EP3571347B1 - Procede de blanchiment d'une pate a papier - Google Patents

Procede de blanchiment d'une pate a papier Download PDF

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Publication number
EP3571347B1
EP3571347B1 EP18703063.0A EP18703063A EP3571347B1 EP 3571347 B1 EP3571347 B1 EP 3571347B1 EP 18703063 A EP18703063 A EP 18703063A EP 3571347 B1 EP3571347 B1 EP 3571347B1
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Prior art keywords
paper pulp
pulp
process according
bleaching
advantageously
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German (de)
English (en)
French (fr)
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EP3571347A1 (fr
Inventor
Gérard MORTHA
Jennifer MARCON
Nathalie MARLIN
Auphélia BURNET
Michel Petit-Conil
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Institut Polytechnique de Grenoble
Centre Technique de lIndustrie des Papiers Cartons et Celluloses
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Institut Polytechnique de Grenoble
Centre Technique de lIndustrie des Papiers Cartons et Celluloses
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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
    • D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
    • 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
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
    • 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
    • D21C9/1005—Pretreatment of the pulp, e.g. degassing the pulp
    • 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
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • 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

  • the present invention relates to a process for bleaching an unbleached or pre-bleached pulp, using chlorine dioxide in an alkaline medium, hydrogen peroxide and, under certain conditions, sulfuric acid. This bleaching takes place in several reaction steps but does not require intermediate washing of the paper pulp between the different steps.
  • the bleaching of pulp is carried out in several stages called stages. Each stage is followed by washing the pulp and most often a change in pH. During these various stages, different chemical reagents such as delignification agents (oxygen, chlorine dioxide or hydrogen peroxide) are generally used to cause the oxidation, the discoloration and the almost complete dissolution of the lignin in the pulp. to paper.
  • delignification agents oxygen, chlorine dioxide or hydrogen peroxide
  • hydrogen peroxide is used in an alkaline medium. It is used independently or sometimes in admixture with gaseous oxygen. Hydrogen peroxide acts by delignification (oxidation then solubilization of the depolymerized lignin) or by discoloration (oxidation of lignin with decrease in the conjugation of the lignin molecule which is not solubilized) of the pulp.
  • Chlorine dioxide (ClO 2 ) is the most commonly used and most effective reagent among bleach reagents. It is used in several places in the bleaching sequence, during stages called stages D, numbered in the order of implementation: stages D 0 , D 1 and D 2 .
  • stages D numbered in the order of implementation: stages D 0 , D 1 and D 2 .
  • AOX organochlorine compounds
  • chlorate ions ClO 3 -
  • Chlorate ions are formed from chlorite ions (ClO 2 - ) and hypochlorous acid (HClO) generated during the reaction between chlorine dioxide and lignin. It is known that chlorate ions act on the flora of aquatic environments and accumulate in the sediments of lakes and rivers. The formation of chlorate ions is therefore detrimental to the ecology of aquatic environments which receive pulp mill effluents.
  • the chlorate ion is an oxidant inert to lignin under the conditions of the bleaching. Its formation during bleaching causes a loss of oxidizing power, resulting in a decrease in delignification. Generally, the loss of delignifying power varies between 10% and 40% depending on the process, which makes it necessary to use an excess of chlorine dioxide to achieve the final target whiteness.
  • the patent US 5,268,075 discloses a process involving a double stage, the first of which is carried out with chlorine dioxide in a quasi-neutral medium at a pH between 6.5 and 7.5 and the second of which is an acidification stage, carried out via a second addition of chlorine dioxide.
  • This acidification step makes it possible to obtain a paper pulp having a final pH of between 3 and 4.
  • This process allows a 24% reduction in the overall consumption of chlorine dioxide and a 45% reduction in the formation of chlorine dioxide.
  • the hydrogen peroxide stage (P) is carried out before the chlorine dioxide stage (D).
  • the chlorine dioxide stage (D) is carried out before the chlorine dioxide stage (D).
  • This process therefore corresponds to the following sequence: C / DE 1 / OD 1 E 2 / PD 2 .
  • the symbol “/” indicates the absence of washing between two steps.
  • this sequence requires intermediate washes between the acid stages (D, O, P) and the alkaline stages (E 1 , D 1 , D 2 ), in order to adjust the pH. In fact, alkaline fiber suspensions are always washed before an acid bleaching stage.
  • hydrogen peroxide is used during an alkaline extraction step. Hydrogen peroxide is used to prolong the oxidation of lignin. The pulp being washed between the introduction of chlorine dioxide and the addition of hydrogen peroxide, there is no reaction between these two chemical agents.
  • the present invention solves these problems.
  • the Applicant has developed a process for bleaching a paper pulp using chlorine dioxide in an alkaline medium, hydrogen peroxide and optionally a Br ⁇ nsted acid. This process does not require intermediate washing between the different steps.
  • D alk P This stage (bleaching stages) combining the sequential use of several reagents is called (D alk P ) or (D alk P A).
  • D alk denotes treatment with chlorine dioxide (D) in an alkaline medium (alk).
  • the index “P” corresponds to the use of hydrogen peroxide while “A” denotes an optional acidification step (Br ⁇ nsted acid).
  • the use of an overall parenthesis is intended to show that the consecutive stages of this bleaching process are grouped together in a single stage, the stages not being interspersed with phases of washing the pulp. A precise description of this process and of its various steps is given in the section “Disclosure of the invention”.
  • the present invention relates to the bleaching of unbleached or pre-bleached pulp.
  • This process replaces the conventional sequences DnD, DE, DEp, DEop, DP or DEo, corresponding to two chlorine dioxide treatments (stage D), spaced by a washing or neutralization stage (DnD), or else a treatment with dioxide.
  • chlorine stage D
  • stage E alkaline extraction stage
  • stage Ep alkaline extraction stage
  • stage Eop or Eo a treatment with chlorine dioxide (stage D) followed by a treatment with hydrogen peroxide in an alkaline medium (stage P)
  • stage P alkaline medium
  • the process according to the invention comprises the stage (D alk P ) corresponding to stage D alk (chlorine dioxide in an alkaline medium) followed by stage P (hydrogen peroxide in an alkaline medium), without washing between the two steps.
  • This method does not include a step for washing the paper pulp before the end of step e), and, where appropriate, before the end of step f).
  • Step c) is carried out on a paper pulp resulting from step b) or, where appropriate, on a paper pulp obtained at the end of step c).
  • Paper pulp also called “pulp”, corresponds to a suspension of lignocellulosic fibers in water.
  • Any kind of paper pulp can be treated according to the invention. It can be obtained mechanically or chemically or from the recycling of recovered paper and cardboard. However, it is preferentially a pulp obtained chemically from virgin fibers (kraft process, with sulphite, bisulphite, soda, etc.).
  • the pulp can be obtained from softwood, hardwood, eucalyptus wood or annual plants. It can also come from paper to be recycled such as newsprint or magazines.
  • the pulp treated according to the invention can be obtained by resuspension in water of a dried pulp, of recovered paper, or directly from a pulping plant, according to the conventional methods of papermaking forming part of the knowledge of those skilled in the art.
  • the pulp is kraft pulp.
  • the unbleached or pre-bleached pulp corresponds to a suspension of lignocellulosic fibers advantageously containing from 20 to 400 grams of lignocellulosic fibers per liter of suspension, more advantageously from 50 to 300 grams of fibers per liter of water, and even more preferably from 50 to 150 grams of fiber per liter of water.
  • the consistency of the unbleached or pre-bleached pulp suspension is advantageously between 2 and 40%, preferably between 5 and 30%, and even more preferably of the order of 10%.
  • the consistency is expressed as a percentage by weight of dry paper pulp in the aqueous suspension, that is to say the number of grams of dry cellulosic fibers contained in 100 g of the suspension of cellulosic fibers in the aqueous phase.
  • the bleaching is carried out on unbleached or pre-bleached paper pulp.
  • the paper pulp can be pre-bleached by any type of pre-bleaching process known to those skilled in the art.
  • the pulp can be delignified by an oxygen stage or pre-bleached by a sequence of TCF type: OOQP, OZ, OZEop, OZEp, OZE ... or of ECF type: ODEop, ODEp, ODE, ODEpDEp , or also other types of pre-bleaching sequence, for example those involving chelating, acidic or reducing stages.
  • TCF type OOQP
  • OZ OZEop
  • OZEp OZE ...
  • ECF type ODEop, ODEp, ODE, ODEpDEp
  • the notations of the stages of bleaching, employed above, are standard.
  • the unbleached or pre-bleached pulp has a kappa number advantageously between 40 and 0.5, more preferably between 5 and 0.5.
  • the kappa index is a measure of oxidability with potassium permanganate. This index makes it possible to evaluate the rate of oxidizable functions of the pulp, including residual lignin, as well as the demand for oxidizing bleaching reagent. The lower the kappa index, the lower the lignin level and the lower the demand for bleaching reagent.
  • the unbleached or pre-bleached pulp has a pH greater than or equal to 8. However, when the pulp has a pH less than 8, at least one Br ⁇ nsted base is added of so as to obtain a paper pulp having a pH greater than or equal to 8.
  • At least one cellulose protective agent can be added to the unbleached or pre-bleached pulp during step a).
  • a chelating and / or sequestering agent can also be added during step a).
  • the protective agent makes it possible to protect the cellulose of the lignocellulosic fibers from possible depolymerization which may subsequently be caused by chlorine dioxide in an alkaline medium or by the presence of hydrogen peroxide.
  • the protective agent can be omitted. In fact, the absence of a protective agent does not affect the efficiency of the process in terms of delignification.
  • the Br ⁇ nsted base and, where appropriate, the cellulose protective agent are introduced into a pipe conveying the unbleached or pre-bleached pulp to a mixer, for example using a pump. piston or directly in the mixer.
  • the amount of cellulose protective agent in an alkaline medium is advantageously between 0.1 and 1% by weight relative to the weight of the dry paper pulp, more advantageously 0.4 to 0.5% by weight relative to the weight of dry pulp.
  • the cellulose protective agent is chosen from magnesium sulfate, or other cellulose protective agents known to those skilled in the art, alone or as a mixture.
  • Sodium silicate, diethylene-triamine-penta acetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA) or other agents can also be added, alone or in admixture, to avoid decomposition of the peroxide. hydrogen during step d).
  • these agents can also be introduced during step c). These agents are preferably added when the paper pulp comprises metal cations.
  • the amount of Br ⁇ nsted base is adjusted so that the unbleached or pre-bleached pulp has a basic pH, advantageously greater than or equal to 8, more advantageously between 8 and 13, even more advantageously between 8.5 and 12, and even more advantageously between 8.5 and 9.5.
  • the Br ⁇ nsted base or bases are chosen from alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal oxides; alkaline earth metal oxides; alone or as a mixture. It may in particular be NaOH, MgO, Mg (OH) 2 , Ca (OH) 2 , KOH, or other bases known to those skilled in the art. They can also be mixtures containing bases, such as some process liquors, such as white kraft liquor after processing to remove reducing species. Even more preferably, the Br ⁇ nsted base is sodium hydroxide.
  • the additions of the cellulose protective agent and of the Br ⁇ nsted base can be successive or simultaneous.
  • the cellulose protective agent in an alkaline medium is introduced before the Br ⁇ nsted base.
  • the paper pulp resulting from step a) has an alkaline pH, greater than or equal to 8, more advantageously between 8 and 13, and even more advantageously between 8.5 and 12, and even more preferably between 8 , 5 and 9.5.
  • step b) the paste obtained at the end of step a) containing at least one Br ⁇ nsted base, and advantageously at least one cellulose protective agent, is brought into contact with chlorine dioxide.
  • the chlorine dioxide is advantageously in the form of an aqueous solution.
  • the chlorine dioxide solution may have a neutral or acidic pH, in accordance with the solutions traditionally employed in conventional D stages. It is not alkalized before it is introduced into the pulp, so that the chlorine dioxide cannot decompose before it comes into contact with the pulp.
  • the paste resulting from step a) is brought into contact with chlorine dioxide in a mixer, or upstream of a mixer.
  • the quantity of active chlorine introduced is determined as a function of the pulp to be bleached and of the pre-bleaching which it may have undergone beforehand. The kappa number of the pulp is used to calculate this quantity of active chlorine.
  • the amount of active chlorine introduced is between 0.1% and 10% by weight relative to the weight of the dry paper pulp.
  • the extent of this range of values results from the very wide range of the kappa index of the pulps to which the process can be applied.
  • the paper pulp has a fairly low kappa number, advantageously less than 10; and even more preferably, less than 5.
  • the amount of active chlorine generally does not exceed about 2.5% by weight relative to the weight of the dry pulp.
  • the contact time between the paper pulp resulting from step a) and the chlorine dioxide is at least a few seconds, advantageously at least 10 seconds.
  • the contact time is short compared to conventional processes in an acidic medium. It is advantageously less than 5 minutes. However, it can be lengthened without prejudice to the dough if the technical conditions of the process do not allow a short reaction time to be achieved.
  • the contacting time is advantageously between a few seconds and 5 minutes.
  • a short time can be chosen in a sufficiently efficient mixer.
  • step b) is carried out at a temperature above 20 ° C, more advantageously between 25 ° C and 90 ° C, even more advantageously between 40 ° C and 80 ° C, and even more advantageously between 40 ° C and 70 ° C.
  • Step b) is advantageously carried out in a mixer.
  • Chlorine dioxide can also be introduced directly onto the pulp using a pump or other method, provided the pulp is in a flow situation to ensure a good level of mixing. with the chlorine dioxide introduced.
  • steps a) and b) can be carried out at the temperature at which the paper pulp is located immediately after the possible step of washing the paper pulp, resulting from baking or pre-bleaching. , preceding step a).
  • step c) at least one Br ⁇ nsted base is added to the pulp from step b) when the pH of the paper pulp from step b) is less than 10.
  • the amount of Br ⁇ nsted base is adjusted so that the paper pulp has a pH advantageously greater than or equal to 9, more advantageously between 9 and 12, and even more advantageously between 10 and 11.
  • the Br ⁇ nsted base or bases are chosen from alkali metal hydroxides; alkaline earth metal hydroxides; alkali metal oxides; alkaline earth metal oxides; alone or as a mixture. It may in particular be NaOH, Mg (OH) 2 , MgO, Ca (OH) 2 , KOH or other bases known to those skilled in the art, that is to say the bases traditionally used in commercially available bleaching plants, such as for example alkaline liquors used for kraft cooking or O stages, after elimination of reducing species. Even more preferably, the Br ⁇ nsted base is sodium hydroxide.
  • the Br ⁇ nsted base or bases added in step c) are the same as that (s) added in step a).
  • Step c) is advantageously carried out in a pipe, for example a pipe connecting a mixer and a bleaching tower, for example using a piston pump.
  • step c) can be carried out at the temperature at which the paper pulp is located immediately after step b).
  • step c) is advantageously carried out at a temperature above 20 ° C, more advantageously between 25 ° C and 90 ° C, even more advantageously between 40 ° C and 80 ° C, and even more advantageously between 40 ° C and 70 ° C.
  • step d hydrogen peroxide is introduced into the paste resulting from step c).
  • This introduction can be carried out in a pipe conveying the pulp to a bleaching tower, for example using a piston pump. This is not an alkaline extraction stage.
  • the amount of hydrogen peroxide is advantageously between 0.1% and 5% by weight relative to the weight of the dry paper pulp, more advantageously between 0.2% and 1% by weight, and even more advantageously between 0.3% and 0.5% by weight.
  • step d) can be carried out at the temperature at which the paper pulp is located immediately after step c).
  • step d) is advantageously carried out at a temperature above 20 ° C, more advantageously between 25 ° C and 90 ° C, even more advantageously between 40 ° C and 80 ° C, and even more advantageously between 40 ° C and 70 ° C.
  • step e) the paste resulting from step d) is introduced and maintained in a first bleaching tower.
  • This bleaching tower can be of any type well known to those skilled in the art. It allows the pulp to be stored for a given period. Generally, the pulp is not agitated in the bleach tower. However, the paste can also be stored in a stirred reactor or in another storage means known to those skilled in the art.
  • the temperature of the paper pulp inside the first bleach tower is between 40 ° C and 95 ° C, more preferably between 65 ° C and 80 ° C, and even more advantageously between 70 ° C and 75 ° C.
  • the passage time of the pulp in the first bleaching tower is between 30 minutes and 180 minutes, more preferably between 60 minutes and 120 minutes, for example of the order of 90 minutes.
  • step e the pulp was bleached.
  • the paper pulp resulting from step e) is not washed but directly involved in a treatment in an acidic medium to remove any residual lignin. It can then be a step f) of acid treatment and passage through a bleaching tower, without washing after step e).
  • Step f) is optional. It includes an acid treatment and passing the pulp through a second bleaching tower. In this case, no washing of the paper pulp is carried out after step e).
  • the acid treatment consists in adding a Br ⁇ nsted acid to the pulp suspension, in order to continue to eliminate all or part of the residual lignin which may still be present in the pulp after step e). This elimination is possibly accompanied by an increase in the whiteness of the pulp.
  • the acid used can in particular be chosen from the group of mineral acids, in particular sulfuric acid, which represents the acid most commonly used in pulp mills.
  • a mineral acid is an acid derived from at least one inorganic compound.
  • This family of acids includes in particular hydrohalic acids (HF, HCl, HBr, HI), sulfuric acid, nitric acid or boric acid, more advantageously sulfuric acid.
  • this mineral acid can also be carried out in a pipe, for example in a pipe connecting two bleaching towers.
  • the pH of the paper pulp thus acidified is advantageously between 2 and 5, more advantageously between 3 and 4.
  • step f) the paste from step e) is introduced and maintained in a second bleaching tower.
  • Step f) (acid + bleach tower) is advantageously carried out at a temperature between 50 and 90 ° C, more advantageously at the temperature of the previous bleaching stage, and even more advantageously between 70 and 80 ° C.
  • the passage time of the pulp in the second bleaching tower is advantageously between 10 minutes and 180 minutes, more advantageously between 10 and 120 minutes, and even more advantageously between 30 and 90 minutes.
  • a reduction in reaction time can be obtained if the pH is lower and / or the temperature is higher.
  • these conditions of faster reaction of chlorite ions, especially a lower pH eventually promote the formation of chlorates.
  • the bleached paper pulp can be washed.
  • step a) to f) the sequence corresponding to the process according to the invention is denoted (D alk P A).
  • this stage is denoted (D alk P ) if stage f) is not carried out (stages a) to e)).
  • the present invention also relates to the bleached paper pulp obtained by the process described above.
  • the pulp resulting from step e) (D alk P ) or, where appropriate, from step f) (D aik P A), is a pre-bleached or bleached paper pulp which has not been diluted with during steps a) to e), or where appropriate, a) to f).
  • liquid such as water
  • additives such as chlorine dioxide, advantageously in aqueous solution, or hydrogen peroxide, which is generally added in the form of an aqueous solution. concentrated.
  • the process according to the invention (D alk P or D aik P A) can therefore be carried out almost at a constant concentration of lignocellulosic fibers throughout steps a) to e) or a) to f).
  • the bleached pulp resulting from step e) (D alk P ) or, where appropriate, from step f) (D alk P A) therefore advantageously contains from 20 to 400 grams of lignocellulosic fibers per liter of suspension, more advantageously from 50 to 300 grams of fiber per liter of water, and even more advantageously from 50 to 150 grams of fiber per liter of water.
  • the dough resulting from step e) or, where appropriate, from step f) has a kappa index advantageously between 20 and 0.5, more advantageously between 5 and 1.
  • the bleached paper pulp according to the invention (D alk P or D alk P A) has optical properties (whiteness) similar to those of a pulp bleached according to the conventional sequence of type DnD, DE, DEp, DEo, DEop, DP and this, even if it can present a higher kappa index.
  • the process according to the invention makes it possible to reduce the quantity of pollutants (-20.6% of COD, -71.1% of AOX) generated compared to a conventional process of the DnD, DE, DEp, DEo, DEop, type. DP, without neglecting or reducing the optical and mechanical properties of the bleached pulp.
  • step b) (ClO 2 ) in an alkaline medium makes it possible to reduce the quantity of organochlorine compounds generated in the effluents.
  • This effect has three origins (1) decrease in the quantity of chlorine dioxide to be introduced, thus reducing the quantity of active chlorine applied, (2) slight decrease in the degree of delignification of the dough, (3) reaction mechanism in an alkaline medium which does not involve the intermediate chlorinated species HClO (hypochlorous acid) and Cl 2 (chlorine or molecular chlorine), these two species being at the origin of the formation of organochlorine compounds by reacting with lignin.
  • this new stage generates less chlorate ions.
  • COD chemical oxygen demand
  • Example 1 process for bleaching a pre-bleached pulp according to the invention (D alk P) and its classic control sequence D 1 nD 2 (counterexample 1)
  • the device illustrated by figure 1 was used to implement this example.
  • Softwood kraft pulp 100 grams of dry lignocellulosic fibers per liter of fibrous suspension pre-bleached by a sequence using molecular oxygen, hydrogen peroxide, sodium hydroxide and a chelating agent (whose kappa index is 4.3; the whiteness 82% ISO and the viscosimetric average polymerization degree 1028) is treated in the laboratory with 0.4% by weight relative to the dry pulp of magnesium sulfate, then with 0.55% by weight based on the dry sodium hydroxide pulp (step a, the pH of this step is 9.5).
  • the pulp thus obtained is placed in a polyethylene plastic bag, then 2% chlorine dioxide by weight of active chlorine relative to the dry paper pulp are added.
  • the polyethylene bag containing the mixture obtained is immersed in a water bath thermostatically controlled at 45 ° C.
  • step c the pH of this step is 10.4.
  • step d 0.3% by weight relative to the dry hydrogen peroxide pulp is introduced.
  • step e the paste contained in the polyethylene bag is again immersed in the thermostatically controlled water bath for 90 minutes at 75 ° C.
  • the paste is then washed on a filter funnel of porosity n ° 2 with 10 L of water.
  • step b the concentrations of chlorate ions, chlorite ions and hypochlorite ions are measured in the bleaching effluents (Table 1).
  • a D 1 nD 2 type process (chlorine dioxide / neutralization / chlorine dioxide) is conventionally carried out in a pre-bleached pulp mill by the same sequence as in the previous paragraph (using molecular oxygen, hydrogen peroxide, sodium hydroxide and a chelating agent) on softwood kraft pulp (100 grams of lignocellulosic fibers per liter of fibrous suspension).
  • the paper pulp is contacted with 0.06% by weight relative to the dry sodium hydroxide pulp, then with 2.6% by weight relative to the dry active chlorine pulp, for 115 minutes at 75 ° C and at 10% consistency (D 1 ) (the pH of this step is 7).
  • the paper pulp is then washed on a filter funnel of porosity n ° 2 with 10 L of water and then it is contacted with 0.06% by weight relative to the dry paper pulp of sodium hydroxide and 0 , 65% by weight relative to the pulp of dry active chlorine for 115 minutes at 80 ° C. and at 10% consistency (D 2 ) (the pH of this step is 7.5).
  • the paste is then washed on a filter funnel of porosity n ° 2 with 10 L of water.
  • step D 1 and D 2 the concentrations of chlorate ions, chlorite ions and hypochlorite ions are measured in the bleaching effluents (Table 1).
  • the chlorite and chlorate ions are assayed after the D alk stage of the (D alk P ) stage; in fact, an iodometric determination of these species after the D alk P stage would be distorted by the presence of residual hydrogen peroxide, which also reacts with the iodide ions. It would then not be possible to obtain the quantities of chlorite, chlorate and hypochlorite ions, separately.
  • the (D alk P ) process according to the invention consumes 38% less chlorine dioxide.
  • the water consumption is greatly reduced (10 L to ensure the washing of the paste between D 1 and D 2 ).
  • the reaction time contact with ClO 2
  • the reaction time is reduced by 135 minutes (90 + 5 minutes vs 2 ⁇ 115 minutes) while maintaining the final whiteness of the pulp and without significantly increasing the depolymerization of the pulp. cellulose.
  • the bleaching process according to the invention is carried out continuously, without any intermediate washing step being necessary.
  • the bleaching process according to the invention thus makes it possible to consume less chlorine dioxide, to reduce the reaction time and to eliminate a washing step, without causing a loss of whiteness and without increasing depolymerization. cellulose.
  • the bleaching process according to the invention makes it possible to reduce the polluting load of the effluents (COD) (Table 3) (-33%).
  • Example 2 process for bleaching a pre-bleached pulp according to the invention (D ak P A) and according to the standard control sequence D 1 nD 2 (counter-example 2)
  • the device illustrated by figure 2 was used to implement this example.
  • Softwood kraft pulp 100 grams of lignocellulosic fibers per liter of fibrous suspension pre-bleached with a sequence using molecular oxygen, hydrogen peroxide, sodium hydroxide and a chelating agent.
  • This pulp has a kappa number of 5.2 as well as a whiteness of 78.6% ISO and an average viscosimetric degree of polymerization of 812. It is treated with 0.4% by weight relative to the dry paper pulp of magnesium sulfate, then with 0.63% by weight based on the dry sodium hydroxide pulp (step a, the pH of this step is 9.5).
  • the pulp thus obtained is introduced into a polyethylene plastic bag, then 2.2% of chlorine dioxide by weight of active chlorine relative to the dry paper pulp are added.
  • the polyethylene bag containing the mixture obtained is immersed in a water bath thermostatically controlled at 75 ° C (step b)
  • step c the pH of this step is 10.2.
  • step d the pH of this step is 10.2.
  • step e the paste contained in the polyethylene bag is again immersed in the thermostatically controlled water bath for 90 minutes at 75 ° C.
  • step f the pH of this step is of 3.8.
  • the acid step is necessary here. Compared to Example No. 1, the amount of lignin present in the paste is higher.
  • the paste is then washed on a filter funnel of porosity n ° 2 with 10 L of water.
  • the D ak P A process according to the invention consumes 32% less chlorine dioxide.
  • the water consumption is greatly reduced (10 L to ensure the washing of the paste between D 1 and D 2 ).
  • the reaction time is reduced by 75 minutes (5 + 90 + 60 minutes instead of 2 ⁇ 115 minutes) while maintaining the final whiteness, the mechanical properties of the pulp and without increasing the depolymerization of the cellulose (DPv ).
  • the treatment process according to the invention is carried out continuously, without any intermediate washing step being necessary.
  • the bleaching process according to the invention thus makes it possible to consume less chlorine dioxide, to reduce the reaction time and to eliminate a washing step, and this, without causing a loss of whiteness, a loss of mechanical properties. (before and after refining) and without increasing the depolymerization of the cellulose.
  • the bleaching process according to the invention makes it possible to reduce the quantity of organochlorine compounds (AOX) formed (-71.1%) and to reduce the polluting load of the effluents (COD) (-20.6%).

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
EP18703063.0A 2017-01-23 2018-01-18 Procede de blanchiment d'une pate a papier Active EP3571347B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1750512A FR3062138B1 (fr) 2017-01-23 2017-01-23 Procede de blanchiment d'une pate a papier
PCT/FR2018/050120 WO2018134525A1 (fr) 2017-01-23 2018-01-18 Procede de blanchiment d'une pate a papier

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EP3571347A1 EP3571347A1 (fr) 2019-11-27
EP3571347B1 true EP3571347B1 (fr) 2020-10-28

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CN (1) CN110177909A (ja)
AR (1) AR110905A1 (ja)
BR (1) BR112019014480B1 (ja)
CA (1) CA3049171A1 (ja)
CL (1) CL2019001865A1 (ja)
FR (1) FR3062138B1 (ja)
PT (1) PT3571347T (ja)
RU (1) RU2747664C2 (ja)
UY (1) UY37578A (ja)
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CN114277599A (zh) * 2021-12-17 2022-04-05 广西大学 一种低温中性二氧化氯漂白方法

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Publication number Priority date Publication date Assignee Title
US3884752A (en) * 1973-09-17 1975-05-20 Int Paper Co Single vessel wood pulp bleaching with chlorine dioxide followed by sodium hypochlorite or alkaline extraction
FR2589494B1 (fr) * 1985-10-30 1988-07-29 Atochem Procede de blanchiment de pates papetieres chimiques
DE69026105T2 (de) * 1989-10-19 1996-09-26 Univ North Carolina Hochleistendes verfahren zum bleichen von zellstoff mit chlordioxyd
US5268075A (en) * 1989-10-19 1993-12-07 North Carolina State University High efficiency two-step, high-low pH chlorine dioxide pulp bleaching process
WO1991005910A1 (en) * 1989-10-19 1991-05-02 North Carolina State University Chlorine dioxide pulp bleaching process using sequential chlorine addition
SE9000340L (sv) * 1990-01-31 1991-08-01 Eka Nobel Ab Foerfarande vid blekning av lignocellulosahaltigt material
NZ237019A (en) * 1990-02-19 1992-11-25 Amcor Ltd Bleaching paper pulp by initially treating with oxygen and/or hydrogen peroxide and subsequently treating with a bleaching agent without intervening washing steps
JPH04126885A (ja) * 1990-09-14 1992-04-27 Akio Onda 化学パルプの製造方法
SE502706E (sv) * 1994-04-05 1999-09-27 Mo Och Domsjoe Ab Framställnng av blekt cellulosamassa genom blekning med klordioxid och behandling av komplexbildare i samma steg
FR2747407B1 (fr) * 1996-04-12 1998-05-07 Atochem Elf Sa Procede de delignification et de blanchiment de pates a papier chimiques
CA2189724A1 (en) * 1996-07-08 1998-01-09 Suezone Chow Method of pulping
EP0925401B1 (fr) * 1996-09-11 2002-01-16 SOLVAY INTEROX (Société Anonyme) Procede de blanchiment de pate a papier
DE102010001001A1 (de) * 2010-01-19 2011-07-21 Evonik Degussa GmbH, 45128 Verfahren zur Delignifizierung und Bleiche von Zellstoff
CN103382671B (zh) 2013-07-29 2015-06-17 四川理工学院 一种高聚合度竹浆粕的清洁制浆技术
JP6194818B2 (ja) * 2014-02-28 2017-09-13 王子ホールディングス株式会社 ケミカルパルプの製造方法、及びそのパルプを含む紙または板紙
SE538752C2 (en) * 2014-11-21 2016-11-08 Innventia Ab Process for the production of a treated pulp, treated pulp, and textile fibers produced from the treated pulp
CN105200837A (zh) 2015-09-24 2015-12-30 广西大学 一种碱预处理辅助竹浆ecf漂白减少aox生成的方法

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JP2020514564A (ja) 2020-05-21
ZA201904595B (en) 2020-02-26
EP3571347A1 (fr) 2019-11-27
KR102531578B1 (ko) 2023-05-12
FR3062138B1 (fr) 2019-06-07
KR20190104340A (ko) 2019-09-09
RU2747664C2 (ru) 2021-05-11
AR110905A1 (es) 2019-05-15
PT3571347T (pt) 2020-12-11
CN110177909A (zh) 2019-08-27
RU2019121768A (ru) 2021-01-11
WO2018134525A1 (fr) 2018-07-26
UY37578A (es) 2018-08-31
CL2019001865A1 (es) 2019-11-22
BR112019014480B1 (pt) 2023-02-23
US11384480B2 (en) 2022-07-12
CA3049171A1 (en) 2018-07-26
US20190345672A1 (en) 2019-11-14
RU2019121768A3 (ja) 2021-03-24
BR112019014480A2 (pt) 2020-02-11
FR3062138A1 (fr) 2018-07-27

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