EP1552052B1 - A method of producing mechanical pulp and the mechanical pulp thus produced - Google Patents
A method of producing mechanical pulp and the mechanical pulp thus produced Download PDFInfo
- Publication number
- EP1552052B1 EP1552052B1 EP03794378A EP03794378A EP1552052B1 EP 1552052 B1 EP1552052 B1 EP 1552052B1 EP 03794378 A EP03794378 A EP 03794378A EP 03794378 A EP03794378 A EP 03794378A EP 1552052 B1 EP1552052 B1 EP 1552052B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber material
- anyone
- pectinase
- refining
- pulp
- 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.)
- Expired - Lifetime
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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
- D21B1/021—Pretreatment of the raw materials by chemical or physical means by chemical 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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
Definitions
- the present invention relates to a method of mechanical pulping based on cellulose fiber material after pretreatment of the fiber material with pectinase prior to mechanical defibration.
- the invention is also related to the mechanical pulp thus produced.
- mechanical pulping wood fibers are separated by mechanical defibration, typically in a refiner or a grinder, with or without pretreatment.
- pretreatment the process can be either TMP, where thermal softening is applied; or CTMP, where for instance sulfite is used for the sulfonation of lignin; or APMP, where alkaline peroxide is applied resulting in a combined effect of chemical softening due to alkali and bleaching or brightening due to peroxide.
- thermal treatment is employed prior to refining to soften the wood material thus leading to reduced energy consumption as well as improved pulp strength.
- alkaline treatment is an effective treatment for reducing energy consumption, it also induces darkening reactions that result in poorer optical properties that are essential for paper products based on mechanical pulps. Besides, the use of alkali results in extensive dissolution of wood material, which results in yield loss and necessitates effluent treatment.
- the examples show that the enzymatic treatment can reduce the refiner energy by 4 to 10%, in addition to the energy reduction of about 4% due to the compression treatment as compared to the reference. At the same time the strength properties of the pulp are improved when compared at the same pulp freeness.
- Another biological pulping process involving pretreatment of wood chips is based on lignin oxidizing fungi treatment ( US 5,055,159 ).
- the refining energy consumption can be reduced by about 30% at the same freeness.
- the treatment however requires long incubation time and the pulp produced has a dark color.
- pectinase has been specifically used in post-treatment of mechanical pulps.
- pectinase is used for alkaline bleached mechanical wood pulp.
- the purpose of such treatment is however to remove pectin remaining after the pulping process in order to reduce the source of so-called "anionic trash" which is harmful in paper machine operation.
- EP-A-0 430 915 relates to enzymes for decomposition of hemicellulose and/or cellulose, in order to achieve a reduction in energy consumption in the production of mechanical pulp.
- the example given shows the efficiency of hemicellulase in reduction of refining energy in the treatment of a coarsely separated pulp.
- pectinase no results are shown for the suggested use of pectinase.
- WO-A-89/02951 teaches how to treat wood pieces having a length in the fibre direction of at least 100 mm, in order to achieve a better pulp strength due to fibre separation. From the document, the skilled person can learn that compression of at least 5 MPa has such an effect, but that the method is difficult to employ generally on chips that are of considerably smaller size and that moreover are more or less randomly oriented at compression.
- the present invention aims at providing a method of mechanical pulping requiring significantly reduced refining energy consumption to reach a certain pulp freeness, or pulp strength, as compared to prior art.
- the invention also aims at improved optical properties in the pulp, such as an improved brightness.
- the method comprises pretreatment of the comminuted cellulose fiber material with pectinase, alone or in combination with a chelating agent, for instance DTPA and/or sulfite, followed by mechanical defibration and refining to produce a mechanical pulp.
- a chelating agent for instance DTPA and/or sulfite
- Pectin is a group of amorphous polysaccharide substances in wood. Although the amount of pectin in softwood and hardwood is normally less than 1%, it is predominantly deposited in the compound middle lamella, and the tori of bordered pit-membranes of coniferous species ( Hafren J. and Westermark U.: Nordic Pulp and Paper 16 (4), 284-290, 2001 ).
- the main component of pectin is polygalacturonan consisting of galacturonic acid units that to various extend are esterified. When in free acid form, the carboxylic groups of the galacturonan having a negative charge can induce local swelling of the fibers in contact with aqueous solutions.
- the esterified groups on the other hand, can be de-esterified through for instance alkaline treatment and thus contributing to swelling.
- the present invention is aimed to utilize the specific features of pectin with respect to its specific location and the potential to induce selective weakening in the fiber wall.
- Enzyme with specific activity towards pectin is used for the pretreatment of cellulose fiber material. Maceration of the fiber material prior to the enzyme treatment proves an efficient way to get the enzyme in place.
- the refining condition is optimized in respect to refining intensity and preheating temperature. The results according to the present invention are a significantly reduced refining energy to reach a given pulp freeness and improved strength and optical properties of the pulp.
- the pretreatment is preferably assisted by a mechanical compression to facilitate liquor uptake and to give a more even treatment of the material.
- Compression screw device or twin roll presses can be used at a compression ratio of 1:1 to 8:1.
- the pretreatment can be further improved if presteaming is conducted prior to the compression.
- Impregnation according to the invention follows immediately after the compression and/or thermal pretreatment.
- the pectinase is charged in an amount required for sufficient treatment, preferably 2,000,000 to 200,000,000 polygalacturonase units/ton material and even more preferred 10,000,000 to 50,000,000 polygalacturonase units/ton.
- the retention time of treatment is 3 min to 24 hours, preferably 3 to 300 min, even more preferred 15 to 240 min and most preferred 30 to 120 min at a temperature of 20 to 100°C, preferably 35 to 70°C, and more preferably about 50°C.
- the treatment condition can be adjusted depending on the charge of the pectinase to allow for a sufficient hydrolysis of the pectins. Other pectinase preparations can be used provided that the pectolytic activity is satisfied.
- Defibration and refining of the pectinase treated material can be carried out either at conventional TMP conditions and high intensity conditions.
- a surprising energy reduction effect is obtained.
- the energy reduction is 400 kWh/t with TMP condition, from 2500 kWh/t without pectinase treatment to 2100 kWh/t with pectinase treatment, or by about 16%.
- the energy reduction is 150 kWh/t with high intensity condition, from 2150 kWh/t without pectinase treatment to 2000 kWh/t with pectinase treatment, or by about 7%.
- the combination of high intensity and pectinase treatment gives a total reduction of 500 kWh/t, from 2500 kWh/t to 2000 kWh/t at a pulp freeness of 100 ml CSF, which is 20% in reduction.
- the shives content decreases more rapidly after the pectinase treatment.
- the strength properties remain the same as compared to conventional TMP, and improved by about 10% as compared to high intensity TMP.
- the brightness of the pulp is also increased by the enzymatic treatment.
- the surprising effects resulting from the pectinase treatment could be explained by a selective weakening of the pectin-enriched region in the fiber wall due to hydrolysis of the pectins, with the consequence of a more efficient fiber separation in defibration and refining of the material. It is evident to those skilled in the art that this process can bring about a significant economical benefit, in terms of improved pulp properties and reduced energy cost. It is also evident to those skilled in the art that any enzyme preparation that contains sufficient pectolytic hydrolysis activity, alone or in combination with other chemicals, can be used for the treatment according to the present invention.
- the present invention describes a mechanical pulping process comprising:
- disc refiners are the defibration and refining equipment used in this study, other mechanical devices can be used for the purpose of defibration and refining. Some of the examples are conical refiners and stone ground wood grinders. The refiners can be of the single disc or double disc type. The refining may be made in a single stage or in multistage. The defibration and refining can also be done at atmospheric pressure, in which case refiner mechanical pulping, or RMP is a more appropriate description of the process instead of TMP.
- any fiber material containing pectins could be treated with this method.
- the fiber material could be hardwood fiber material, non-wood fibers such as bagasse, bamboo, reed and straw.
- the embodiment as described here can be modified according to the source of fiber material and the process set-up.
- the pulp obtained can depending on the application of the pulp be subject to further treatment such as washing, screening, post-refining and bleaching according to conventional processes.
- Mechanical pulps are produced by different chemical treatments, in a pilot refiner plant.
- the process conditions are as follows.
- Wood chips consisting of approximately one third white spruce, one third red and black spruce and one third balsam fir, all of Canadian origin in the Nova Scotia region. The chips are prepared with mill-size chipper and well mixed prior to the trials.
- the chips are pre-steamed at atmospheric pressure for 15 min. After pre-steaming the chips are fed into a plug-screw device with a compression ratio of 4:1. At the outlet of the device, the chips are released into a solution containing various chemicals, including pectinase in the trials according to the invention.
- the pH of the solution is kept at about 5 adjusted by use of sodium hydroxide or sulfuric acid.
- the pectinase used in this study is a highly pectolytic enzyme preparation. This enzyme also hydrolyzes the methyl-esterified galacturonic acid in the pectins.
- the pectinase used is generated by submerged fermentation of a group of microorganisms containing Aspergillus aculeatus and Aspergillus oryzae .
- the charge of pectinase in this study is 30,800,000 polygalacturonase units/ton.
- the charges of DTPA and sodium sulfite are 4 kg/t and 12 kg/t, respectively, were applicable.
- the primary refiner is of the Sprout-Bauer 36-1 CP single disc refiner type. Two pulping conditions, conventional TMP and high intensity HI-TMP, are applied. The preheating steam pressure is 2.8 bar for TMP and 5.9 bar for high intensity (HI-TMP). The retention time at preheating is 3.4 min for TMP and 12 sec for HI-TMP. The refiner rotation speed is 1800 rpm for TMP and 2600 rpm for HI-TMP. The secondary refining is carried out with a double disc atmospheric refiner to reach the final freeness levels.
- the obtained pulps are evaluated both for strength properties and optical properties including a bleachability study with hydrogen peroxide bleaching.
- Sample 1 TMP condition with only water impregnation with pH adjusted to 5.
- Sample 2 TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
- Sample 1 Sample 2 Freeness, ml CSF 665 230 148 129 57 656 115 57 36 SEC (kWh/t) 902 1889 2028 2237 3078 824 1993 2386 3000 Density (kg/m3) 309,6 344,83 371,75 440,53 205,76 384,62 446,43 462,96 Bulk (cm3/g) 3,23 2,9 2,69 2,27 4,86 2,6 2,24 2,16 Burst ind. (kPam2/g) 1,65 1,98 2,29 3,04 0,34 2,46 3,1 3,35 Tear ind. (mNm2/g) 10,9 9,6 9,5 7,9 4,8 8,7 8 7,4 Tens ind.
- Sample 3 HI-TMP condition with only water in the impregnation adjusted to pH 5.
- Sample 4 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
- Table 2. Sample 3 Sample 4 Freeness, ml CSF 714 293 197 126 54 725 254 236 121 72 SEC (kWh/t) 531 1482 1652 1897 2655 412 1362 1462 1793 2344 Density(kg/m3) 311,53 362,32 389,11 454,55 317,46 321,54 387,6 423,73 Bulk (cm3/g) 3,21 2,76 2,57 2,2 3,15 3,11 2,58 2,36 Burst ind. (kPa.m2/g) 1,47 1,78 2,07 2,96 1,82 1,85 2,6 3,2 Tearind.
- the enzymatic treatment has a surprising effect on energy reduction also with the high intensity condition.
- the specific energy consumption is reduced by about 150 kWh/t.
- the reduction is less pronounced at lower freeness.
- the pulp properties at the same time are improved by about 10% both for tensile strength and tear strength, while the optical properties remain at the same level.
- the potential of the enzymatic treatment makes is obvious to people skilled in the art that even better strength can be achieved if the same amount of energy is applied to the enzymatically treated pulps, or even less energy is required if the same strength properties are to be acquired.
- Sample 3 HI-TMP condition with only water in the impregnation adjusted to pH 5.
- Sample 4 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
- Sample 5 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA, pH 5.
- Sample 6 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA and 12 kg/t sodium sulfite, pH 5.
- Table 3 Sample 3 Sample 4 Sample 5 Sample 6 Freeness, ml CSF 293 197 126 54 254 236 121 72 201 148 87 52 184 150 97 55 SEC (kWh/t) 1482 1652 1897 2655 1362 1462 1793 2344 1539 1681 2022 2676 1934 2082 2303 3040 Density (kg/m3) 311,53 362,32 389,11 454,55 317,46 321,54 387,6 423,73 340,14 362,32 413,22 446,43 384,62 358,42 398,41 436,68 Bulk (cm3/g) 3,21 2,76 2,57 2,2 3,15 3,11 2,58 2,36 2,94 2,76 2,42 2,24 2,6 2,79 2,51 2,29 Burst ind.
- the refining energy consumption, SEC is not affected by additional charge of DTPA or DTPA/sulfite.
- the SEC is at the same level for all samples with pectinase treatment, about 150 kWh/t lower compared to Sample 3, i.e. high intensity condition without pectinase treatment, also see Figure 3.
- a surprising effect is however obtained in the brightness of unbleached pulp. With DTPA together with pectinase, the brightness is increased by about 2 units ISO. With a combined of pectinase, DTPA and sulfite, the brightness improvement is even higher, 4-5 units ISO. The brightness improvement is fairly constant in the entire freeness range.
- Pulps with different treatments are bleached with alkaline peroxide with following bleach conditions:
- Sample 7 TMP condition with only water impregnation with pH adjusted to 5.
- Sample 8 TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
- Sample 9 HI-TMP condition with only water in the impregnation adjusted to pH 5.
- Sample 10 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, pH 5.
- Sample 11 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA, pH 5.
- Sample 12 HI-TMP condition with 30,800,000 polygalacturonase units/t pectinase, 4 kg/t DTPA and 12 kg/t sodium sulfite, pH 5. Table 4 Unbl. ISO% Bleached ISO% Res. H2O2 % Sample 7 52,3 68,1 7,5 Sample 8 54,7 70,6 16,8 Sample 9 53,9 68,3 5,6 Sample 10 54,4 71,9 19,9 Sample 11 56.0 71,4 12,9 Sample 12 59,5 74,3 25,3
- the residual peroxide is much higher with the enzymatically treated samples. This is beneficial because the residual chemicals are recycled back to the process after bleaching. The need of make-up peroxide is reduced accordingly.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Paper (AREA)
- Crushing And Grinding (AREA)
- Debarking, Splitting, And Disintegration Of Timber (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE0202629 | 2002-09-06 | ||
SE0202629A SE525872C2 (sv) | 2002-09-06 | 2002-09-06 | Metod att tillverka mekanisk massa med reducerad energikonsumtion |
PCT/SE2003/001296 WO2004022842A1 (en) | 2002-09-06 | 2003-08-21 | A method of producing mechanical pulp and the mechanical pulp thus produced |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1552052A1 EP1552052A1 (en) | 2005-07-13 |
EP1552052B1 true EP1552052B1 (en) | 2007-10-03 |
Family
ID=20288904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03794378A Expired - Lifetime EP1552052B1 (en) | 2002-09-06 | 2003-08-21 | A method of producing mechanical pulp and the mechanical pulp thus produced |
Country Status (11)
Country | Link |
---|---|
US (1) | US20050241785A1 (pt) |
EP (1) | EP1552052B1 (pt) |
CN (1) | CN1681992A (pt) |
AT (1) | ATE374856T1 (pt) |
AU (1) | AU2003253540A1 (pt) |
BR (1) | BR0314017B1 (pt) |
CA (1) | CA2497904A1 (pt) |
DE (1) | DE60316712T2 (pt) |
RU (1) | RU2322540C2 (pt) |
SE (1) | SE525872C2 (pt) |
WO (1) | WO2004022842A1 (pt) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017102542A1 (en) | 2015-12-15 | 2017-06-22 | Metgen Oy | Method for producing mechanical pulp from a biomass comprising lignocellulosic material |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
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FI20031818A (fi) * | 2003-12-11 | 2005-06-12 | Valtion Teknillinen | Menetelmä mekaanisen massan valmistamiseksi |
CN1997791B (zh) | 2004-05-03 | 2011-01-26 | 纸、纸板和纤维素工业技术中心 | 机械纸浆的制备方法 |
US20070062654A1 (en) * | 2005-09-16 | 2007-03-22 | Enzymatic Deinking Technologies, Llc | Treatment of wood chips using enzymes |
US7988824B2 (en) * | 2005-12-15 | 2011-08-02 | Kimberly-Clark Worldwide, Inc. | Tissue product having a transferable additive composition |
CA2687594C (en) * | 2007-05-23 | 2016-01-19 | Alberta Research Council Inc. | Decortication process |
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 |
FI122169B (fi) * | 2010-01-29 | 2011-09-30 | Mzymes Oy | Puuhakkeen käsittely kuumahierremassan valmistusta varten |
EP2395147A1 (en) | 2010-05-10 | 2011-12-14 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Freeness of paper products |
FR2965570B1 (fr) * | 2010-09-30 | 2012-11-02 | Arjo Wiggins Fine Papers Ltd | Procede de raffinage en milieu enzymatique d'une pate papetiere comportant des fibres cellulosiques afin de reduire leur longueur |
BR112013015837A2 (pt) * | 2010-12-22 | 2018-05-15 | Stora Enso Oyj | método para controlar um processo de polpação de uma maneira de alimentação avante. |
SE539914C2 (sv) * | 2014-04-29 | 2018-01-09 | Stora Enso Oyj | Process för framställning av åtminstone ett skikt hos ett papper eller en kartong samt ett papper eller en kartong som framställts enligt processen |
WO2016145276A1 (en) | 2015-03-11 | 2016-09-15 | Andritz Inc. | Processes and systems for the pulping of lignocellulosic materials |
CN108252134A (zh) * | 2018-01-24 | 2018-07-06 | 齐鲁工业大学 | 一种降低木材化机浆制备过程中磨浆能耗的方法 |
CN109338775B (zh) * | 2018-09-30 | 2020-12-01 | 山东世纪阳光纸业集团有限公司 | 一种环保秸秆生物机械法制浆工艺 |
CN109695172A (zh) * | 2018-12-28 | 2019-04-30 | 江苏秸宝生物质新材料有限公司 | 秸秆生物机械制浆方法和设备 |
CN109457532B (zh) * | 2018-12-29 | 2021-03-02 | 齐鲁工业大学 | 一种麦草叶鞘制备生物机械浆的方法 |
CN109706771B (zh) * | 2018-12-29 | 2020-12-22 | 齐鲁工业大学 | 一种热蒸汽协同生物酶处理麦草制备原色生物机械浆的方法 |
CN109577059B (zh) * | 2018-12-29 | 2020-05-01 | 齐鲁工业大学 | 一种麦草秸秆制备生物机械本色浆的方法 |
CN109577072B (zh) | 2018-12-29 | 2019-12-06 | 齐鲁工业大学 | 一种麦草秸秆制备生物机械原色浆的方法 |
CN109680530B (zh) * | 2018-12-29 | 2020-12-11 | 齐鲁工业大学 | 一种热蒸汽协同生物酶处理麦草制备本色生物机械浆的方法 |
CN109629296B (zh) * | 2018-12-29 | 2020-12-11 | 齐鲁工业大学 | 一种热水处理协同生物酶处理的生物机械浆制备方法 |
CN109629318B (zh) * | 2018-12-29 | 2020-12-25 | 齐鲁工业大学 | 一种麦草叶制备生物机械浆的方法 |
CN109577060B (zh) * | 2018-12-29 | 2020-12-11 | 齐鲁工业大学 | 一种热水协同碱性生物酶处理麦草制备本色生物机械浆的方法 |
CN112726254B (zh) * | 2020-12-31 | 2023-07-28 | 齐鲁工业大学 | 一种热水处理协同生物酶处理麦草制备本色生物机械浆及副产物全利用的方法 |
CN118461348B (zh) * | 2024-07-11 | 2024-10-15 | 临邑县临兴木业有限公司 | 一种利用植物纤维原料的制浆工艺 |
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CA2466505A1 (en) * | 2001-11-09 | 2003-05-15 | Biopulping International, Inc. | Microwave pre-treatment of logs for use in making paper and other wood products |
AU2003253919A1 (en) * | 2002-07-19 | 2004-02-09 | Andritz Inc. | High defiberization chip pretreatment |
WO2004101889A2 (en) * | 2003-05-06 | 2004-11-25 | Novozymes North America, Inc. | Use of hemicellulase composition in mechanical pulp production |
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2002
- 2002-09-06 SE SE0202629A patent/SE525872C2/sv not_active IP Right Cessation
-
2003
- 2003-08-21 CN CNA038212218A patent/CN1681992A/zh active Pending
- 2003-08-21 DE DE60316712T patent/DE60316712T2/de not_active Expired - Lifetime
- 2003-08-21 US US10/526,469 patent/US20050241785A1/en not_active Abandoned
- 2003-08-21 AT AT03794378T patent/ATE374856T1/de not_active IP Right Cessation
- 2003-08-21 EP EP03794378A patent/EP1552052B1/en not_active Expired - Lifetime
- 2003-08-21 RU RU2005105039/12A patent/RU2322540C2/ru not_active IP Right Cessation
- 2003-08-21 AU AU2003253540A patent/AU2003253540A1/en not_active Abandoned
- 2003-08-21 BR BRPI0314017-2B1A patent/BR0314017B1/pt not_active IP Right Cessation
- 2003-08-21 WO PCT/SE2003/001296 patent/WO2004022842A1/en active IP Right Grant
- 2003-08-21 CA CA002497904A patent/CA2497904A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017102542A1 (en) | 2015-12-15 | 2017-06-22 | Metgen Oy | Method for producing mechanical pulp from a biomass comprising lignocellulosic material |
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Publication number | Publication date |
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BR0314017A (pt) | 2005-07-19 |
ATE374856T1 (de) | 2007-10-15 |
SE0202629L (sv) | 2004-03-07 |
US20050241785A1 (en) | 2005-11-03 |
RU2005105039A (ru) | 2005-10-10 |
BR0314017B1 (pt) | 2014-07-22 |
CA2497904A1 (en) | 2004-03-18 |
DE60316712D1 (de) | 2007-11-15 |
SE525872C2 (sv) | 2005-05-17 |
SE0202629D0 (sv) | 2002-09-06 |
CN1681992A (zh) | 2005-10-12 |
EP1552052A1 (en) | 2005-07-13 |
AU2003253540A1 (en) | 2004-03-29 |
WO2004022842A1 (en) | 2004-03-18 |
RU2322540C2 (ru) | 2008-04-20 |
DE60316712T2 (de) | 2008-07-24 |
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