[go: up one dir, main page]

EP1954871B1 - Process of producing high-yield pulp - Google Patents

Process of producing high-yield pulp Download PDF

Info

Publication number
EP1954871B1
EP1954871B1 EP06813080A EP06813080A EP1954871B1 EP 1954871 B1 EP1954871 B1 EP 1954871B1 EP 06813080 A EP06813080 A EP 06813080A EP 06813080 A EP06813080 A EP 06813080A EP 1954871 B1 EP1954871 B1 EP 1954871B1
Authority
EP
European Patent Office
Prior art keywords
pulp
tmp
containing material
process according
previous
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
EP06813080A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1954871A1 (en
Inventor
Karin Susanne Maria Walter
Eva Linnea Elisabeth Wackerberg
Magnus Lars Paulsson
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.)
Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Akzo Nobel NV
Eka Chemicals AB
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 Akzo Nobel NV, Eka Chemicals AB filed Critical Akzo Nobel NV
Priority to EP06813080A priority Critical patent/EP1954871B1/en
Publication of EP1954871A1 publication Critical patent/EP1954871A1/en
Application granted granted Critical
Publication of EP1954871B1 publication Critical patent/EP1954871B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • D21B1/02—Pretreatment of the raw materials by chemical or physical means
    • 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 producing a high-yield pulp from a lignocellulose containing material.
  • thermomechanical pulp Enhanced production and efficient utilization of lignocellulosic products are issues of high importance to both the pulp and paper industry and society.
  • the production of mechanical and chemimechanical pulps is an efficient way of using the world's natural resources since the yield of these manufacturing processes is high and the environmental impact is relatively low.
  • Mechanical and chemimechanical pulping constitute about 25% of the total virgin fibre production in the world.
  • One drawback with mechanical pulping processes is the high energy consumption that represents about 20% of the energy demand of papermaking in the world. The energy alone represents 25-50% of the total manufacturing cost of a thermomechanical pulp (TMP) depending on where in the world the mechanical pulp mill is located.
  • TMP thermomechanical pulp
  • EP 494 519 A1 relates to a process comprising impregnating chips with an alkaline peroxide solution containing stabilizers for peroxide followed by mechanical defibration, in which the wood chips are pre-treated prior to peroxide impregnation.
  • the process of EP 494 519 A1 involves extensive capital investment and does not result in sufficient energy saving with maintained pulp yield and pulp properties.
  • One object of the invention is to reduce the energy consumption in a process which is simple to install in a high-yield pulping process and without substantially reducing the fibre length or strength properties of the produced pulp.
  • a further object of the present invention is to provide such a process while maintaining the pulp yield at an acceptable level.
  • a further intention of the present invention is to provide a facilitated process without need of considerable capital investments.
  • a further intention is to provide a process in the absence of alkaline treatment stages while improving or at least not substantially affecting properties of the obtained high-yield pulp, e.g. strength properties.
  • the present invention relates to a process for preparing a high-yield pulp comprising
  • the pH is from about 2.5 to about 6, for example from about 2.5 to about 5.5 or from about 3 to about 5.5 such as from about 3 to about 4. According to one embodiment, the pH is from about 3.5 to about 5.
  • the lignocellulose containing material is not chemically treated between stages a) and b) at a pH from about 7 to about 14, for example from about 8 to about 14 or from about 9 to about 14, e.g. from about 10 to about 14 or from about 10.5 to about 14 or from about 11 to about 14.
  • the lignocellulose containing material is not chemically treated before stage a) at a pH from about 7 to about 14, for example from about 8 to about 14 or from about 9 to about 14, e.g. from about 10 to about 14 or from about 10.5 to about 14 or from about 11 to about 14 or from about 11.5 to about 14.
  • high-yield pulp may comprise e.g. mechanical pulp (MP), refiner mechanical pulp (RMP), pressurized refiner mechanical pulp (PRMP), thermomechanical pulp (TMP), thermomechanical chemical pulp (TMCP), high-temperature TMP (HT-TMP) RTS-TMP, Thermopulp, groundwood pulp (GW), stone groundwood pulp (SGW), pressure groundwood pulp (PGW), super pressure groundwood pulp (PGW-S), thermo groundwood pulp (TGW), thermo stone groundwood pulp (TSGW), chemimechanical pulp (CMP), chemirefinermechanical pulp (CRMP), chemithermomechanical pulp (CTMP), high-temperature CTMP (HT-CTMP), sulphite-modified thermomechanical pulp (SMTMP), reject CTMP (CTMP R ), groundwood CTMP (G-CTMP), semichemical pulp (SC), neutral sulphite semi chemical pulp (NSSC), high-yield sulphite pulp (HYS), biomechanical pulp (BRMP), pulps produced according to the r
  • the high-yield pulp has a yield of at least about 60%, for example at least about 70%, or at least about 80%, or at least about 85%. According to one embodiment, the high-yield pulp has a yield of at least about 90% such as at least about 95%.
  • the pulp may be a bleached or non-bleached pulp.
  • the lignocellulose containing material comprises non-defibrated wood.
  • the lignocellulose containing material comprises mechanically treated lignocellulose containing material.
  • the oxidising system is applied between two mechanical treatment stages.
  • the lignocellulose containing material may comprise e.g. wood logs, finely-divided raw materials, including woody materials, such as wood particles (e.g. in the form of wood chips, wood shavings, wood fibres and saw dust) and fibres of annual or perennial plants including non-wood.
  • the woody raw material can be derived from hardwood or softwood species, such as birch, beech, aspen such as European aspen, alder, eucalyptus, maple, acacia, mixed tropical hardwood, pine such as loblolly pine, fir, hemlock, larch, spruce such as Black spruce or Norway spruce, and mixtures thereof.
  • Non-wood plant raw material can be provided from e.g. straws of grain crops, reed canary grass, reeds, flax, hemp, kenaf, jute, ramie, sisal, abaca, coir, bamboo, bagasse or combinations thereof.
  • the oxidant is selected from peroxy compounds, halogen containing oxidants, oxygen, nitrogen oxides or combinations thereof.
  • the oxidising system, including the non-enzymatic oxidant, being substantially free from ozone can be advantageous due to the fact that ozone does not provide a sufficient pulp yield due to low selectivity and is usually a more expensive alternative.
  • substantially free from ozone is meant that the oxidising system comprises less than 5 wt%, for example less than 2 wt% or less than 1 wt% ozone (calculated as 100%) based on the total weight of the oxidising system.
  • the oxidising system comprises less than 5 wt%, or less than 2 wt% or less than 1 wt% chlorine dioxide (calculated as 100%) based on the total weight of oxidising system.
  • the non-enzymatic oxidant and the activator can be added at any position prior to or during any mechanical treatment stage.
  • the oxidising system is applied to the lignocellulose containing material at one or several stages before or during mechanical treatment.
  • the oxidising system is applied as an inter-stage treatment between two mechanical treatment stages.
  • the process uses two or three mechanical treatment stages such as refining stages between which treatment of the lignocellulose containing material can be performed with the oxidising system.
  • any other number of stages may also be used including one or several reject refining stages.
  • the oxidising system is applied to a reject refining stage.
  • the activator may be any suitable substance capable of accelerating the oxidation in the presence of a non-enzymatic oxidant.
  • the activator is selected from metal ions, TAED, cyanamide, cupper sulfate, iron sulfate, and mixtures thereof.
  • the activator is a transition metal.
  • the oxidising system comprises an enhancer that facilitates/controls the oxidation.
  • the enhancer is selected from nitrogen-containing polycarboxylic acids, nitrogen-containing polyphosphonic acids, nitrogen-containing polyalcohols, oxalic acid, oxalate, glycolate, ascorbic acid, citric acid nitrilo acetate, gallic acid, fulvic acid, itaconic acid, haemoglobin, hydroxybenzenes, catecholates, quinolines, dimethoxybenzoic acids, dihydroxybenzoic acids, dimethoxybenzylalcohols, pyridine, histidylglycine, phthalocyanine, acetonitrile, 18-crown-6-ether, mercaptosuccinic acid, cyclohexadienes, polyoxomethalates, and combinations thereof.
  • the enhancer is selected from nitrogen-containing organic compounds, primarily nitrogen-containing polycarboxylic acids, nitrogen-containing polyphosphonic acids, nitrogen-containing polyalcohols, and mixtures thereof.
  • the enhancer is selected from diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and combinations thereof.
  • the enhancer is selected from compounds based on other aminopolycarboxylic acids, polyphosphates or polyphosphonic acids, hydroxycarboxylates, hydrocarboxylic acids, dithiocarbamate, oxalic acid, iminodisuccinic acid, [S,S']-etylenediaminedisuccinic acid, glycolate, ascorbic acid, citric acid, nitrilo acetate, gallic acid, fulvic acid, itaconic acid.
  • the enhancer is selected from oxalate, haemoglobin, dihydroxybenzene (e.g. hydroquinone), trihydroxybenzene, catecholates (e.g.
  • the oxidising system comprises as an enhancer also at least one enzyme.
  • the lignocellulose containing material is treated with the oxidising system for from about one second to about ten hours. According to one embodiment, the lignocellulose containing material is treated with the oxidising system for from about five seconds to about five hours. According to one embodiment, the lignocellulose containing material is treated with the oxidising system for from about ten seconds to about three hours.
  • the lignocellulose containing material is treated at a temperature from about 30 to about 200°C. According to one embodiment, the lignocellulose containing material is treated at a temperature from about 50 to about 180°C. According to one embodiment, the lignocellulose containing material is treated at a temperature from about 80 to about 180°C.
  • the non-enzymatic oxidant (calculated as 100%) is added in an amount from about 0.1 to about 5 wt% based on the weight of the lignocellulose containing material. According to one embodiment, the non-enzymatic oxidant (calculated as 100%) is added in an amount from about 0.2 to about 3 wt% based on the weight of the lignocellulose containing material. According to one embodiment, the non-enzymatic oxidant (calculated as 100%) is added in an amount from about 0.3% to about 2 wt% based on the weight of the lignocellulose containing material.
  • an activator (calculated as 100%) is added in an amount from about 0.0001 to about 1 wt% based on the weight of the lignocellulose containing material. According to one embodiment, an activator (calculated as 100%) is added in an amount from about 0.001 to about 0.5 wt% based on the weight of the lignocellulose containing material. According to one embodiment, an activator (calculated as 100%) is added in an amount from about 0.0025 to about 0.1 wt% based on the weight of the lignocellulose containing material. According to one embodiment, an activator is added prior to or during any mechanical treatment stage, either separately or simultaneously with a non-enzymatic oxidant.
  • the activator may thus be added either before, simultaneously or after the addition of a non-enzymatic oxidant. This may be just before the addition of a non-enzymatic oxidant before a mechanical treatment stage such as a refiner, but may also be before e.g. a primary refiner whereas the non-enzymatic oxidant is added after the primary refiner but before a secondary refiner.
  • an enhancer (calculated as 100%) is added in an amount from about 0.001 to about 1 wt% based on the weight of lignocellulose containing material. According to one embodiment, an enhancer (calculated as 100% pure compound) is added in an amount from about 0.01 to about 0.5 wt% based on the weight of the lignocellulose containing material. According to one embodiment, an enhancer (calculated as 100%) is added in an amount from about 0.05 to about 0.3 wt% based on the weight of the lignocellulose containing material. According to one embodiment, an enhancer is added prior to or during any mechanical treatment stage, either separately or simultaneously with a non-enzymatic oxidant and optionally an activator.
  • the enhancer may thus be added either before, simultaneously or after the addition of a non-enzymatic oxidant. This may be just before the addition of the non-enzymatic oxidant before a mechanical treatment stage such as a refiner, but may also be before e.g. a primary refiner whereas the non-enzymatic oxidant is added after the primary refiner but before a secondary refiner.
  • the mechanical treatment may be performed in one or several stages. Typically, the mechanical treatment may be performed in two stages or more including a reject mechanical treatment stage where up to 60 wt% of the lignocellulose containing material may be passed through.
  • the mechanical treatment stages usually are performed by passing the lignocellulose containing material through grinders and/or refiners. However, other mechanical treatments may also be performed in equipments as, e.g. plug screws (e.g. impressafiner), roller mills (e.g. Szego mill), double shaft extruders (Bi-Vis screw extruder), the reciprocating apparatus, RT Fiberizer TM , dispersers or in any combinations thereof.
  • the non-enzymatic oxidant is selected from inorganic peroxy compounds such as hydrogen peroxide or hydrogen peroxide generating compounds such as salts of percarbonate, perborate, peroxysulfate, peroxyphosphate, peroxysilicate or corresponding weak acids.
  • inorganic peroxy compounds such as hydrogen peroxide or hydrogen peroxide generating compounds such as salts of percarbonate, perborate, peroxysulfate, peroxyphosphate, peroxysilicate or corresponding weak acids.
  • the non-enzymatic oxidant is selected from organic peroxy compounds such as peroxy carboxylic acids, e.g. peracetic acid and perbenzoic acid.
  • the oxidising system comprises halogen containing oxidants such as chlorite, hypochlorite, chloro sodium salt of cyanuric acid.
  • the oxidising system comprises oxygen and/or nitrogen oxides such as NO or NO 2 .
  • the oxidizing system comprises combinations of different oxidants, which can be either added or re-used from the process steps which generate the non-enzymatic oxidants.
  • the oxidising system further comprises activators such as metal ions, e.g. Fe, Mn, Co, Cu, W or Mo, or TAED, cyanamide or combinations thereof.
  • activators such as metal ions, e.g. Fe, Mn, Co, Cu, W or Mo, or TAED, cyanamide or combinations thereof.
  • metal ions such as transistion metal ions may be used in the form of acids or salts or complexes with common organic or inorganic compounds.
  • ultraviolet radiation or other radiation is applied to the non-enzymatic oxidant or to the lignocellulose containing material being treated with the non-enzymatic oxidant, optionally in combination with an enhancer.
  • enhancers e.g. complexing agents, chelating agents or ligands are comprised in the oxidising system. These enhancers may facilitate/control the oxidising effect depending on the amount thereof being added.
  • both an enhancer and an activator are comprised in the oxidising system.
  • Black spruce ( Picea mariana ) wood was used for the production of thermomechanical pulp (TMP).
  • TMP thermomechanical pulp
  • the wood logs were debarked and chipped and washed prior to preheating (4.14 bar steaming pressure, 40 s retention time) and refining operations.
  • a three-stage refining setup was used and the energy input was varied in the last refining stage to obtain pulps with different freeness (refining) levels.
  • a single disc 36" pressurized refiner (model 36-1CP run at 1800 rpm) was used in the first refining stage and a double disc 36" atmospheric refiner (model 401, 1200 rpm) in the second and third stages.
  • the energy input in the primary refiner was about 500 kWh/bone dry metric ton (bdmt) and in the second refining stage approximately 1000 kWh/bdmt. In most cases, three tertiary refining stages with a targeted energy input of 400, 800 and 1200 kWh/bdmt were performed. All trials were run at constant conditions which mean that the variation in specific energy consumption and pulp and paper properties is a result of the chemicals added during the trials.
  • the energy consumption measured in the pilot plant for the references (TMP Ref1 and TMP Ref2 , see tables and figures below) is comparable to commercial operation.
  • TMP Ref1 in figures and tables below was produced without addition of chemicals.
  • the degree of refining (freeness) as a function of the specific energy consumption (SEC) can be seen in Figure 1 and the strength of the resulting pulp in Tables 1 and 2.
  • Figure 2 shows the fibre length distribution and Figure 3 the fibre width distribution of the resulting pulp (freeness of approximately 100 ml CSF).
  • TMP Ref2 A TMP reference produced under more acidic conditions (denoted TMP Ref2 ) was also provided to make sure that the energy reduction obtained is a consequence of the method described in the present invention and not an effect of lowering the pH during refining.
  • the pH was lowered by adding 0.19 wt% sulphuric acid (H 2 SO 4 ) based on the weight of bone dry wood to the refiner eye (inlet) of the primary refiner.
  • the pH of the resulting pulp was 3.8.
  • the TMP properties of the produced pulp can be found in Figures 1-3 and Tables 1-2 below.
  • a TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.08 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood to the refiner eye of the primary refiner and 1.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the blow line of the primary refiner.
  • the pH of the resulting pulp was 3.6.
  • the pulp is denoted TMP HP1Fe in figures and tables below.
  • a second TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.15 wt% (of bone dry wood) iron sulfate (FeSO 4 x 7 H 2 O) to the refiner eye of the primary refiner and 1.1 wt% (of bone dry wood) hydrogen peroxide (H 2 O 2 ) to the blow line of the primary refiner.
  • the pH of the resulting pulp was 3.4.
  • the pulp is denoted TMP HP2Fe in Figures 1-3 and Tables 1-2 below.
  • the degree of refining measured as the freeness value of a pulp, is the most important parameter that influences pulp and paper properties such as strength and light scattering ability. It is therefore necessary to compare pulps at a constant freeness value. Both measured and interpolated values (to freeness 100 ml CSF) are thus provided in the text below.
  • FIG. 1 illustrates the freeness as a function of the specific energy consumption (SEC) for the references (TMP Ref1 and TMP Ref2 ) and the pulps produced according to the invention (TMP HP1Fe and TMP HP2Fe ). It is evident from Figure 1 that a substantial energy saving is obtained for the pulps produced according to the invention whereas there was no significant difference between the TMP Ref1 and TMP Ref2 when it comes to energy consumption.
  • the pulps produced according to the invention consume 20% (TMP HP1Fe ) and 25% (TMP HP2Fe ) less energy to a constant freeness level (100 ml CSF) when compared to the energy consumption of the references (TMP Ref1 and TMP Ref2 , see Table 2).
  • the energy saving for TMP HP1Fe and TMP HP2Fe was obtained with 1.0 and 1.1 wt% (on bone dry wood) H 2 O 2 , respectively.
  • TMP HP1Fe and TMP HP2Fe are similar to the strength properties of the TMP references (see Tables 1 and 2).
  • Table 1 The pulp characteristics and energy consumption of the produced pulps Freeness (ml CSF) Energy consumption (kWh/bdt) Tensile index (Nm/g) Burst index (kPam 2 /g) TEA (J/m 2 ) Fibre length 1 (mm) TMP Ref1 119 2687 42.4 2.6 30.4 1.6 TMP Ref2 91 2825 54.0 3.2 54.0 1.5 TMP HP1Fe 2 109 2250 44.3 2.9 34.3 1.6 TMP HP2Fe 2 75 2265 54.2 3.0 46.0 1.5 1 The average (length weighted) fibre length was measured with the Kajaani FS-100 fibre size analyzer. 2 Produced according to the invention.
  • Table 2 The pulp characteristics and energy savings of the produced pulps interpolated to a constant freeness value (100 ml CSF) Energy saving 1 (%) Tensile index (Nm/g) Burst index (kPam 2 /g) TEA (J/m 2 ) Fibre length 2 (mm) TMP Ref1 49.5 2.7 32.3 1.6 TMP Ref2 54.3 3.2 54.0 1.6 TMP HP1Fe 3 20 50.7 3.0 40.3 1.6 TMP HP2Fe 3 25 51.1 2.8 42.6 1.5 1 The energy saving is given relative to the energy consumption of the TMP references (TMP Ref1 and TMP Ref2 ). 2 The average (length weighted) fibre length was measured with the Kajaani FS-100 fibre size analyzer. 3 Produced according to the invention.
  • TMP thermomechanical pulp
  • TMP Ref1 A TMP reference (denoted TMP Ref1 ) was produced without addition of chemicals in the same manner as was described in Example 1.
  • TMP Ref2 A reference TMP produced under more acidic conditions (denoted TMP Ref2 ) was produced by adding 0.19 wt% sulphuric acid (H 2 SO 4 ) based on the weight of bone dry wood to the refiner eye (inlet) of the primary refiner in the same manner as was described in Example 1.
  • a TMP produced according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by mixing 0.12 wt% Na 4 EDTA based on the weight of bone dry wood and 0.08 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood and then adding the mixture to the refiner eye of the primary refiner. Hydrogen peroxide (H 2 O 2 , 1.1 wt% based on the weight of bone dry wood) was added to the blow line of the primary refiner. The pH of the resulting pulp was 3.7. The pulp is denoted TMP HP1FeEDTA in Figures 2-4 and Tables 3-4.
  • the degree of refining measured as the freeness value of the pulp, is the most important parameter that influences pulp and paper properties such as strength and light scattering ability. It is therefore necessary to compare pulps at a constant freeness value. Both measured and interpolated values (to freeness 100 ml CSF) are thus provided in the figures and tables.
  • FIG 4 illustrates freeness as a function of the specific energy consumption (SEC) for the TMP references (TMP Ref1 and TMP Ref2 ) and TMP HP1FeEDTA produced according to the invention.
  • TMP HP1FeEDTA consumes 19% less energy to a constant freeness value (100 ml CSF) compared to the energy consumption of the references TMPs (TMP Ref1 and TMP Ref2 , see Table 4).
  • Table 3 The pulp characteristics and energy consumption of the produced pulps Freeness (ml CSF) Energy consumption (kWh/bdt) Tensile index (Nm/g) Burst index (kPam 2 /g) TEA (J/m 2 ) Fibre length 1 (mm) Light scattering coefficient (m 2 /kg) TMP Ref1 119 2687 42.4 2.6 30.4 1.6 53.2 TMP Ref2 91 2825 54.0 3.2 54.0 1.5 53.1 TMP HP1FeEDTA 2 118 2173 52.0 2.9 51.6 1.6 54.4 TMP HP1Fe 2,3 109 2250 44.3 2.9 34.3 1.6 49.4 1 The average (length weighted) fibre length was measured with the Kajaani FS-100 fibre size analyzer.
  • TMP HP1FeEDTA The level of energy saving for TMP HP1FeEDTA is the same as for TMP HP1Fe , i.e. about 20% when compared to the energy consumption of the references (TMP Ref , and TMP Ref2 ).
  • the strength properties i.e. tensile index and TEA
  • TMP Ref1 and TMP Ref2 the strength properties
  • the light scattering ability is maintained at the same level as for the references (TMP Ref1 and TMP Ref2 ).
  • TMP thermomechanical pulp
  • TMP Ref1 A reference TMP (denoted TMP Ref1 ) was produced without addition of chemicals in the same manner as described in Example 1.
  • TMP Ref2 A TMP reference produced under more acidic conditions (denoted TMP Ref2 ) was produced by adding 0.19 wt% (of bone dry wood) sulphuric acid (H 2 SO 4 ) to the refiner eye (inlet) of the primary refiner in the same manner as described in Example 1.
  • a TMP produced according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.08 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood to the refiner eye of the primary refiner and 2.2 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the blow line of the primary refiner.
  • the pH of the resulting pulp was 3.3.
  • the pulp is denoted TMP HP3Fe , in Figure 5 and Tables 5-6.
  • a TMP produced according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.14 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood to the refiner eye of the primary refiner and 2.1 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the blow line of the primary refiner.
  • the pH of the resulting pulp was 3.2.
  • the pulp is denoted TMP HP4Fe , in Figures 2-3 and 5 and Tables 5-6.
  • the degree of refining measured as the freeness value of a pulp, is the most important parameter that influences pulp and paper properties such as strength and light scattering ability. It is therefore necessary to compare pulps at a constant freeness value. Both measured and interpolated values (to freeness 100 ml CSF) are thus provided in the tables below.
  • Figure 5 illustrates freeness as a function of the specific energy consumption (SEC) for TMP Ref1 , TMP Ref2 and the pulps produced according to the invention (TMP HP3Fe and TMP HP4Fe ).
  • the pulps produced according to the described method consume 33% (TMP HP3Fe ) and 37% (TMP HP4Fe ) less energy to a constant freeness value (100 ml CSF) when compared to the energy consumption of the references (TMP Ref1 , TMP Ref2 ).
  • Table 5 The pulp characteristics and energy consumption of the produced pulps Freeness (ml CSF) Energy cons.
  • Table 6 The pulp characteristics and energy savings of the produced pulps interpolated to a constant freeness value (100 ml CSF) Energy saving 1 (%) Tensile index (Nm/g) Burst index (kPam 2 /g) TEA (J/m 2 ) Fibre length 2 (mm) TMP Ref1 49.5 2.7 32.3 1.6 TMP Ref2 54.3 3.2 54.0 1.6 TMP HP3Fe 3 33 48.0 2.5 40.6 1.5 TMP HP4Fe 3 37 49.2 2.6 41.1 1.5 1 The energy saving is given relative to the TMP references (TMP Ref1 and TMP Ref2 ). 2 The average (length weighted) fibre length was measured with the Kajaani FS-100 fibre size analyzer. 3 Produced according to the invention.
  • thermomechanical pulp TMP
  • the wood logs were debarked and chipped and washed prior to preheating and refining operations.
  • a 20 inch pressurized refiner (model OVP-MEC run at 1500 rpm) was used to produce a high-freeness pulp (about 540 ml CSF).
  • the energy input in the refiner was about 1150 kWh/bone dry metric ton (bdmt).
  • the activator and oxidant were then added to the defibrated pulp in a mixer (Electrolux BM 10S) immediately before further refining in a Wing refiner.
  • the activator was first added to the pulp followed by the addition of the oxidant.
  • the mixing time was 30 seconds for both activator and oxidant.
  • the reference pulp (TMP Ref3 ) was treated in the same way with the exception that deionized water was added to the mixer to give the same pulp consistency as for the pulp treated according to the invention. This was done since it is well known that the pulp consistency influences the resulting pulp properties and refining energy consumption. The pulps were then transferred to the wing refiner for further treatment.
  • the wing refiner is a laboratory equipment that gives a higher energy consumption to a fixed freeness level due to its smaller size compared to a commercial refiner.
  • TMP Ref3 A TMP reference (TMP Ref3 ) was produced without addition of chemicals as described above.
  • the degree of refining (freeness) as a function of the specific energy consumption (SEC) can be seen in Figure 6 .
  • a TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.13 wt% copper sulfate (CuSO 4 x 5 H 2 O) based on the weight of bone dry wood and 2.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 3.5.
  • the pulp is denoted TMP HP5Cu in Figure 6 .
  • FIG. 6 illustrates the freeness as a function of the specific energy consumption (SEC) for the reference (TMP Ref3 ) and the pulp produced according to the invention (TMP HP5Cu ). It is evident from Figure 6 that a substantial energy saving is obtained for the pulp produced according to the invention. TMP HP5Cu consume 37% less energy to a constant freeness level (175 ml CSF) when compared to the energy consumption of the reference pulp (TMP Ref3 ). The energy saving for TMP HP5Cu was obtained with 2.0 wt% (on bone dry wood) H 2 O 2 and 0.13 wt% (on bone dry wood) CuSO 4 x 5 H 2 O.
  • SEC specific energy consumption
  • the average fibre length (at 175 ml CSF, measured with the Pulp Quality Monitor PQM 1000 instrument) was 1.7 mm for the reference (TMP Ref3 ) and 1.8 mm for the pulp produced according to the invention (TMP HP5Cu ), i.e., no reduction in fibre length occurred.
  • Example 4 shows that substantially energy savings is obtained by using copper sulfate as activator and hydrogen peroxide as oxidant according to the method described in the invention.
  • Black spruce (Picea mariana) wood was used for the production of thermomechanical pulp (TMP).
  • TMP thermomechanical pulp
  • the wood logs were debarked and chipped and washed prior to preheating (4.14 bar steaming pressure, 40 s retention time) and refining operations.
  • a single disc 36" pressurized refiner (model 36-1CP run at 1800 rpm) was used to produce a high-freeness pulp (about 750 ml CSF).
  • the energy input in the refiner was about 500 kWh/bone dry metric ton (bdmt).
  • the activator and oxidant were then added to the defibrated pulp in a mixer (Electrolux BM 10S) immediately before further refining in a Wing refiner.
  • the activator was first added to the pulp followed by the addition of the oxidant.
  • the mixing time was 30 seconds for both activator and oxidant.
  • the reference pulp (TMP Ref4 ) was treated in the same way with the exception that deionized water was added to the mixer to give the same pulp consistency as for the pulp treated according to the invention. This was done since it is well known that the pulp consistency influences the resulting pulp properties and refining energy consumption.
  • the pulps were then transferred to the wing refiner for further treatment.
  • the wing refiner is a laboratory equipment that gives a higher energy consumption to a fixed freeness level due to its smaller size compared to a commercial refiner. It is well known that a smaller refiner has a higher energy consumption compared to a larger one.
  • TMP Ref4 A TMP reference (TMP Ref4 ) was produced without addition of chemicals as described above.
  • the degree of refining (freeness) as a function of the specific energy consumption (SEC) can be seen in Figure 7 .
  • a TMP produced by only adding an oxidant (H 2 O 2 ) and no activator or enhancer was produced by adding 1.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 4.0.
  • the pulp is denoted TMP HPref in Figure 7 .
  • a TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.02 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood and 1.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 3.9.
  • the pulp is denoted TMP HP6Fe in Figure 7 .
  • a TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.08 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood and 1.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 3.8.
  • the pulp is denoted TMP HP7Fe in Figure 7 .
  • a TMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.14 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood and 1.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 3.7.
  • the pulp is denoted TMP HP8Fe in Figure 7 .
  • Figure 7 illustrates the freeness as a function of the specific energy consumption (SEC) for the reference pulps (TMP Ref4 and TMP HPref ) and the pulps produced according to the invention (TMP HP6Fe , TMP HP7Fe and TMP HP8Fe ). It is evident from Figure 7 that a substantial energy saving is obtained for the pulps produced according to the invention whereas no energy savings is obtained when only hydrogen peroxide (oxidant) is present (TMP HPref ).
  • SEC specific energy consumption
  • the pulp produced according to the invention consume 10% (TMP HP6Fe ), 15% (TMP HP7Fe ) and 33% (TMP HP8Fe ) less energy to a constant freeness level (175 ml CSF) when compared to the energy consumption of the reference pulps (TMP Ref4 and TMP HPref ).
  • the energy saving for TMP HP6Fe was obtained with 1.0 wt% (on bone dry wood) H 2 O 2 and 0.02 wt% (on bone dry wood) FeSO 4 x 7 H 2 O.
  • the average fibre length (at 175 ml CSF, measured with the Kajaani FS-100 fibre size analyzer) was 1.7 mm for the reference pulp TMP Ref4 and 1.7 mm (TMP HP6Fe ), 1.7 mm (TMP HP7Fe ) and 1.6 mm (TMP HP8Fe ) for the pulps produced according to the invention.
  • the average fibre length for TMP HPref was 1.8 mm. It is evident that no extensive fibre shortening occurs as a result of the chemical treatment described in this invention.
  • Aspen (Populus tremula) wood was used for the production of chemithermomechanical pulp (CTMP).
  • CMP chemithermomechanical pulp
  • the wood logs were debarked and chipped and washed prior to preheating and refining operations.
  • a 20 inch pressurized refiner (model OVP-MEC run at 1500 rpm) was used to produce a high-freeness pulp (about 420 ml CSF).
  • the energy input in the refiner was about 1450 kWh/bone dry metric ton (bdmt).
  • the activator and oxidant were then added to the defibrated pulp in a mixer (Electrolux BM 10S) immediately before further refining in a Wing refiner.
  • the activator was first added to the pulp followed by the addition of the oxidant.
  • the mixing time was 30 seconds for both activator and oxidant.
  • the reference pulp (CTMP Ref ) was treated in the same way with the exception that deionized water was added to the mixer to give the same pulp consistency as for the pulp treated according to the invention. This was done since it is well known that the pulp consistency influences the resulting pulp properties and refining energy consumption. The pulps were then transferred to the wing refiner for further treatment.
  • the wing refiner is a laboratory equipment that gives a higher energy consumption to a fixed freeness level due to its smaller size compared to a commercial refiner. It is well known that a smaller refiner has a higher energy consumption compared to a larger one.
  • TMP Ref TMP reference
  • a CTMP manufactured according to the present invention using acid hydrogen peroxide (H 2 O 2 ) was produced by adding 0.14 wt% iron sulfate (FeSO 4 x 7 H 2 O) based on the weight of bone dry wood and 2.0 wt% hydrogen peroxide (H 2 O 2 ) based on the weight of bone dry wood to the high-freeness pulp.
  • the pH of the resulting pulp was 3.8.
  • the pulp is denoted CTMP HPFe in Figure 8 .
  • FIG 8 illustrates the freeness as a function of the specific energy consumption (SEC) for the reference pulp (CTMP Ref ) and the pulp produced according to the invention (CTMP HPFe ). It is evident from Figure 8 that a substantial energy saving is obtained for the pulp produced according to the invention.
  • CTMP HPFe consume 32% less energy to a constant freeness level (175 ml CSF) when compared to the energy consumption of the reference pulp (CTMP Ref ).
  • the energy saving for CTMP HPFe was obtained with 2.0 wt% (on bone dry wood) H 2 O 2 and 0.14 wt% (on bone dry wood) FeSO 4 x 7 H 2 O.
  • the average fibre length (at 175 ml CSF, measured with the Pulp Quality Monitor PQM 1000 instrument) was 0.95 mm for the reference pulp (CTMP Ref ) and 0.94 mm for the pulp produced according to the invention (CTMP HPFe ). It is evident that no fibre shortening occurs as a result of the chemical treatment described in this invention.
  • Example 6 It is evident from the results presented in Example 6 that the method according to the invention also generates substantial energy savings for an aspen chemitermomechanical pulp without cutting the fibres during refining.

Landscapes

  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP06813080A 2005-12-02 2006-11-08 Process of producing high-yield pulp Not-in-force EP1954871B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06813080A EP1954871B1 (en) 2005-12-02 2006-11-08 Process of producing high-yield pulp

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05111643 2005-12-02
PCT/SE2006/050460 WO2007064287A1 (en) 2005-12-02 2006-11-08 Process of producing high-yield pulp
EP06813080A EP1954871B1 (en) 2005-12-02 2006-11-08 Process of producing high-yield pulp

Publications (2)

Publication Number Publication Date
EP1954871A1 EP1954871A1 (en) 2008-08-13
EP1954871B1 true EP1954871B1 (en) 2011-06-29

Family

ID=35636794

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06813080A Not-in-force EP1954871B1 (en) 2005-12-02 2006-11-08 Process of producing high-yield pulp

Country Status (13)

Country Link
EP (1) EP1954871B1 (es)
JP (1) JP5091154B2 (es)
CN (1) CN101321908B (es)
AR (1) AR057948A1 (es)
AT (1) ATE514813T1 (es)
AU (1) AU2006321020B2 (es)
BR (1) BRPI0619765B1 (es)
CA (1) CA2631545C (es)
NO (1) NO339754B1 (es)
NZ (1) NZ568622A (es)
RU (1) RU2380466C1 (es)
WO (1) WO2007064287A1 (es)
ZA (1) ZA200805755B (es)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080308239A1 (en) 2007-06-12 2008-12-18 Hart Peter W Fiber blend having high yield and enhanced pulp performance and method for making same
WO2008153565A1 (en) 2007-06-12 2008-12-18 Meadwestvaco Corporation A fiber blend having high yield and enhanced pulp performance and method for making same
US20090008049A1 (en) * 2007-07-05 2009-01-08 Stantec Consulting Ltd. Non-scaling chip conditioning system for energy reduction in mechanical pulping
US8282773B2 (en) * 2007-12-14 2012-10-09 Andritz Inc. Method and system to enhance fiber development by addition of treatment agent during mechanical pulping
FI20105862A0 (fi) * 2010-08-18 2010-08-18 Bo Akademi University Menetelmä hekseeniuronihappojen poistamiseksi
CN103864940A (zh) * 2014-03-26 2014-06-18 郑州大学 一种选择性氧化纤维素的方法
CN105821693A (zh) * 2016-06-11 2016-08-03 苏州思创源博电子科技有限公司 一种酶改性环保纸浆的制备方法
CN108589368B (zh) * 2018-02-07 2020-07-31 江苏海德新材料有限公司 一种利用木材浆生产高纯纤维的方法
RU2721503C2 (ru) * 2018-11-19 2020-05-19 федеральное государственное бюджетное образовательное учреждение высшего образования "Пермский национальный исследовательский политехнический университет" Способ получения полуцеллюлозы
CN110318278B (zh) * 2019-05-16 2021-04-23 云南天木生物科技有限公司 一种工业大麻废弃纤维的提取方法
CA3174099A1 (en) * 2020-04-03 2021-10-07 Dorte BARTNIK JOHANSSON Method for producing oxidized lignins and system for producing oxidized lignins

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1505076A (en) * 1974-06-11 1978-03-22 Canadian Ind Strenghening of mechanical pulp by chemical treatment
JPS5891865A (ja) * 1981-11-21 1983-05-31 上原　基靖 過酸化物を用いる漂白方法
US4849053A (en) * 1985-09-20 1989-07-18 Scott Paper Company Method for producing pulp using pre-treatment with stabilizers and defibration
BR8606875A (pt) * 1985-09-20 1987-11-03 Scott Paper Co Processo de polpacao de alto rendimento para material lignocelulosico em forma de cavacos;polpa nao sulfonada;polpa de pinho nao sulfonada;polpa de faia preta nao sulfonada;polpa de eucalipto nao sulfonada;e polpa de gmelinia nao sulfonada
DE3544398A1 (de) * 1985-12-16 1987-06-19 Sueddeutsche Kalkstickstoff Verfahren zur bleiche und delignifizierung von zellstoffhaltigen produkten
NZ235983A (en) * 1989-11-08 1993-01-27 Novo Nordisk As Process for hydrolysis of resins in lignocellulosic pulp using enzymes simultaneously with peroxy bleaching; ctmp fluff-pulp and absorbent articles produced therefrom
CA2057231A1 (en) * 1991-01-07 1992-07-08 Ulrike Tschirner Method of pretreating lignocellulosic materials prior to alkaline peroxide high yield pulping
RU2015234C1 (ru) * 1992-06-03 1994-06-30 Товарищество с ограниченной ответственностью "Регул" Способ получения волокнистого полуфабриката
AU4271596A (en) * 1995-12-19 1997-07-14 Kvaerner Hymac Inc. Process for treating refiner pulp
RU2106447C1 (ru) * 1996-07-22 1998-03-10 Камский целлюлозно-бумажный комбинат Способ получения древесной массы
FI104502B (fi) * 1997-09-16 2000-02-15 Metsae Serla Oyj Menetelmä paperirainan valmistamiseksi
ES2209420T3 (es) * 1998-04-17 2004-06-16 Alberta Research Council, Inc. Metodo de produccion de pulpa lignocelulosica a partir de especies no leñosas.
US6348128B1 (en) * 1998-06-01 2002-02-19 U.S. Borax Inc. Method of increasing the causticizing efficiency of alkaline pulping liquor by borate addition

Also Published As

Publication number Publication date
WO2007064287A1 (en) 2007-06-07
CN101321908B (zh) 2011-08-17
JP2009529609A (ja) 2009-08-20
CA2631545A1 (en) 2007-06-07
CN101321908A (zh) 2008-12-10
EP1954871A1 (en) 2008-08-13
NZ568622A (en) 2010-10-29
CA2631545C (en) 2014-08-19
ATE514813T1 (de) 2011-07-15
NO20082435L (no) 2008-07-01
JP5091154B2 (ja) 2012-12-05
BRPI0619765B1 (pt) 2016-12-13
AU2006321020B2 (en) 2011-02-10
NO339754B1 (no) 2017-01-30
AU2006321020A1 (en) 2007-06-07
BRPI0619765A2 (pt) 2011-10-18
ZA200805755B (en) 2009-04-29
RU2380466C1 (ru) 2010-01-27
AR057948A1 (es) 2007-12-26

Similar Documents

Publication Publication Date Title
US8268122B2 (en) Process of producing high-yield pulp
NO339754B1 (no) Fremgangsmåte for fremstilling av høyutbyttemasse
EP1266994B1 (en) High temperature peroxide bleaching of mechanical pulps
EP0670928B1 (en) Process for delignification of lignocellulose-containing pulp
US4160693A (en) Process for the bleaching of cellulose pulp
EP2406425B1 (en) Method and chemical composition to improve efficiency of mechanical pulp
JP2007530818A (ja) パルプの白色度の増進及び漂白薬品の使用における最適化の方法
WO2010139589A1 (en) Process for producing mechanical pulp
US6752904B2 (en) Process for removal of lignin from lignocellulosic material
EP0670929B1 (en) Process for bleaching of lignocellulose-containing pulp
US11725338B2 (en) Method for producing bleached wood fibre material
EP1702100B1 (en) Process for removing interfering substances in the production of mechanical pulp and process for producing mechanical pulp
EP2443280B1 (en) Alkaline peroxide treatment of rejects in an integrated neutral-alkaline paper mill
CA2399772A1 (en) Pulping process
More Structural changes to Pinus radiata wood lignin during kraft pulping and bleaching

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080514

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: PAULSSON, MAGNUS, LARS

Inventor name: WALTER, KARIN, SUSANNE, MARIA

Inventor name: WACKERBERG, EVA, LINNEA, ELISABETH

17Q First examination report despatched

Effective date: 20080925

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAC Information related to communication of intention to grant a patent modified

Free format text: ORIGINAL CODE: EPIDOSCIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006022827

Country of ref document: DE

Effective date: 20110825

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & PARTNER AG

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111031

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111029

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

26N No opposition filed

Effective date: 20120330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111130

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006022827

Country of ref document: DE

Effective date: 20120330

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111010

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110929

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110629

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: AKZO NOBEL N.V., NL

Free format text: FORMER OWNER: AKZO NOBEL N.V., NL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20131127

Year of fee payment: 8

Ref country code: CH

Payment date: 20131127

Year of fee payment: 8

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20141108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141108

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006022827

Country of ref document: DE

Representative=s name: VOSSIUS & PARTNER PATENTANWAELTE RECHTSANWAELT, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602006022827

Country of ref document: DE

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NL

Free format text: FORMER OWNER: AKZO NOBEL N.V., ARNHEM, NL

REG Reference to a national code

Ref country code: AT

Ref legal event code: PC

Ref document number: 514813

Country of ref document: AT

Kind code of ref document: T

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NL

Effective date: 20180117

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NL

Effective date: 20180731

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20181128

Year of fee payment: 13

Ref country code: FI

Payment date: 20181128

Year of fee payment: 13

Ref country code: DE

Payment date: 20181128

Year of fee payment: 13

Ref country code: AT

Payment date: 20181019

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20181127

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602006022827

Country of ref document: DE

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191108

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 514813

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191202