ro) 2002-09-30
JPH09505115A (ja) 1997-05-20
CA2184706A1 (en) 1995-09-08
PL316144A1 (en) 1996-12-23
JP2876428B2 (ja) 1999-03-31
FI118348B (fi) 2007-10-15
EP0748412B1 (de) 1998-10-21

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