US3663357A - Bleaching of mechanical cellulosic pulp with ozone in the presence of a peroxygen compound - Google Patents

Bleaching of mechanical cellulosic pulp with ozone in the presence of a peroxygen compound Download PDF

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Publication number
US3663357A
US3663357A US20824A US3663357DA US3663357A US 3663357 A US3663357 A US 3663357A US 20824 A US20824 A US 20824A US 3663357D A US3663357D A US 3663357DA US 3663357 A US3663357 A US 3663357A
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United States
Prior art keywords
pulp
ozone
percent
brightness
peroxygen compound
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Expired - Lifetime
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US20824A
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English (en)
Inventor
Norman Liebergott
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Pulp and Paper Research Institute of Canada
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Pulp Paper Res Inst
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Publication of US3663357A publication Critical patent/US3663357A/en
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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
    • D21C9/00After-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
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/1073Bleaching ; Apparatus therefor with O3

Definitions

  • the most commonly used reducing agents are hydrosulphides whence bleaching is conducted in the aqueous phase at 3 to 4 percent consistency, at a pH from 4.5 to 6.0, at a temperature of about 60 C. with a 1-hour retention time and normally chelating or sequestering agents are also present.
  • oxidizing agents for the bleaching of mechanical pulps are peroxides which in contrast to hydrosulphides involve an alkaline pH, a relatively high pulp consistency of 15 to 25 percent, moderate temperatures of about 60 C., and a retention time of 2 to 3 hours.
  • stabilizers such as sodium silicate and magnesium sulphate in the bleach liquor to prevent decomposition thereof and further the mechanical pulp is normally pretreated at low consistency with organic chelating agents, such as sodium diethylenetriamine penta-acetate (DPTA), to remove naturally occurring trace metals in the mechanical pulps.
  • DPTA sodium diethylenetriamine penta-acetate
  • An object of a broad aspect of this invention is the provision of a process for the bleaching of a mechanical pulp with ozone whereby the brightness and/or the strength properties of the pulp are enhanced.
  • a process for the bleaching of pulp comprising carrying out the bleaching on moist pulp, having a consistency of 15 to 60 per cent by weight solids in the form of fiber and fiber aggregates by treating with a gaseous ozone-oxygen or ozone-air mixture, in the presence of a peroxygen compound containing a peroxygen equivalent of 0.025-l.0 per cent by weight, at a temperature of from 20 to C. for a period of from 1 to 60 minutes at a pH offrom 3.5 to 11.5.
  • the process comprises adding a small quantity of peroxygen compound containing a peroxygen equivalent of 0.025 1.0 per cent by weight of the dry pulp, then comminuting the pulp to the form of fiber and fiber aggregates having a consistency of 15 to 60 per cent by weight solids and then treating the pulp with a gaseous ozone-oxygen or ozone-air mixture at a temperature of from 20 to 80 C. for a period of from 1 to 60 minutes at a pH offrom 3.5 to 11.5.
  • the peroxygen compound may be added during or after the pulp comminution stage.
  • the essential feature of the invention is that the bleaching with ozone takes place in the presence of the peroxygen compound while the pulp is in the form of fiber and fiber aggregates.
  • the peroxygen compound is added to the unbleached mechanical pulp, either prior to comminution or during comminution, e.g. by spraying the solution on the fiber and fiber aggregates.
  • the comminuted pulp, in the form of fiber and fiber aggregates is then passed into a reactor in which it is treated with an ozone-bearing gas for a period of from 1 60 minutes at a pH offrom 3.5 to 11.5.
  • the peroxygen compound may be any conventional inorganic peroxide, including hydrogen peroxide and sodium peroxide or organic peroxide including benzoyl peroxide and ditertiarybutyl peroxide.
  • the ozone may be prepared in concentration of 4 percent on a weight/weight basis 0 /0, using a commercial laboratory ozonizer, or may be obtained and used (with proper precautions) from pressurized tanks.
  • Fluffed mechanical cellulosic pulp (sometimes referred to as shredded mechanical cellulosic pulp) is the product obtained by fragmentation of a mechanical cellulosic pulp into fiber and fiber aggregates or flocks. Each discrete fiber aggregate or flock is spongy, compressible and readily gas permeable. Each of the fiber aggregates or flocks is usually of an average size of about A 1 inch in diameter and presents a fluffed-up, dry appearance even with about 40 percent by weight moisture in the cellulosic pulp.
  • One preferred manner of flufiing or shredding the mechanical pulp to the form above-described is provided in Canadian Pat. application Ser. No. 068,411 filed Nov. 26, 1969, now Canadian Pat. No. 869,267 issued Aug. 27, 1971.
  • the mechanical pulp may be treated with a peroxide solution of inorganic or organic nature, then comminuted or shredded as described in the above-identified Canadian patent and finally treated with an ozone-bearing gas.
  • the resulting oxidized pulp will then have reached a suitable brightness with the strength properties suitably enhanced.
  • EXAMPLE I A commercial spruce-balsam mechanical pulp, brightness 57.3 was pressed to 35 percent consistency. The pressed pulp was sprayed with a solution containing hydrogen peroxide (0.2 percent H on o.d. pulp), sodium silicate (2.5 percent Na SiO on o.d. pulp), sodium hydroxide (1 percent NaOl-l on o.d. pulp), magnesium sulphate (0.05 percent MgSO, on o.d. pulp) and water sufficient to reduce the pulp consistency to 30 percent. The pulp was then comminuted into fiber and fiber aggregates.
  • hydrogen peroxide 0.2 percent H on o.d. pulp
  • sodium silicate 2.5 percent Na SiO on o.d. pulp
  • sodium hydroxide 1 percent NaOl-l on o.d. pulp
  • magnesium sulphate 0.05 percent MgSO, on o.d. pulp
  • EXAMPLE ll A commercial spruce-balsam mechanical pulp, brightness 57.3 was pressed to 35 percent consistency.
  • the pressed pulp tary vessel which was set in a bath and the temperature maintained at 40 C.
  • a gaseous ozone-oxygen mixture was passed into the rotary vessel so that within 30 minutes time 1 percent ozone on o.d. pulp basis was passed into the vessel.
  • the pH of the moist comminuted pulp was 3.5.
  • a portion of the bleached pulp was washed and air-dried and the brightness measured.
  • the brightness tabs were then placed in a hot air circulatory oven at C. for 1 hour, then conditioned in a constant atmosphere, relative humidity 50 percent at 70 F.
  • the brightness and loss of brightness were measured after aging, and the strength properties of the pulp tested on standard handsheets are set out in Table l.
  • a process for bleaching of mechanical pulp which comprises adding a peroxygen compound containing a peroxygen equivalent of 0.025 1.0 per cent by weight of the peroxygen compound on the oven dry weight of the pulp to moist pulp having a consistency of to 60 per cent by weight solids and in the form of fiber and fiber aggregates to provide a mixture of said pulp and said peroxygen compound, and thereafter treating, said resultant mixture with a gaseous mixture selected from the group consisting of ozone-oxygen, ozoneair, and mixtures thereof, until the pulp has been contacted with at least about 1 per cent by weight ozone on an oven-dry basis, said treating being conducted at a temperature of from about C. to about 80 C. for a period of from about 1 to about 60 minutes at a pH of from about 3.5 to about 11.5.
  • the gaseous mixture comprises ozone oxygen in concentrations of 4 percent on a weight/weight basis 0 /0 10.
  • the gaseous mixture has been prepared by passing oxygen through an ozonizer.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Detergent Compositions (AREA)
US20824A 1969-11-27 1970-03-18 Bleaching of mechanical cellulosic pulp with ozone in the presence of a peroxygen compound Expired - Lifetime US3663357A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA68520 1969-11-27

Publications (1)

Publication Number Publication Date
US3663357A true US3663357A (en) 1972-05-16

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US20824A Expired - Lifetime US3663357A (en) 1969-11-27 1970-03-18 Bleaching of mechanical cellulosic pulp with ozone in the presence of a peroxygen compound

Country Status (9)

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US (1) US3663357A (no)
AT (1) AT302012B (no)
CA (1) CA902861A (no)
DE (1) DE2058232C3 (no)
FI (1) FI50552C (no)
FR (1) FR2056606A5 (no)
GB (1) GB1274615A (no)
NO (1) NO127410B (no)
SE (1) SE354492B (no)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3868219A (en) * 1972-06-14 1975-02-25 Akzona Inc Determination of HCG glucose and galactose in body fluids with chromogenic indicators
US4008120A (en) * 1973-12-21 1977-02-15 Groupement Europeen De La Cellulose Process of delignification and bleaching a lignocellulose product
US4080249A (en) * 1976-06-02 1978-03-21 International Paper Company 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
US4410397A (en) * 1978-04-07 1983-10-18 International Paper Company Delignification and bleaching process and solution for lignocellulosic pulp with peroxide in the presence of metal additives
TR22594A (tr) * 1987-04-07 1987-12-15 Nur Emaye San Ve Tic Tic A S Soba borusu uzatma aparati
US5133946A (en) * 1989-12-22 1992-07-28 Schmidding-Werke Wilhelm Schmidding Process for bleaching cellulosic materials and plant for carrying out the process
US5164043A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5164044A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5174861A (en) * 1990-10-26 1992-12-29 Union Camp Patent Holdings, Inc. Method of bleaching high consistency pulp with ozone
US5181989A (en) * 1990-10-26 1993-01-26 Union Camp Patent Holdings, Inc. Reactor for bleaching high consistency pulp with ozone
US5188708A (en) * 1989-02-15 1993-02-23 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification followed by ozone relignification
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
WO1994021856A1 (en) * 1993-03-22 1994-09-29 Solvay Interox Improved ozone/peracid process for delignifying a lignocellulosic material
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
US5472572A (en) * 1990-10-26 1995-12-05 Union Camp Patent Holding, Inc. Reactor for bleaching high consistency pulp with ozone
US5520783A (en) * 1990-10-26 1996-05-28 Union Camp Patent Holding, Inc. Apparatus for bleaching high consistency pulp with ozone
AU670195B2 (en) * 1993-04-06 1996-07-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Bleaching recycled pulp with a reductive-oxidative sequence
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
US5618385A (en) * 1992-03-24 1997-04-08 Albright & Wilson Limited Method of peroxide bleaching of pulp using a peroxide decomposing inactivator
US5658429A (en) * 1991-04-30 1997-08-19 Eka Nobel Ab Process for bleaching of lignocellulose-containing pulp using a chelating agent prior to a peroxide-ozone-peroxide sequence
US5755925A (en) * 1993-04-06 1998-05-26 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Bleaching recycled pulp with ozone and hydrogen peroxide
US6120556A (en) * 1996-06-21 2000-09-19 Nippon Peroxide Co., Ltd. Stabilizing agent for peroxide-bleaching procedure and methods of bleaching a fiber material by using same
US6231718B1 (en) 1992-02-28 2001-05-15 International Paper Company Two phase ozone and oxygen pulp treatment

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2801327B1 (fr) * 1999-11-18 2002-07-12 Papeteries Matussiere Forest Procede de desencrage, de decoloration, de desinfection et de blanchiment de papiers de recuperation
DE102009046797A1 (de) * 2009-11-18 2011-05-19 Voith Patent Gmbh Bleiche

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838459A (en) * 1955-02-01 1958-06-10 Pennsalt Chemicals Corp Stabilization of solutions containing peroxygen compounds
US2859087A (en) * 1955-03-28 1958-11-04 Du Pont Process for bleaching webs of fibrous cellulose material with hydrogen peroxide vapor containing water vapor
US3451888A (en) * 1965-04-30 1969-06-24 Progil Bleaching pulp having high consistency with ozone having moisture content near 100%
US3492199A (en) * 1966-10-04 1970-01-27 Fmc Corp Bleaching fluffed mechanical wood pulp with hydrogen peroxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838459A (en) * 1955-02-01 1958-06-10 Pennsalt Chemicals Corp Stabilization of solutions containing peroxygen compounds
US2859087A (en) * 1955-03-28 1958-11-04 Du Pont Process for bleaching webs of fibrous cellulose material with hydrogen peroxide vapor containing water vapor
US3451888A (en) * 1965-04-30 1969-06-24 Progil Bleaching pulp having high consistency with ozone having moisture content near 100%
US3492199A (en) * 1966-10-04 1970-01-27 Fmc Corp Bleaching fluffed mechanical wood pulp with hydrogen peroxide

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3868219A (en) * 1972-06-14 1975-02-25 Akzona Inc Determination of HCG glucose and galactose in body fluids with chromogenic indicators
US4008120A (en) * 1973-12-21 1977-02-15 Groupement Europeen De La Cellulose Process of delignification and bleaching a lignocellulose product
US4080249A (en) * 1976-06-02 1978-03-21 International Paper Company 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
US4410397A (en) * 1978-04-07 1983-10-18 International Paper Company Delignification and bleaching process and solution for lignocellulosic pulp with peroxide in the presence of metal additives
TR22594A (tr) * 1987-04-07 1987-12-15 Nur Emaye San Ve Tic Tic A S Soba borusu uzatma aparati
US5188708A (en) * 1989-02-15 1993-02-23 Union Camp Patent Holding, Inc. Process for high consistency oxygen delignification followed by ozone relignification
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
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
US5133946A (en) * 1989-12-22 1992-07-28 Schmidding-Werke Wilhelm Schmidding Process for bleaching cellulosic materials and plant for carrying out the process
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
US5164043A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5441603A (en) * 1990-05-17 1995-08-15 Union Camp Patent Holding, Inc. Method for chelation of pulp prior to ozone delignification
US5164044A (en) * 1990-05-17 1992-11-17 Union Camp Patent Holding, Inc. Environmentally improved process for bleaching lignocellulosic materials with ozone
US5520783A (en) * 1990-10-26 1996-05-28 Union Camp Patent Holding, Inc. Apparatus for bleaching high consistency pulp with ozone
US5174861A (en) * 1990-10-26 1992-12-29 Union Camp Patent Holdings, Inc. Method of 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
US5181989A (en) * 1990-10-26 1993-01-26 Union Camp Patent Holdings, Inc. Reactor for 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
US5658429A (en) * 1991-04-30 1997-08-19 Eka Nobel Ab Process for bleaching of lignocellulose-containing pulp using a chelating agent prior to a peroxide-ozone-peroxide sequence
US5451296A (en) * 1991-05-24 1995-09-19 Union Camp Patent Holding, Inc. Two stage pulp bleaching reactor
US6231718B1 (en) 1992-02-28 2001-05-15 International Paper Company Two phase ozone and oxygen pulp treatment
US5618385A (en) * 1992-03-24 1997-04-08 Albright & Wilson Limited Method of peroxide bleaching of pulp using a peroxide decomposing inactivator
AU683461B2 (en) * 1993-03-22 1997-11-13 Research Foundation Of The State University Of New York, The Improved ozone/peracid process for delignifying a lignocellulosic material
WO1994021856A1 (en) * 1993-03-22 1994-09-29 Solvay Interox Improved ozone/peracid process for delignifying a lignocellulosic material
US5755925A (en) * 1993-04-06 1998-05-26 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Bleaching recycled pulp with ozone and hydrogen peroxide
AU670195B2 (en) * 1993-04-06 1996-07-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Bleaching recycled pulp with a reductive-oxidative sequence
US5693184A (en) * 1993-10-01 1997-12-02 Union Camp Patent Holding, Inc. Reduction of salt scale precipitation by control of process stream pH and salt concentration
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
US6120556A (en) * 1996-06-21 2000-09-19 Nippon Peroxide Co., Ltd. Stabilizing agent for peroxide-bleaching procedure and methods of bleaching a fiber material by using same

Also Published As

Publication number Publication date
CA902861A (en) 1972-06-20
FR2056606A5 (no) 1971-05-14
DE2058232C3 (de) 1974-10-24
SE354492B (no) 1973-03-12
AT302012B (de) 1972-09-25
DE2058232A1 (de) 1971-06-09
NO127410B (no) 1973-06-18
DE2058232B2 (de) 1974-03-14
GB1274615A (en) 1972-05-17
FI50552B (no) 1975-12-31
FI50552C (fi) 1976-04-12

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