WO1993021106A1 - Production d'agents chimiques blanchissants sur le site dans une usine de pate a papier - Google Patents

Production d'agents chimiques blanchissants sur le site dans une usine de pate a papier Download PDF

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Publication number
WO1993021106A1
WO1993021106A1 PCT/FI1993/000148 FI9300148W WO9321106A1 WO 1993021106 A1 WO1993021106 A1 WO 1993021106A1 FI 9300148 W FI9300148 W FI 9300148W WO 9321106 A1 WO9321106 A1 WO 9321106A1
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WO
WIPO (PCT)
Prior art keywords
oxygen
stage
bleaching
recited
ozone
Prior art date
Application number
PCT/FI1993/000148
Other languages
English (en)
Inventor
Kaj Henricson
Original Assignee
A. Ahlstrom Corporation
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
Application filed by A. Ahlstrom Corporation filed Critical A. Ahlstrom Corporation
Publication of WO1993021106A1 publication Critical patent/WO1993021106A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/022—Preparation from organic compounds
    • C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
    • 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
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • bleaching In conventional bleach plants for bleaching of cellulose (paper) pulp, bleaching has typically been done with chlorine and chlorine dioxide, and also often oxygen and hydrogen peroxide. In a typical bleach plant which uses oxygen and hydrogen peroxide, the consumption of oxygen has been about 15-25 kg per ton of pulp produced, while the peroxide consumption has been about 0-5 kg per ton of pulp produced. The rest of the bleaching chemical consumption has been of chlorine and chlorine dioxide. It has conventionally been considered uneconomical to manufacture oxygen and peroxide on site at a pulp mill. Therefore these chemicals typically have been purchased and brought to the mill, at a cost of about 20 cents per kg of oxygen, and about $1.20 per kg of hydrogen peroxide.
  • a method which greatly reduces the chemical costs for non-chlorine pulp mills.
  • the total cost for non-chlorine bleaching chemicals are expected to be about $2,000 per day for a 1,000 ton per day plant, or about $700,000 per year.
  • the production costs can be greatly reduced according to the invention compared with the prior art.
  • the yearly savings in bleaching chemical purchased for only one or a few years can pay all the capital costs, and any additional chemical costs, associated with the production of the non-chlorine bleaching chemicals according to the invention.
  • a method of producing bleaching chemicals on site at a mill for bleaching cellulose pulp comprises the steps of: (a) Producing hydrogen and oxygen from raw material on site. (b) Producing hydrogen peroxide on site from the hydrogen from step (a). And, (c) utilizing the hydrogen peroxide from step (b) and the oxygen from step (a) on site for bleaching cellulose pulp.
  • Step (a) may be practiced by using water as a raw material and disassociating the water into hydrogen and oxygen, e.g. by electrolysis.
  • Step (b) is typically practiced utilizing an oxygen containing gas, water (which may include bleach plant effluent), and a catalyst, which may include anthraquinone.
  • Step (c) may be practiced to produce ozone from the oxygen to provide a bleaching gas containing oxygen as the carrier gas and about 3 to 12% ozone as a the active bleaching agent, and bleaching the cellulose pulp with ozone in a Z stage.
  • Oxygen is recovered from the Z stage, and at least some of the recovered oxygen is used for oxygen bleaching the pulp in an 0 stage. Any remaining oxygen from the Z stage may be purified and combined with the oxygen from step (a).
  • the hydrogen peroxide produced according to the invention has a concentration of about 15-35% which is a desirable concentration for use directly in a P stage. Therefore the costs of evaporating, transporting, and diluting the hydrogen peroxide in the prior art are eliminated.
  • a method of bleaching cellulose pulp using only non-chlorine bleaching chemicals, in a bleach plant having at least one each of O, Z, and P stages comprising the steps of (a) producing non-chlorine bleaching chemicals on site (e.g. all or most of the chemicals) at the bleach plant from raw materials, and (b) using the produced 5 bleaching chemicals -in the O, Z, and P bleaching stages.
  • the hydrogen peroxide produced according to the invention has a concentration of about 15-35%, which is a desirable concentration for use directly
  • FIGURE is a schematic representation of an exemplary system for practicing 25 exemplary methods according to the present invention.
  • the drawing FIGURE schematically ill ⁇ istrates 30 apparatus utilizable for the practice of the present invention-
  • the continuous digester 10, or the like, or other equipment for producing paper pulp is utilized in association with a bleach plant that includes at least one oxygen stage 11, at least one ozone stage 12, and at least one peroxide stage 13.
  • a bleach plant that includes at least one oxygen stage 11, at least one ozone stage 12, and at least one peroxide stage 13.
  • alkali extraction, hot alkali extraction, (ZE), metal ion removal, and like stages may also be utilized, such as disclosed in co-pending application serial no. 07/839,389 filed February 21, 1992.
  • bleached cellulosic pulp in line 14 is produced.
  • the pulp typically is kraft rnilp, but also may be other types of bleached cellulosic pulp.
  • the apparatus 15 is provided on site at the pulp mill for the production of non-chlorine bleaching chemicals, such as for the stages 11, 12, and 13 (as well as any additional stages that are utilized, not shown in the drawing).
  • raw material such as water in line 17
  • the apparatus 18 for producing hydrogen and oxygen.
  • the apparatus 18 comprises conventional apparatus for disassociating water into hydrogen and oxygen, such as electrolytic apparatus for producing hydrogen and oxygen by electrolysis.
  • the produced hydrogen is discharged from the apparatus 18 in line 19, and goes to the hydrogen peroxide production apparatus 20.
  • the apparatus 20 may be any desired conventional apparatus for producing hydrogen peroxide, such as apparatus capable of practicing the AO-process. Hydrogen peroxide produced by the apparatus 20 is fed in line 21, on site in the pulp mill, directly to a P stage 13 to effect bleaching of the cellulosic pulp thereat.
  • the AO-process, as well as other conventional peroxide production processes typically use an oxygen containing gas (such as air), water or a high water concentration liquid, and catalysts, such as anthraquinone.
  • the water containing liquid added at 22 may comprise filtrate or other effluent from the bleach plant ("e.g. from one or more of the washers associated with stages 11 through 13) .
  • the chemical in line 21 typically has a concentration of about 15-35% hydrogen peroxide. At this strength it can be used directly for bleaching in a P stage 13. This is compared to the prior art purchased peroxide which has been evaporated to a strength of about 50-80% in order to reduce transportation costs, and which must be diluted before use in a P stage.
  • the invention with on site production of hydrogen peroxide of suitable strength for bleaching, eliminates evaporation, transportation, and dilution costs associated with prior art purchased bleaching chemical.
  • the oxygen produced by the apparatus 18 passes into line 23 and may be added directly to an oxygen stage 11 (by a conduit not shown in the drawing) , and/or may be fed to ozonator 24.
  • the ozonator 24 produces ozone from the oxygen in line 23, typically producing a bleaching gas in line 23 that includes oxygen as the carrier gas and about 3-12% by weight ozone (e.g. about 8 kilograms ozone and about 92 kilograms oxygen per every 100 kilograms of gas in line 25).
  • the ozonator 24 may be of the type that pressurizes the ozone and oxygen carrier gas before it is led into line 25 so that it is at greater than atmospheric pressure.
  • the gas in line 25, containing ozone as the active bleaching agent, is led to one or more Z-stages 12 to bleach the cellulosic pulp.
  • oxygen off gases are provided in line 26.
  • Line 26 may pass to a valve 27, with a portion of the flow -- which contains primarily oxygen gas -- provided in line 28 to one or more 0 stages 11.
  • the amount of oxygen gas from line 26 diverted by valve 27 to line 28 typically is about 25 kilograms per 100 kilograms of gas introduced in line 25, with about 70-80 kilograms diverted into line 29.
  • the gas in line 29, which contains primarily oxygen but with some other undesirable ' constituents, may be purified in conventional purifying apparatus 30, and then merged with the oxygen produced by apparatus 18, in line 23, via line 31.
  • an oxygen carrier gas can be replaced by nitrogen, air, or another carrier gas before the ozone is fed to stage 12, in which case what was the oxygen carrier gas is then fed directly to the O stage(s) 11, and/or recirculated to the ozonator 24.
  • a bleach plant would use about 8 kilograms of ozone per ton of pulp produced, about 25 kilograms of oxygen per ton of pulp produced, and about 25 kilograms of hydrogen peroxide per ton of pulp produced.
  • Hydrogen gas is produced by the apparatus 18 at a cost of 1 kWh/kg, or 25 kWh/ton of pulp.
  • Hydrogen peroxide is produced by the apparatus 20 at a cost of about 1 kWh/kg or 25 kWh/ton of pulp.
  • the total cost for oxygen and peroxide produced on site is about 50 kWh/ton of pulp.
  • the chemical balance may require that some 0 quarter inch is bought or some Hgan0 medicine sold. If the consumption of H Volume0 dose is increased and consumption of 0_ decreased the balance may change. While it is important that both 0 cough and H_0 cough are used, the amount (in kg's) does not have to balance.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

Les agents chimiques décolorants sans chlore (c'est-à-dire tous ou presque tous) nécessaires pour une usine de blanchiment de pâte cellulosique sont produits sur le site. L'oxygène et l'hydrogène sont produits par dissociation de l'eau (par exemple par electroyse). L'hydrogène est utilisé (par exemple avec un effluent de l'usine de blanchiment, et un catalyseur tel que l'anthraquinone) pour produire l'eau oxygénée qui est utilisée dans l'étape P de décoloration d'une usine de blanchiment. L'oxygène est fourni à un générateur d'ozone pour produire un gaz décolorant contenant de l'oxygène en tant que gaz porteur et environ 3 à 12 % en poids d'ozone en tant qu'agent actif de blanchiment et la pâte cellulosique est blanchie par l'ozone dans une étape Z. L'oxygène peut aussi être envoyé directement vers une étape O, ou l'oxygène provenant des gaz de l'étape Z peut être divisé, une partie étant laissée à l'étape O et une autre partie purifiée et combinée avec l'oxygène nouvellement produit. La production sur le site est extrêmement économique par rapport à l'achat d'agents chimiques blanchissants sans chlore.
PCT/FI1993/000148 1992-04-15 1993-04-07 Production d'agents chimiques blanchissants sur le site dans une usine de pate a papier WO1993021106A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86849892A 1992-04-15 1992-04-15
US868,498 1992-04-15

Publications (1)

Publication Number Publication Date
WO1993021106A1 true WO1993021106A1 (fr) 1993-10-28

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Family Applications (1)

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PCT/FI1993/000148 WO1993021106A1 (fr) 1992-04-15 1993-04-07 Production d'agents chimiques blanchissants sur le site dans une usine de pate a papier

Country Status (3)

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AU (1) AU3892493A (fr)
TW (1) TW259827B (fr)
WO (1) WO1993021106A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2731021A1 (fr) * 1995-02-28 1996-08-30 Chemoxal Sa Procede et installation de fabrication de pate a papier utilisant les effluents de traitement basiques d'une installation de production de peroxyde d'hydrogene
FR2730984A1 (fr) * 1995-02-28 1996-08-30 Chemoxal Sa Installation pour l'alimentation en peroxyde d'hydrogene d'une unite de traitement d'un site industriel
FR2746091A1 (fr) * 1996-03-18 1997-09-19 Air Liquide Procede et installation de fourniture de peroxyde d'hydrogene a debit variable

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE409884B (sv) * 1974-01-02 1979-09-10 Hooker Chemicals Plastics Corp Forfarande for frastellning av klordioxid, veteperoxid, klor, vete och vesentligen alkalimetallfri vattenhaltig alkalimetallhydroxid
AT384837B (de) * 1985-06-27 1988-01-11 Steyrermuehl Papier Verfahren und anordnung zur delignifizierung von zellstoff mit sauerstoff
WO1990012637A2 (fr) * 1989-03-15 1990-11-01 Pulp And Paper Research Institute Of Canada Procede d'hydrofractionnement electrodialytique pour le traitement d'electrolytes aqueux

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE409884B (sv) * 1974-01-02 1979-09-10 Hooker Chemicals Plastics Corp Forfarande for frastellning av klordioxid, veteperoxid, klor, vete och vesentligen alkalimetallfri vattenhaltig alkalimetallhydroxid
AT384837B (de) * 1985-06-27 1988-01-11 Steyrermuehl Papier Verfahren und anordnung zur delignifizierung von zellstoff mit sauerstoff
WO1990012637A2 (fr) * 1989-03-15 1990-11-01 Pulp And Paper Research Institute Of Canada Procede d'hydrofractionnement electrodialytique pour le traitement d'electrolytes aqueux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAMES P. CASEY, "Pulp end Paper Chemistry and Chemical Technology", 1980, JOHN WILEY & SONS, (NEW YORK), page 734 - page 746. *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2731021A1 (fr) * 1995-02-28 1996-08-30 Chemoxal Sa Procede et installation de fabrication de pate a papier utilisant les effluents de traitement basiques d'une installation de production de peroxyde d'hydrogene
FR2730984A1 (fr) * 1995-02-28 1996-08-30 Chemoxal Sa Installation pour l'alimentation en peroxyde d'hydrogene d'une unite de traitement d'un site industriel
WO1996027046A1 (fr) * 1995-02-28 1996-09-06 Chemoxal S.A. Procede et installation de fabrication de pate a papier utilisant les effluents de traitement basiques d'une installation de production de peroxyde d'hydrogene
WO1996026897A1 (fr) * 1995-02-28 1996-09-06 Chemoxal S.A. Installation pour l'alimentation en peroxyde d'hydrogene d'une unite de traitement d'un site industriel
FR2746091A1 (fr) * 1996-03-18 1997-09-19 Air Liquide Procede et installation de fourniture de peroxyde d'hydrogene a debit variable
WO1997034828A1 (fr) * 1996-03-18 1997-09-25 Elf Atochem Sa Procede et installation de fourniture de peroxyde d'hydrogene a debit variable
US6340410B1 (en) 1996-03-18 2002-01-22 Atofina Method for delivering a variable flow of hydrogen peroxide to a bleaching vessel
CN1094896C (zh) * 1996-03-18 2002-11-27 埃尔夫阿托化学有限公司 供应流率可变过氧化氢的方法及装置

Also Published As

Publication number Publication date
TW259827B (fr) 1995-10-11
AU3892493A (en) 1993-11-18

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