EP2350381B1 - Procede de fabrication de pate a papier - Google Patents

Procede de fabrication de pate a papier Download PDF

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Publication number
EP2350381B1
EP2350381B1 EP09756054.4A EP09756054A EP2350381B1 EP 2350381 B1 EP2350381 B1 EP 2350381B1 EP 09756054 A EP09756054 A EP 09756054A EP 2350381 B1 EP2350381 B1 EP 2350381B1
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EP
European Patent Office
Prior art keywords
pulp
equal
less
deacidification
bleaching
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.)
Not-in-force
Application number
EP09756054.4A
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German (de)
English (en)
French (fr)
Other versions
EP2350381A1 (fr
Inventor
Christophe Calais
Jean-Christophe Hostachy
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.)
Arkema France SA
ITT Manufacturing Enterprises LLC
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Arkema France SA
ITT Manufacturing Enterprises LLC
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Publication of EP2350381A1 publication Critical patent/EP2350381A1/fr
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/14—Disintegrating in mills
    • D21B1/16—Disintegrating in mills in the presence of chemical 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
    • 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
    • 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 a method of manufacturing paper pulp.
  • Paper pulps called "mechanical pulps” or “high-performance pulps” or “wood pulp” are obtained directly from the wood by a series of mechanical treatments (grinding and refining) carried out using grinding wheels and / or refiners .
  • the dough can then undergo a bleaching phase in one or more steps.
  • the ozone treatment causes particular problems, namely a decrease in the whiteness of the dough, a difficulty of subsequent whitening, a loss of yield relative to the wood, an increase in the chemical oxygen demand of the effluents of laundering.
  • the document FR 2329794 also describes an ozone treatment. After the treatment, the treated pulp is mixed with lye (soda) to stabilize the properties imparted to the dough by the ozone treatment. The dough is then stored and subsequently directly used without being bleached for papermaking.
  • lye lye
  • a treatment of mechanical pulp with ozone is described.
  • the treatment is followed by a maturation step of less than 30 minutes, preferably less than 10 minutes, during which the ozonated paste remains in an alkaline medium, optionally by being mixed with bleaching chemicals.
  • the document EP 0276608 provides an illustration of an ozone treatment method.
  • the examples of the document show that the treatment with ozone induces a loss of whiteness of the dough.
  • WO 2008/081078 describes the use of soda and other bases during the ozone treatment itself, in order to limit the harmful effect of organic acids produced during ozonation on the subsequent bleaching and corrosion.
  • the deacidification step has a duration greater than or equal to 1 hour and 30 minutes, preferably greater than or equal to 2 hours, ideally greater than or equal to 3 hours.
  • the pH at the end of the deacidification step is between 7 and 8.
  • the pH varies by less than 0.1 units during the last 30 minutes of the deacidification step, preferably less than 0.05 units.
  • the method comprises a step of chelation, preferably between the deacidification step and the bleaching step, comprising contacting the deacidified dough with a chelating composition comprising a chelating agent, preferably ethylene diamine tetra-acetic acid or one of its sodium salts or diethylene triamine penta-acetic acid or a sodium salt thereof.
  • a chelating agent preferably ethylene diamine tetra-acetic acid or one of its sodium salts or diethylene triamine penta-acetic acid or a sodium salt thereof.
  • alkaline agent preferably 15 kg or less, more preferably 10 kg or less, per ton of mechanical pulp are used during the deacidification step.
  • the loss of wood yield at the end of the bleaching step is less than or equal to 20%, preferably less than or equal to 16%, ideally less than or equal to 13%, or even less than or equal to equal to 10%.
  • the whiteness of the dough at the end of the bleaching step is greater than or equal to 65%, preferably greater than or equal to 66.5%, ideally greater than or equal to 68%, or even greater or equal to 70%.
  • the process produces effluents whose chemical oxygen demand is less than or equal to 210 kg per ton of pulp, preferably less than or equal to 180 kg per ton of pulp, more preferably less than or equal to at 160 kg per tonne of dough, or even less than or equal to 145 kg per tonne of dough.
  • the mechanical pulp is a paste SGW, PGW, RMP, TMP, HTMP or CTMP.
  • the wood is a softwood, hardwood or mixture thereof, preferably a softwood, and more preferably a pine or spruce wood.
  • the invention also relates to a papermaking process, comprising the manufacture of paper pulp according to the method described above, as well as the use of this paper pulp to produce paper.
  • the present invention overcomes the disadvantages of the state of the art. In particular, it provides a more efficient pulp bleaching process, with better yield and / or using a smaller amount of chemicals and / or generating less effluent to be treated.
  • the acids located inside the fibers tend to be released gradually; the nature and the duration of the deacidification according to the invention are therefore adapted to obtain a stable pH before the bleaching step, which makes it possible to neutralize all the acidic species and to obtain an improved bleaching.
  • the figure 1 represents an example of pH evolution during a deacidification step according to the invention (experimental measurement).
  • the abscissa is the time in minutes, and the ordinate is the pH.
  • the expression "the pH varies by less than X unit during the last 30 minutes of the deacidification step” means that the absolute value of the difference between the pH measured at the end of the deacidification step and the pH measured 30 minutes before the end of the deacidification step is less than X unit.
  • the "end of the deacidification step” coincides with the beginning of the next step.
  • the beginning of the next step can refer to the beginning of the chelation step or the beginning of the bleaching step; but it may also designate the beginning of an intermediate washing step or the beginning of an intermediate step of consistency change.
  • the next step is a new action, which differs from the deacidification action and immediately follows it.
  • the refining and the ozone treatment of the wood are carried out conventionally in the field.
  • the raw material is any kind of suitable wood: especially resinous, leafy or a mixture of both.
  • suitable wood especially resinous, leafy or a mixture of both.
  • softwood By way of example of suitable species, mention may be made of pine and spruce.
  • the wood may undergo one or more preliminary treatments before refining, such as debarking, removal of knots from wood, heat treatment, pressurization, chipping, logs, logs or other ...
  • Refining includes grinding or grating (grinding) by grinding (under water flow) or in a disc refiner.
  • Refining can include several stages. For example, after a first grinding / grinding, the product can be separated into an accepted fraction and a rejected fraction, and the rejected fraction can be refined again before mixing with the accepted fraction. It is possible to provide for such intermediate separations several times.
  • ozone treatment ozonation
  • the ozone treatment thus makes it possible to reduce the specific energy required for separating the fibers and to increase the mechanical properties of the pulp thus treated.
  • the ozone treatment is carried out according to the methods known to those skilled in the art, for example according to the methods described in the documents of the state of the art mentioned in the introduction of the present application.
  • the ozone charge is typically 0.5 to 8%, preferably 1 to 4%.
  • the ozone treatment may concern all the pulp or a fraction only, for example the fraction released from the separation after the first refining.
  • a pH adjustment may optionally be carried out during ozonation or before ozonation, for example by means of an addition of alkaline agent, especially sodium hydroxide.
  • alkaline agent especially sodium hydroxide.
  • Deacidification preferably occurs after refining / ozone treatment, ie once the refining / ozone treatment is complete. It consists in neutralizing the acidic by-products generated by the action of ozone on the constituents of the wood, acid by-products that have accumulated inside and outside. outside (immediate environment) of wood fibers. Even if a base has been used before or during ozonation, the deacidification in question here is still useful for neutralizing the acid species, since the acids inside the fibers are released after the ozonation and the dough suspension tends to become more and more acidic over time.
  • the deacidification comprises, preferably consists of bringing the mechanical pulp resulting from the first step into contact with a deacidification composition.
  • the placing in contact is preferably carried out by simple mixing.
  • the pH is in a range of pH 3 to 5, depending on the treatment with ozone (amount of ozone, addition or no sodium hydroxide before or during ozonation).
  • the pH is in a range of 6 to 12, preferably 7 to 8.
  • the deacidification composition is preferably an aqueous solution comprising an alkaline agent.
  • This alkaline agent may be selected from oxides, hydroxides, silicates and carbonates of alkali metals and alkaline earth metals, ammonia, ammonia and mixtures thereof.
  • the basic species preferred for the choice of the alkaline agent mention may be made of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate magnesium carbonate and mixtures thereof.
  • the alkaline agent comprises a mild base.
  • soft base is meant a base which dissociates only partially in water (pKb> 0) and / or which has a low solubility.
  • the alkaline agent may comprise a mild base selected from magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate, magnesium carbonate and mixtures thereof, preferably magnesium hydroxide .
  • the alkaline agent comprises a mild base as mentioned above in combination with another base, for example sodium hydroxide (or potassium hydroxide). But it is preferred that the deacidification composition does not contain sodium hydroxide (or potassium hydroxide) and that the alkaline agent consists of a mild base as defined above.
  • the use of a mild base such as magnesium hydroxide minimizes the phenomenon of extraction and dissolution of some components of the wood oxidized after the action of ozone. As a result, the yield loss is lower and the pollutant load resulting from the extraction phenomenon is reduced.
  • the amount of alkaline agent used in the deacidification step is preferably less than or equal to 20 kg, more preferably less than or equal to 15 kg, ideally less than or equal to 10 kg, per tonne of mechanical pulp.
  • the duration of the deacidification step is preferably greater than 1 hour, more preferably greater than or equal to 1 hour and 30 minutes, ideally greater than or equal to 2 hours or even greater than or equal to 3 hours, in order to optimize the positive effect of this step on total yield, effluent production and whiteness.
  • the deacidification step is preferably carried out at a temperature of between 4 and 95 ° C, more preferably between 25 and 85 ° C, most preferably between 35 and 80 ° C. A temperature of about 70 ° C is particularly suitable.
  • the consistency during the deacidification step is preferably between 0.5 and 10%, more preferably between 1 and 5%, ideally between 2 and 3%.
  • the value of the consistency or dryness of the dough corresponds to the percentage of dry matter expressed relative to water.
  • the consistency is the ratio of the dough mass to the mass of the suspension (which includes paste, water and added chemical compounds). In other words, it is the mass concentration of paste in the aqueous medium.
  • the chelation is preferably carried out after the deacidification, that is to say once the deacidification step is complete.
  • the chelation comprises, preferably consists of bringing the mechanical pulp from the second step into contact with a chelating composition.
  • the chelating composition is preferably an aqueous solution comprising a chelating agent.
  • the chelating agent may be any chemical compound conventionally used for this purpose in the field. Preferably it is ethylene diamine tetra-acetic acid or a sodium salt thereof, or diethylene triamine penta-acetic acid or a sodium salt thereof.
  • the chelating agent has a particular affinity for trace metal cations in the pulp.
  • the purpose of the chelation treatment is to neutralize these cations by sequestering them and removing them from the dough by washing it. Performing the chelation step helps to improve the performance of the hydrogen peroxide bleaching treatment.
  • the amount of chelating agent used during the chelation step is typically between 0.5 and 30 kg, preferably between 1 and 20 kg, more preferably between 2 and 10 kg, ideally between 3 and 5 kg. , per ton of mechanical pulp.
  • the duration of the chelation step is preferably greater than or equal to about 30 minutes.
  • the chelation step is preferably carried out at a temperature of between 4 and 95 ° C, more preferably between 25 and 85 ° C, most preferably between 35 and 80 ° C. A temperature of about 70 ° C is particularly suitable.
  • the consistency during the chelation step is preferably between 0.5 and 10%, more preferably between 1 and 5%, ideally between 2 and 3%.
  • the bleaching preferably occurs after the chelation (or after the deacidification if the chelation is absent), that is to say once the chelation step (or the deacidification step if the chelation is absent) is completed. .
  • the bleaching comprises, preferably, the contacting of the mechanical pulp from the third step with a bleaching composition.
  • the consistency during the bleaching step is preferably between 5 and 50%, more preferably between 10 and 45%, ideally between 20 and 40%.
  • Bleaching has faster kinetics at high consistency (whereas for chelation, kinetics are fast even at low consistency).
  • the consistency of the paste can be increased by pressing it for example, and by eliminating filtrates comprising in particular the chelated metals.
  • the placing in contact is preferably carried out by simple mixing of the bleaching composition with the paste.
  • the type of equipment used for mixing is adapted according to the consistency of the dough: direct mixing by means of an injection pump if the consistency is low or medium (less than 10%); mixer or mixer for a higher consistency up to about 40%).
  • the bleaching composition is preferably an aqueous solution comprising a bleaching agent and an alkaline agent.
  • the bleaching agent may be any chemical compound conventionally used for this purpose in the field. Preferably it is hydrogen peroxide. It is also possible to use sodium hydrosulphite.
  • the alkaline agent may comprise (or consist of) a soft base as defined in the second step.
  • the alkaline agent may comprise (or consist of) a base other than a mild base as defined in the second step, for example comprising (or consist of) sodium hydroxide (or potassium hydroxide). ).
  • the alkaline agent may comprise (or consist of) a mixture of a soft base as defined in the second step and a base different from such a soft base (for example sodium or potassium hydroxide).
  • a base different from such a soft base for example sodium or potassium hydroxide.
  • a mixture of sodium hydroxide and magnesium hydroxide is a preferred alkaline agent in the bleaching composition.
  • the mass ratio between the soft base and the base different from a mild base is between 0.001 and 1000, preferably between 0.01 and 100, more preferably between 0.1 and 10, and most preferably between 0.2 and 5.
  • a soft base in the bleaching composition minimizes the phenomenon of extraction and dissolution of some oxidized wood components after the action of ozone. Consequently, the use of a soft base makes it possible to further improve the wood yield, to reduce the effluents and the consumption of chemicals, and even to improve the whiteness of the dough.
  • the mass ratio between the soft base and the base different from a soft base generally results from a compromise between whiteness and efficiency.
  • the alkaline agent of the bleaching composition comprises sodium silicate.
  • Sodium silicate has an auxiliary stabilizing function of the bleaching agent (especially hydrogen peroxide). It is also possible to provide in the bleaching composition another stabilizing agent in addition to or instead of sodium silicate. Polyhydroxyacrylate compounds are possible stabilizing agents.
  • the amount of bleaching agent used is typically between 5 and 100 kg, preferably between 10 and 50 kg, more preferably between 20 and 40 kg per tonne of mechanical pulp.
  • the amount of alkaline agent used is typically between 5 and 100 kg, preferably between 10 and 70 kg per ton of mechanical pulp.
  • the bleaching composition may also comprise a chelating agent as defined above, especially if the chelation step is absent or has resulted in incomplete chelation.
  • the bleaching composition can be prepared separately and then brought into contact with the dough, but it can also be prepared directly in contact with the dough. In this second case, the various compounds of the bleaching composition are successively directly added to the dough.
  • the duration of the bleaching step varies depending on the type of agent used.
  • this duration is typically between 10 minutes and 8 hours, preferably between 30 minutes and 6 hours, more preferably between 2 hours and 4 hours.
  • the bleaching step is preferably carried out at a temperature of between 4 and 95 ° C, more preferably between 25 and 85 ° C, most preferably between 35 and 80 ° C. A temperature of about 70 ° C is particularly suitable.
  • the whiteness of the dough is defined according to ISO 2470.
  • the yield loss of the process is the sum of the yield losses observed for each of the deacidification steps (when it is implemented), chelation and bleaching. This value does not take into account the ozonation step.
  • the chemical oxygen demand of the effluents is defined according to the ISO 15705 standard, the measurement being carried out using a Hach DR / 2000 spectrophotometer.
  • a pine paste is prepared according to the TMP process.
  • the pulp undergoes an ozone treatment during the refining phase. Specifically, primary refiner releases are treated with 2% ozone, pH being adjusted with 5 kg of soda per tonne of pulp; then the ozone-treated rejects are mixed with the accepted fraction of the secondary refiner.
  • the whiteness of the pulp after the refining / treatment with ozone is 47.3%.
  • a chelation step is planned, during which the pulp is treated with 4 kg of DTPA per ton of pulp, at a consistency of 4% and at a temperature of 70 ° C., at pH 6-7, for 1 hour.
  • the pulp undergoes a bleaching step, at a consistency of 20%, at a temperature of 70 ° C and for a period of 2 hours.
  • pulp A on the one hand and pasta B, C and D on the other hand reveals that the presence of the deacidification step makes it possible to improve the whiteness of the dough, the wood yield of the process and to reduce the COD.
  • pulp B and pulp C reveals that the use of magnesium hydroxide in place of sodium hydroxide during the deacidification step, with a reduction of 30% of the amount of chemical required, improve the wood yield of the process and reduce the COD, for a whiteness only slightly lower.
  • pulp C and pulp D reveals that a reduction of about 75% of the mass of sodium hydroxide used during the bleaching step, and the replacement of about 41% of this sodium hydroxide.
  • magnesium hydroxide can reduce yield loss and COD by 20%.
  • a pine paste is prepared according to the TMP process.
  • the pulp undergoes an ozone treatment during the refining phase. Specifically, releases of the primary refiner are treated with 2% ozone, the pH not being adjusted; then the ozone-treated rejects are mixed with the accepted fraction of the secondary refiner.
  • the whiteness of the pulp after the refining / treatment with ozone is 48.3%.
  • a chelation step is provided, during which the pulp is treated with 4 kg of DTPA per ton of pulp, at a consistency of 2-3% and at a temperature of 70 ° C, at pH 6-7, for 1 hour.
  • the pulp undergoes a bleaching step, at a consistency of 20%, at a temperature of 70 ° C and for a period of 2 hours.
  • a spruce paste is prepared according to the TMP process.
  • the pulp undergoes an ozone treatment during the refining phase. Specifically, releases of the primary refiner are treated with 2% ozone, the pH not being adjusted; then the ozone-treated rejects are mixed with the accepted fraction of the secondary refiner.
  • the whiteness of the pulp after the refining / treatment with ozone is 51.2%.
  • a chelation step is provided, during which the pulp is treated with 4 kg of DTPA per ton of pulp, at a consistency of 2-3% and at a temperature of 70 ° C, at pH 6-7, for 1 hour.
  • the pulp undergoes a bleaching step, at a consistency of 20%, at a temperature of 70 ° C and for a period of 2 hours.
  • the same parameters as for the paste I are used, except that there is no deacidification step, and the amount of sodium hydroxide used in the bleaching composition is 37.5 kg / ton of dough.
  • the same parameters are used as for the pulp J, except that the duration of the deacidification step is only 30 minutes.
  • the same parameters as for the paste J are used, except that the duration of the deacidification step is 90 minutes.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Paper (AREA)
EP09756054.4A 2008-10-24 2009-10-23 Procede de fabrication de pate a papier Not-in-force EP2350381B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0805907A FR2937656B1 (fr) 2008-10-24 2008-10-24 Procede de fabrication de pate a papier
PCT/IB2009/007208 WO2010046768A1 (fr) 2008-10-24 2009-10-23 Procede de fabrication de pate a papier

Publications (2)

Publication Number Publication Date
EP2350381A1 EP2350381A1 (fr) 2011-08-03
EP2350381B1 true EP2350381B1 (fr) 2016-08-17

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EP09756054.4A Not-in-force EP2350381B1 (fr) 2008-10-24 2009-10-23 Procede de fabrication de pate a papier

Country Status (8)

Country Link
US (1) US20120118518A1 (zh)
EP (1) EP2350381B1 (zh)
JP (1) JP5275472B2 (zh)
CN (1) CN102197174B (zh)
CA (1) CA2739694C (zh)
FR (1) FR2937656B1 (zh)
RU (1) RU2445413C1 (zh)
WO (1) WO2010046768A1 (zh)

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JP5822101B2 (ja) 2010-08-04 2015-11-24 愛媛県 セルロース溶液の製造方法、セルロース析出体の製造方法、及びセルロースの糖化方法
CN102268842B (zh) * 2011-07-28 2013-03-13 广东工业大学 可溶性四硼酸盐作为纸张脱酸剂用于纸张脱酸的方法
CN102828443B (zh) * 2011-07-28 2014-08-13 广东工业大学 利用可溶性四硼酸盐在超临界co2状态下进行脱酸的方法
FR3007044B1 (fr) * 2013-06-13 2016-01-15 Air Liquide Procede de traitement des pates papetieres chimiques par traitement a l'ozone en presence d'ions magnesium
CN105133408A (zh) * 2015-09-01 2015-12-09 安庆市新宜纸业有限公司 一种纸浆的生产工艺
CN113930998B (zh) * 2021-09-15 2022-09-30 华南理工大学 一种臭氧联合过氧化氢的化学机械浆生产方法

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FI67413C (fi) * 1977-04-27 1985-03-11 Myrens Verksted As Foerfarande foer behandling av finfoerdelad fiberhaltig eller cellulosahaltig massa samt anordning foer utfoerande av foerfarandet
NO142091C (no) * 1977-10-17 1980-06-25 Myrens Verksted As Fremgangsmaate ved ozonbehandling av raffinoermekanisk og termomekanisk masse.
FR2609067B1 (fr) * 1986-12-31 1990-06-15 Beghin Say Sa Procede pour le traitement a l'ozone d'une pate cellulosique
FR2661431B1 (fr) * 1990-04-30 1992-07-17 Atochem Procede de blanchiment au peroxyde de l'hydrogene de pates a papier a haut rendement.
RU2084574C1 (ru) * 1992-04-06 1997-07-20 А.Альстрем Корпорейшн Способ получения целлюлозной массы
WO2001055502A1 (en) * 2000-01-28 2001-08-02 Martin Marietta Magnesia Specialties, Inc. Process employing magnesium hydroxide in peroxide bleaching of mechanical pulp
JP4738662B2 (ja) * 2001-08-03 2011-08-03 日本製紙株式会社 新聞用紙
FI119062B (fi) * 2006-12-28 2008-07-15 Upm Kymmene Corp Menetelmä mekaanisen massan valmistamiseksi

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US20120118518A1 (en) 2012-05-17
RU2445413C1 (ru) 2012-03-20
CN102197174A (zh) 2011-09-21
CA2739694C (fr) 2013-05-28
EP2350381A1 (fr) 2011-08-03
WO2010046768A1 (fr) 2010-04-29
FR2937656B1 (fr) 2010-11-19
CN102197174B (zh) 2013-04-24
FR2937656A1 (fr) 2010-04-30
CA2739694A1 (fr) 2010-04-29
JP2012506501A (ja) 2012-03-15
JP5275472B2 (ja) 2013-08-28

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