EP0308314A1 - Verfahren zur Ozonbehandlung von Lignocellulosematerialien, insbesondere Papiermassen, und Reaktor zum Ausführen des Verfahrens - Google Patents

Verfahren zur Ozonbehandlung von Lignocellulosematerialien, insbesondere Papiermassen, und Reaktor zum Ausführen des Verfahrens Download PDF

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Publication number
EP0308314A1
EP0308314A1 EP88402296A EP88402296A EP0308314A1 EP 0308314 A1 EP0308314 A1 EP 0308314A1 EP 88402296 A EP88402296 A EP 88402296A EP 88402296 A EP88402296 A EP 88402296A EP 0308314 A1 EP0308314 A1 EP 0308314A1
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EP
European Patent Office
Prior art keywords
treated
ozone
reactor
reaction
enclosure
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.)
Granted
Application number
EP88402296A
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English (en)
French (fr)
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EP0308314B1 (de
Inventor
Christian Coste
Pierre Jan
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.)
Suez International SAS
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Degremont SA
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Publication date
Application filed by Degremont SA filed Critical Degremont SA
Priority to AT88402296T priority Critical patent/ATE82340T1/de
Publication of EP0308314A1 publication Critical patent/EP0308314A1/de
Application granted granted Critical
Publication of EP0308314B1 publication Critical patent/EP0308314B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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 present invention relates to the treatment with ozone of lignocellulosic material and in particular of paper pulp.
  • ozone has an action on lignocellular materials in general and in particular on lignin. This action, which leads to chemical degradation resulting in elimination of the wood structure, has been used for bleaching, in particular pulp. It has been found that the treatment of paper pulps with ozone, applied during the refining phase, leads to a reduction in the overall energy necessary for this refining, at the cost, however, of an increase in the duration of this phase, therefore treatment, due to the slow reaction of the ozone on the dough.
  • ozonation has not made evident the favorable influence of ozone on the improvement of the paper qualities, in particular of the mechanical qualities of certain pulps, like that of so-called “thermomechanical” “mechanical”, “chemico-thermo-mechanical” dough, that is to say dough obtained by grating logs in a humid environment on grinding wheels, or by shredding chips previously softened with water or steam, with a light chemical and / or heat treatment.
  • FR-A 2 474 550 discloses a process for bleaching cellulosic pulp with ozone, which consists in treating a pulp previously brought to a desired hygrometric state so as to ensure that the ozonation treatment runs smoothly. Such a process is not entirely satisfactory, in particular as regards the mechanical properties of the material obtained.
  • the present invention proposes to provide a method of treatment with ozone, improved compared to the prior art and providing unexpected results which will be reported below.
  • this invention relates to a process for the treatment with ozone of lignocellulosic material, in particular paper pulp, according to which the material is brought beforehand to the desired hygrometric state so that the ozone reaction can take place in optimal conditions characterized in that the material, brought to the desired hygrometric state is reduced to a state of sufficient division to ensure between the carrier gas of the ozone and the fibrous solid, an interface of maximum value and in that then said material is subjected to ozonation by means of a carrier gas in which the ozone concentration is between 4 and 10% by mass relative to said carrier gas.
  • the material is treated before ozonation by any means whatsoever, so that its dryness is in a range between 20 and 50%.
  • the improvement of the paper qualities of the finished products obtained after treatment with ozone according to the process according to the invention also makes it possible to increase the productivity by a significant gain on the speed of manufacture of paper or cardboard, as well as by an increase. speeds of machines ensuring processing or final use, printing, for example.
  • the Applicant has also been able to demonstrate that, when the ozone treatment is carried out in accordance with the process according to the invention, the compounds with an aromatic structure which constitute the lignin framework are transformed into by-products which no longer have the benzene function.
  • This transformation has the advantage of limiting the weight loss due to the disappearance of the lignin to a minimal value and of retaining an excellent yield by weight of the lignocellulosic materials thus treated.
  • a manufacture of paper pulp according to a conventional chemical process makes it possible to obtain an overall yield of the order of 45 to 60% while a manufacture of pulp according to a process in accordance with the invention provides a weight yield of about 90% with equal levels of ozone 5 0/0 in mass compared to the material considered dry. Thanks to the process according to the invention, it is possible to obtain paper pulps whose paper qualities, such as for example, the length of break or the burst index are close to those of pulps obtained by conventional chemical transformation with the advantage of a clearly favorable weight yield.
  • the process according to the invention can be implemented by means of a reactor which has been described below solely by way of nonlimiting example, a possible embodiment, this description being given with reference to the appended drawing which shows schematically an installation comprising such a reactor.
  • Ozone is produced from oxygen carried by a pipe (1) and introduced into a generator (2) electrically supplied at medium frequency and cooled with chilled water brought by a pipe (3) and evacuated by a pipe ( 4).
  • the characteristics of this generator are chosen so as to obtain high ozone concentrations of between 70 and 140 g / Nm3.
  • the high concentration ozone gas thus produced is sent via a pipe (5) to a reactor (6) constituted by an elongated enclosure slightly inclined on the horizontal in which the flow and mixing of the cellulosic material to be ozonated is ensured. by a simple screw system (7) like an Archimedes screw provided with a cleaning device (not shown) and ensuring a propulsion and a flow of the lignocellulosic material to be treated and favoring a continuous renewal of the material interface- gas.
  • the reactions of ozone on the lignocellulosic structures passing through a maximum depending on the height of the layer of material to be treated, the assembly is designed and adjusted so that the height of the layer of material being in the reactor remains weak and is advantageously around ten cm.
  • the ozonated gas is injected at several points (8) distributed over the length of the reactor by means of orifices provided in the part of the pipeline (5) located inside the reactor so as to ensure a radial flow of interest over the entire volume. reactive.
  • a conventional flow control device (not shown) allows this flow to be adjusted in each of the reaction zones defined by the injection points.
  • the introduction of lignocellulosic material into the reactor (6) takes place using a hopper (9) supplying a screw (10) of the plug type ensuring both the regulation of the rate of introduction of the material in the reaction vessel and the seal necessary to prevent leakage of ozonated gas to the atmosphere.
  • the extraction of the lignocellulosic material treated at the outlet of the reactor is carried out by means of a screw (11) also of the plug type ensuring both the regulation of the flow rate of the extracted product and the tightness necessary to prevent leakage of ozonated gas to the atmosphere.
  • the lignocellulosic material is brought, before its introduction into the ozonization reactor, by any means or any device suitable for a state of controlled dryness between 30 and 45% humidity.
  • the residence time of the lignocellulosic material necessary for obtaining the desired paper qualities is adjusted by adjusting the speed of rotation of the screw (7) ensuring the progression of the material in the treatment enclosure.
  • the small quantity of ozone which has not reacted with the lignocellulosic material is extracted from the reactor by suction and directed by a pipe (12) to a unit (14) for ozone destruction by thermal means.
  • the breaking length represents the length in meters of a strip of uniform width thickness supposed to be suspended by one of its ends and breaking under the effect of its own weight.
  • the burst index is an index reflecting the force to be applied, by means of a device capable of exerting hydrostatic pressure on a paper sample to cause it to burst.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Fertilizers (AREA)
EP88402296A 1987-09-17 1988-09-12 Verfahren zur Ozonbehandlung von Lignocellulosematerialien, insbesondere Papiermassen, und Reaktor zum Ausführen des Verfahrens Expired - Lifetime EP0308314B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88402296T ATE82340T1 (de) 1987-09-17 1988-09-12 Verfahren zur ozonbehandlung von lignocellulosematerialien, insbesondere papiermassen, und reaktor zum ausfuehren des verfahrens.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8712890 1987-09-17
FR8712890A FR2620744A1 (fr) 1987-09-17 1987-09-17 Procede de traitement par l'ozone de materiaux ligno-cellulosiques, notamment de pates a papier et reacteur pour la mise en oeuvre de ce procede

Publications (2)

Publication Number Publication Date
EP0308314A1 true EP0308314A1 (de) 1989-03-22
EP0308314B1 EP0308314B1 (de) 1992-11-11

Family

ID=9354988

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88402296A Expired - Lifetime EP0308314B1 (de) 1987-09-17 1988-09-12 Verfahren zur Ozonbehandlung von Lignocellulosematerialien, insbesondere Papiermassen, und Reaktor zum Ausführen des Verfahrens

Country Status (10)

Country Link
EP (1) EP0308314B1 (de)
JP (1) JP2731822B2 (de)
AT (1) ATE82340T1 (de)
BR (1) BR8804806A (de)
CA (1) CA1314664C (de)
DE (2) DE308314T1 (de)
ES (1) ES2035339T3 (de)
FI (1) FI93867C (de)
FR (1) FR2620744A1 (de)
NO (1) NO174781C (de)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5087326A (en) * 1991-02-20 1992-02-11 Union Camp Patent Holding, Inc. Rotating pulp bleaching reactor having inner and outer shells and lifting means on the interior surface of the inner shell
WO1992007999A1 (en) * 1990-10-26 1992-05-14 Union Camp Patent Holding, Inc. Pulp bleaching reactor and method
EP0492040A1 (de) * 1990-12-21 1992-07-01 Kamyr, Inc. Drehender Ozonreaktor für Zellstoff
EP0492039A1 (de) * 1990-12-27 1992-07-01 Kamyr, Inc. Pneumatischer Reaktor zum Ozonbleichen von Zellstoff
US5174861A (en) * 1990-10-26 1992-12-29 Union Camp Patent Holdings, Inc. Method of bleaching high consistency pulp with ozone
US5211811A (en) * 1989-02-15 1993-05-18 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification of alkaline treated pulp followed by ozone delignification
US5296099A (en) * 1990-05-17 1994-03-22 Union Camp Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with oxygen, ozone and chlorine dioxide
EP0627029A1 (de) * 1992-01-15 1994-12-07 Union Camp Patent Holding, Inc. Vorrichtung und verfahren zum bleichen von zellstoff
US5409570A (en) * 1989-02-15 1995-04-25 Union Camp Patent Holding, Inc. Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone
US5441603A (en) * 1990-05-17 1995-08-15 Union Camp Patent Holding, Inc. Method for chelation of pulp prior to ozone delignification
US5451296A (en) * 1991-05-24 1995-09-19 Union Camp Patent Holding, Inc. Two stage pulp bleaching reactor
US5520783A (en) * 1990-10-26 1996-05-28 Union Camp Patent Holding, Inc. Apparatus for bleaching high consistency pulp with ozone
USRE36033E (en) * 1989-08-16 1999-01-12 Maschinenfabrik Andritz Actiengesellschaft Process for the comminution of materials and plants for carrying out the process
US6174409B1 (en) 1997-09-19 2001-01-16 American Air Liquide Inc. Method to improve final bleached pulp strength properties by adjusting the CI02:03 ration within a single (D/Z) stage of the bleaching process
AP1537A (en) * 2000-07-06 2006-01-10 Servier Lab A crystalline form of perindopril tert-butylamine salt.

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188708A (en) 1989-02-15 1993-02-23 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification followed by ozone relignification
FI89516B (fi) * 1989-05-10 1993-06-30 Ahlstroem Oy Foerfarande foer blekning av cellulosamassa med otson
US5164043A (en) 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5411633A (en) * 1991-04-30 1995-05-02 Kamyr, Inc. Medium consistency pulp ozone bleaching
FI925558A (fi) * 1992-04-22 1993-10-23 Ahlstroem Oy Foerfarande och anordning foer blekning av massa
US5387317A (en) * 1993-01-28 1995-02-07 The Mead Corporation Oxygen/ozone/peracetic aicd delignification and bleaching of cellulosic pulps
US5810973A (en) * 1993-09-21 1998-09-22 Beloit Technologies, Inc. Apparatus for producing small particles from high consistency wood pulp
US5554259A (en) 1993-10-01 1996-09-10 Union Camp Patent Holdings, Inc. Reduction of salt scale precipitation by control of process stream Ph and salt concentration
CA2197190A1 (en) * 1994-08-11 1996-02-22 Lewis D. Shackford Means for gas-sealingly conveying shredded pulp
US5944952A (en) * 1995-07-26 1999-08-31 Beloit Technologies, Inc. Method for bleaching high consistency pulp with a gaseous bleaching reagent
US6077396A (en) * 1997-05-16 2000-06-20 Lariviere; Christopher J. Apparatus for fluffing and contacting high consistancy wood pulp with a gaseous bleaching reagent
SE514416C2 (sv) * 1999-06-10 2001-02-19 Valmet Fibertech Ab Metod och system för gastät inmatning av massa till en reaktor för ozonblekning

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1591070A (en) * 1925-02-27 1926-07-06 Robert B Wolf Bleaching apparatus
US2013115A (en) * 1931-09-21 1935-09-03 Thorne Carl Busch Process and apparatus for the refining of pulp
US2466633A (en) * 1948-05-26 1949-04-05 James M Daily Method of bleaching cellulosic pulp
FR1441787A (fr) * 1965-04-30 1966-06-10 Progil Procédé de blanchiment des pâtes à papier
FR2329794A1 (fr) * 1975-10-31 1977-05-27 Myrens Verksted As Procede et appareil pour traiter un materiau finement divise avec un gaz
EP0030158A1 (de) * 1979-12-03 1981-06-10 The Black Clawson Company Apparat und Verfahren zum Delignifizieren einer Pulpe mittlerer Konsistenz mittels Sauerstoff
FR2474550A1 (fr) * 1980-01-24 1981-07-31 Scott Paper Co Procede de blanchiment de pate cellulosique
EP0276608A1 (de) * 1986-12-31 1988-08-03 Beghin-Say Societe Anonyme Verfahren zur Ozon-Behandlung von Cellulosebrei

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5319404A (en) * 1976-04-19 1978-02-22 Toyo Pulp Co Ltd Process and apparatus for treating cellulose material
CA1090510A (en) * 1976-06-02 1980-12-02 Arthur W. Kempf Delignification and bleaching of a lignocellulosic pulp slurry with ozone
JPS5536313A (en) * 1978-08-30 1980-03-13 Hokusan Kk Production of mechanical pulp

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1591070A (en) * 1925-02-27 1926-07-06 Robert B Wolf Bleaching apparatus
US2013115A (en) * 1931-09-21 1935-09-03 Thorne Carl Busch Process and apparatus for the refining of pulp
US2466633A (en) * 1948-05-26 1949-04-05 James M Daily Method of bleaching cellulosic pulp
FR1441787A (fr) * 1965-04-30 1966-06-10 Progil Procédé de blanchiment des pâtes à papier
FR2329794A1 (fr) * 1975-10-31 1977-05-27 Myrens Verksted As Procede et appareil pour traiter un materiau finement divise avec un gaz
EP0030158A1 (de) * 1979-12-03 1981-06-10 The Black Clawson Company Apparat und Verfahren zum Delignifizieren einer Pulpe mittlerer Konsistenz mittels Sauerstoff
FR2474550A1 (fr) * 1980-01-24 1981-07-31 Scott Paper Co Procede de blanchiment de pate cellulosique
EP0276608A1 (de) * 1986-12-31 1988-08-03 Beghin-Say Societe Anonyme Verfahren zur Ozon-Behandlung von Cellulosebrei

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5211811A (en) * 1989-02-15 1993-05-18 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification of alkaline treated pulp followed by ozone delignification
US5409570A (en) * 1989-02-15 1995-04-25 Union Camp Patent Holding, Inc. Process for ozone bleaching of oxygen delignified pulp while conveying the pulp through a reaction zone
USRE36033E (en) * 1989-08-16 1999-01-12 Maschinenfabrik Andritz Actiengesellschaft Process for the comminution of materials and plants for carrying out the process
US5441603A (en) * 1990-05-17 1995-08-15 Union Camp Patent Holding, Inc. Method for chelation of pulp prior to ozone delignification
US5296099A (en) * 1990-05-17 1994-03-22 Union Camp Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with oxygen, ozone and chlorine dioxide
US5181989A (en) * 1990-10-26 1993-01-26 Union Camp Patent Holdings, Inc. Reactor for bleaching high consistency pulp with ozone
EP0512098B1 (de) * 1990-10-26 1998-03-04 Union Camp Patent Holding, Inc. Bleichen von zellstoff und reaktor
US5174861A (en) * 1990-10-26 1992-12-29 Union Camp Patent Holdings, Inc. Method of bleaching high consistency pulp with ozone
US5863389A (en) * 1990-10-26 1999-01-26 Union Camp Patent Holding, Inc. Pulp bleaching reactor for dispersing high consistency pulp into a gaseous bleaching agent containing ozone
WO1992007999A1 (en) * 1990-10-26 1992-05-14 Union Camp Patent Holding, Inc. Pulp bleaching reactor and method
US5520783A (en) * 1990-10-26 1996-05-28 Union Camp Patent Holding, Inc. Apparatus for bleaching high consistency pulp with ozone
US5472572A (en) * 1990-10-26 1995-12-05 Union Camp Patent Holding, Inc. Reactor for bleaching high consistency pulp with ozone
EP0492040A1 (de) * 1990-12-21 1992-07-01 Kamyr, Inc. Drehender Ozonreaktor für Zellstoff
EP0492039A1 (de) * 1990-12-27 1992-07-01 Kamyr, Inc. Pneumatischer Reaktor zum Ozonbleichen von Zellstoff
US5087326A (en) * 1991-02-20 1992-02-11 Union Camp Patent Holding, Inc. Rotating pulp bleaching reactor having inner and outer shells and lifting means on the interior surface of the inner shell
US5451296A (en) * 1991-05-24 1995-09-19 Union Camp Patent Holding, Inc. Two stage pulp bleaching reactor
EP0627029A4 (en) * 1992-01-15 1995-12-06 Union Camp Patent Holding Pulp bleaching apparatus and method.
EP0627029A1 (de) * 1992-01-15 1994-12-07 Union Camp Patent Holding, Inc. Vorrichtung und verfahren zum bleichen von zellstoff
US6174409B1 (en) 1997-09-19 2001-01-16 American Air Liquide Inc. Method to improve final bleached pulp strength properties by adjusting the CI02:03 ration within a single (D/Z) stage of the bleaching process
AP1537A (en) * 2000-07-06 2006-01-10 Servier Lab A crystalline form of perindopril tert-butylamine salt.

Also Published As

Publication number Publication date
FI884267A (fi) 1989-03-18
FI884267A0 (fi) 1988-09-16
JPH0197290A (ja) 1989-04-14
FI93867B (fi) 1995-02-28
ES2035339T3 (es) 1993-04-16
DE3875893D1 (de) 1992-12-17
DE3875893T2 (de) 1993-03-18
DE308314T1 (de) 1989-10-05
EP0308314B1 (de) 1992-11-11
JP2731822B2 (ja) 1998-03-25
BR8804806A (pt) 1989-04-25
NO884128L (no) 1989-03-20
ATE82340T1 (de) 1992-11-15
NO174781C (no) 1994-07-06
NO174781B (no) 1994-03-28
CA1314664C (fr) 1993-03-23
NO884128D0 (no) 1988-09-16
FR2620744A1 (fr) 1989-03-24
FI93867C (fi) 1995-06-12

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