EP1702100A2 - Process for removing interfering substances in the production of mechanical pulp and process for producing mechanical pulp - Google Patents
Process for removing interfering substances in the production of mechanical pulp and process for producing mechanical pulpInfo
- Publication number
- EP1702100A2 EP1702100A2 EP04805208A EP04805208A EP1702100A2 EP 1702100 A2 EP1702100 A2 EP 1702100A2 EP 04805208 A EP04805208 A EP 04805208A EP 04805208 A EP04805208 A EP 04805208A EP 1702100 A2 EP1702100 A2 EP 1702100A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- peracid
- ton
- impregnation
- lignocellulosic material
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/04—Pretreatment of the finely-divided materials before digesting with acid reacting compounds
Definitions
- the invention relates to a method for removing extractives and optionally electrolytes during mechanical pulp production and a method for producing mechanical pulp.
- Methods for producing and bleaching mechanical pulps differ from methods for de- fibrating and bleaching chemical pulps with respect to efforts to avoid delignifica- tion.
- the pulp yield is maintained on a high level.
- Bleaching is intended to decolourise the chromophore groups of lignin.
- Mechanical pulps can be divided into two main classes, purely mechanical pulps and chemi-mechanical pulps. Pulps can be further divided into subgroups, with mechanical pulps including groundwood (SGW), pressure groundwood (PGW), re- fined mechanical pulp (RMP), thermomechanical pulp (TMP) and others, such as TRMP and PRMP. Accordingly, chernimechanical pulps include low sulphonated (chemithermomechanical pulp CTMP and BCTMP), chemically modified (OPCO) and high sulphonated pulps (CMP, TJHYS).
- SGW groundwood
- PGW pressure groundwood
- RMP re- fined mechanical pulp
- TMP thermomechanical pulp
- chernimechanical pulps include low sulphonated (chemithermomechanical pulp CTMP and BCTMP), chemically modified (OPCO) and high sulphonated pulps (CMP, TJHYS).
- Chernimechanical pulps typically differ from purely mechanical pulps in that the wood chips are pre-treated with alkaline solutions containing sulphite or alkaline solutions containing peroxide before mechanical defibration.
- the pre-treatment is intended to enhance the def ⁇ brating process e.g. by decreasing energy consumption or to improve the technical quality of the paper.
- Mechanical pulps are used in the production of e.g. newsprint and magazine paper and porous paper grades (tissue papers).
- a number of highly bleached chemi- mechanical pulps (BCTMP qualities) are also used as a replacement of chemical pulp in bleached printing papers.
- Wood entrains a number of substances that interfere with the papermaking process, degrade the pulp and paper quality and hamper closed water circulation.
- the main interfering substances derived from wood comprise lipophilic extractives, i.e. wood pitch and polyvalent metals.
- lipophilic extractives i.e. wood pitch and polyvalent metals.
- the most frequent problems caused by lipophilic extractives include various contamination and clogging problems, impaired runnabil- ity of the papermaking machine and impaired quality of the end product.
- Polyvalent metals again, are problematic, because they generate deposits e.g. together with lipophilic extractives, oxalates and inorganic anions, reduce the washing effect of extractives, hamper the activity of chemicals used in paper production and hamper the peroxide bleaching process.
- US patent specification 4,756,799 discloses a method for producing chemi- mechanical pulp from chips, comprising steaming, single-step impregnation with alkali and peroxide, liquid removal, preheating, one or two-step refining and bleaching of the chips.
- the alkaline treatment softens the material, and this favours defi- bration, given the better preservation of the geometrical shape of the fibres. It is also known that alkaline treatment gives the pulp a darker shade.
- US patent specification 4,356,213 discloses a method for treating wood chips, which comprises impregnation of the chips with an impregnating solution containing sodium sulphite, sodium hydroxide and/or sodium bisulphite.
- the impregnated chips are dewatered and the chips are washed with a washing liquid.
- This patent sets fort that the impregnating solution fills up the cavities in the chips, thus avoiding absorption of washing liquor into the chips.
- US patent specification 4,486,267 discloses a method for preparing chemi- thermomechanical pulp (CTMP) from hardwood, the method comprising a two-step chemical treatment preceding refining.
- the chips are impreg- nated with an alkaline solution having a pH of at least 7.5 and containing sodium hydroxide, whereby the chips soften and swell by chemical means.
- the alkaline solution is removed and a second chemical treatment is carried out, in which the chips are impregnated with a sulphite solution containing sodium sulphite and/or sodium bisulphite.
- the chips are digested with a sulphite solution in order to sulphonise the lignin contained in the chips, followed by defibration of the chips thus obtained.
- US patent specification 3,428,520 discloses a method for producing chemical pulp, the method comprising impregnation of chips with a solution of an organic peroxygen compound, such as peroxygen acid, and then the chips are digested in the vapour phase, the organic peroxygen compound oxidising the lignin so that it can be extracted with an alkali solution.
- the organic peroxygen compound has the explicit purpose of converting the lignin into a form that can be extracted, in other words, the method aims at delignification.
- FI patent specification 107545 B discloses a method for treating mechanical pulp by adding aliphatic percarboxylic acid at a rate of 0.5-5 kg/ton of pulp as an agent acting on the opacity of the pulp.
- the percarboxylic acid is added into the peroxide bleaching of defibrated mechanical pulp or into the after-treatment after peroxide bleaching.
- EP patent specification 0 464 110 Bl discloses a method for bleaching mechanical or chemi-mechanical pulp, the method comprising a first step for treating the pulp with a reducing agent such as sodium bisulphite or sodium borohydride, and a second step for treating the pulp with a peroxygen compound, and a third step for treat- ing the pulp with a peroxygen compound.
- This peroxygen compound may be e.g. hydrogen peroxide or peractic acid.
- This method relates to the bleaching of mechanically defibrated pulp.
- US patent specification 6,364,999 Bl discloses a method for removing an extractive from wood chips by extracting the wood chips with organic solvents, among which acetone is said to be particularly advantageous.
- Acetone extraction removes up to 65% of the extractive.
- the weight ratio of solvent to wood chips is in the range 6:1-1:1, in other words, very large amounts of solvent are required for extraction.
- the extractive can be removed from the solvent and purified solvent, can be recirculated to extraction.
- Example 1 of this patent specification gives a comparative ex- ample using peracetic acid, Caron acid and hypochlorous acid as the solvent.
- the patent specification notes with respect to these solvents that the effect of oxidised acids is based on chemical reactions, which modify the wood resins so that they can be extracted, which is not efficient in terms of thermodynamics.
- peracids can be utilised in chip soaking and further in digestion, such as Milox digestion and in the treatment of various wood components, when it is desirable to analyse extractives, cellulose components etc.
- the invention has the purpose of providing a method allowing the removal of extractives and optionally electrolytes during the production of mechanical pulp, while allowing pulp production with a small amount of water.
- a method for removing extractives during the production of mechanical pulp comprising a step for impregnating chopped lignocellulosic material used in the pulp production before mechanical defibration with a solution containing a peracid at a maximum pH value of 7, the amount of the peracid being 0.5-20 kg/ton of dry lignocellulosic ma- terial, indicated as 100% peracid.
- This method can also comprise a liquid removal step, wherein a liquid containing unreacted feed liquor, soluble reaction products, e.g. reaction products of extractives, and optionally electrolytes, is removed from the impregnated material.
- chopped lignocellulosic material is impregnated with a solution containing a peracid at a maximum pH value of 7, the amount of the peracid being 0.5-20 kg/ton of dry lignocellulosic material, indicated as 100% peracid,
- the material having reduced extractive and electrolyte concentration is defibrated mechanically in one or more steps, and iv) the mechanical pulp thus obtained is bleached.
- Said chopped lignocellulosic material mainly implies chip softwood or hardwood and or a material having typically an average length of 5-60 mm and an average length of typically 1-10 mm.
- the typical softwood species comprise the following, for instance:
- - spruces such as e.g. Picea abies, Picea mariana, Picea glauca,
- - firs such as e.g. Abies balsamea, Abies alba,
- pines such as e.g. Pinus radiata, Pinus sylvestris, Pinus strobes, Pinus resinosa, Pinus banksiana, Pinus contorta, Pinus ponderosa, Pinus caribaea, Pinus patula, Pinus virginiana,
- - hemlocks such as e.g. Tsuga heterophylla, Tsuga canadensis.
- Thuja occidentalis e.g. Thuja occidentalis, Thuja plicata
- Larix laricina Larix decidua
- Typical hardwood species comprise the following, for instance:
- - birches such as e.g. Betula papyrifera
- - aspens such as e.g. Populus tremula, Populus tremuloides, Populus deltoides,
- eucalyptus such as e.g. E. grandis, E. globulus, E. viminalis,
- the extractive mainly consists of wood pitch, containing among other things fatty acids, resin acids, triglycerides, steryl esters, sterols and lignans.
- the electrolytes chiefly consist of polyvalent metals derived from wood, such as e.g. calcium, copper, magnesium, manganese and iron.
- the peracid impregnation of the invention does not substantially affect lignin.
- the peracid may be an organic or an inorganic peracid.
- the peracid is preferably an organic peracid, such as peracetic acid, performic acid or perpropionic acid, or a mixture of these peracids.
- organic peracid one may use peracid solutions puri- fied either by distillation or in some other manner, or equilibrium solutions of per- acids.
- Caron acid is a preferred inorganic peracid. It is also possible to use different mixtures of peracids.
- the amount of peracid is preferably about 0.5-15 kg/ton of dry fibre material, more advantageously about 0.5-10 kg/ton of dry fibre material and particularly advantageously about 0.5-7 kg/ton of dry fibre material.
- the amount of peracid is indicated as 100% peracid.
- Impregnation can be performed using methods and devices known per se, with impregnation carried out e.g. after the material has been treated with a device of screw press type.
- the pulp is compressed in a screw press, and as the pulp is subsequently released from pressure, i.e. underpressure is generated, the pulp absorbs impregnating liquid.
- the impregnation period may be approx. in the range 1-60 minutes, preferably approx. 5-60 minutes, this effective period including the duration of an optional post-steaming and the liquid removal period.
- the impregnation period signifies the period from the moment impregnation starts until liquid removal has been completed.
- Impregnation and liquid removal can be performed in one or several steps.
- the method of the invention may comprise one or more steaming steps, which are performed before and/or after impregnation.
- the material can be steam-treated before or after impregnation, or the material can be steam-treated both before impregnation and after impregnation.
- Steaming preceding impregnation aims at preheating of the material, reducing the air content and homogenising the material.
- Steaming after impregnation and liquid removal aims at heating of the material and enhancing peracid reactions with respect to interfering substances.
- Impregnation is preferably performed in the presence of a chelating agent.
- the che- lating agent is preferably added into the impregnation.
- a particularly suitable chelating agent is a chemical whose chelating capacity is preserved in the presence of peracid.
- the amount of chelating agent is preferably about 0.1-2 kg/ton of dry lignocellulosic material, more preferably about 0.5-1 kg/ton of dry lignocellulosic material.
- the following chelating agents are suitable:
- (b) (poly)aminopolycarboxylic acids such as ethylene diamine tetraacetic acid, i.e. EDTA, diethylene triamine pentaacetic acid, i.e. DTP A, 2,2'-iminodisuccinic acid, i.e. ISA, and ethylene diamine-N,N'-disuccinic acid, i.e. EDDS, and
- N-bis- or N-tris-[(l,2-dicarboxy ethoxy)ethyl]amine derivatives such as N-bis- [(1,2-dicarboxy ethoxy) ethyl] amine and N-bis[(l,2-dicarboxy ethoxy) ethyl] as- partic acid, which have been described in WO 97/45396 and FI 106258.
- the chelating agents in group (c) are particularly advantageous.
- the chelating agents my appear in acid form or as alkali metal and alkaline earth metal salts.
- the pH value is maximally 7, preferably about 2-7, more ad- vantageous approx. in the range 3-5 and particularly advantageously approx. in the range 3.5-5.
- the impregnation temperature is preferably maximally about 140 °C and at least about 20 °C and more advantageously maximally about 120 °C.
- the preferred impregnation temperature is about 20-100 °C and a particularly advantageous impreg- nation temperature is about 20-80 °C.
- At least a portion of the liquid obtained in the liquid removal step containing unreacted feed liquor, soluble reaction products, e.g. reaction products of extractives, and optionally electrolytes, can be returned to any of the preceding steps, such as washing of chopped lignocellulosic material, during which sand and other solids are removed from the material.
- the liquid obtained in the liquid removal step or a portion of this can also be conducted to waste water purification or evaporation and the dry matter to combustion or any other purpose of use.
- the liquid removal step ii) can be performed by means of a screw press or by means of other known methods and/or devices.
- the pH value of the material can be regulated to the range of approx. 4.5-8.
- the pH value is preferably raised by means of a base, such as sodium hydroxide, e.g. to the pH value 7 or a value close to this.
- a pH increase is advantageous, because defibration at a low pH value results in inadequate strength properties.
- the liquid removal step ii) comprises liquid removal preferably so as to obtain liquid in the impregnated material at a rate of 0.2-2 ton/ton of dry lignocellulosic material, preferably 0.3-1.6 ton/ton of dry lignocellulosic material.
- step iii) the material is mechanically defibrated using one or more refiners, e.g. a disc refiner.
- refiners e.g. a disc refiner.
- the pulp obtained in step iii) can be screened/classified and thickened.
- the pulp obtained in step iv) is bleached.
- the bleaching is preferably carried out using a process that comprises alkaline peroxide bleaching.
- the bleaching may comprise one or more alkaline peroxide steps and/or a combination of an alkaline peroxide bleaching and a reducing bleaching step, such as e.g. dithionite bleaching.
- the stock can be treated with a chelating agent before bleaching.
- the chelating treatment is followed by precipitation before bleaching, if necessary.
- Chemi-mechanical pulps are prepared by the method of the invention.
- the invention also relates to the use of a peracid for removing extractives and optionally electrolytes from chopped lignocellulosic material, which is intended for use in mechanical pulp production, the peracid batch being 0.5-20 kg/ton of dry lignocellulosic material, indicated as 100% peracid.
- the peracid batch is preferably about 0.5-15 kg/ton, more advantageously about 0.5-10 kg/ton and particularly ad- vantageously about 0.5-7 kg/ton.
- the invention allows removal of extractives and polyvalent metals from the chips before the actual pulp production process owing to peracid impregnation. This achieves interfering substance removal with higher efficiency than present effi- ciency, yet with considerably smaller amounts of water than those currently employed.
- the chip extractive concentration has been decreased to almost half in the optimal case, and the chip metal concentration to about 40% from the original concentration.
- the water amount to be removed was as low as 0.7-0.8 m 3 /t, which constitutes only about 3—16% of the water amount to be removed at the present time.
- a large and expensive water-treatment plant would be required, and especially metal removal would require e.g.
- peracid impregnation has the advantage of modifying extractives e.g. by oxidation/polymerisation, resulting in a lower (COD) (TOC) concentration of water fraction to be removed than in current process solutions, such as sulphite impregnation. This results in lower loads on the waste water plant, and a decrease in the amount of poorly biodegradable extractives facilitates waste water purification.
- the chips 1 are conducted to washing 2 and from there to impregnation 3, to which a peracid solution 4 and a chelating agent 5 are fed.
- Liquid 6 is removed from chip wash 2.
- the chips are conducted to liquid removal 7, during which liquid 8 containing extractives and electrolytes is removed.
- the liquid 8 can be removed as a flow 9 from the system, or a portion of the liquid 8 can be recirculated to chip washing 2 and/or impregnation 3.
- Liquid 10 can also be removed from the impregnation step 3.
- Line 11 illustrates an optional recycling, stirring or liquid replacement provisions.
- the chips are conducted to defibration 12, from where the pulp is then taken to further processing, such as bleaching.
- Chips were impregnated at a temperature of 70 °C with peracetic acid (peracid A), perpropionic acid (peracid B) or performic acid (peracid C), without pH regulation and using an impregnation period of 45 minutes.
- the feed liquor had a concentration of peracetic acid of about 10 g/1.
- the ratio water: chips was 6:1.
- a chelating agent was used at a rate of 0.2%> by weight of dry chips.
- the chelating agent was of a mixture of N-bis[(l,2-dicarboxyethoxy)ethyl]amine and N-bis[(l,2- dicarboxy ethoxy)ethyl]aspartic acid. Comparative tests were conducted, in which chips were impregnated at a temperature of 70 °C with pure water alone, with sulphite (CTMP process) or with formic acid, without pH regulation, using an impregnation period of 45 minutes.
- CMP process sulphit
- Example 2 Chips were impregnated with peracids in the same manner as in example 1, but the pH was regulated to 3, 5 and 7, respectively.
- the test results are shown in the following table 2.
- Chips were impregnated at a temperature of 70 °C with peracetic acid (peracid A) at pH 2-3. The effect of the peracid amounts, the impregnation periods and the chelating agent on the extractive concentration was examined.
- the fed liquor had a peracetic acid concentration of about 10-20 g/1.
- the ratio water:chips was 6:1.
- the test results are given in the following table 3.
- the chelating agent was the same substance as in example 1.
- Chips were impregnated with sulphite (comparison), peracetic acid (peracid A) and performic acid (peracid C) and were subjected to post-steaming. A short impregnation period was used. The impregnation temperature was 70 °C in the last array and 90 °C in the remaining ones. Steaming was carried out under overpressure of 2 bar and at a temperature of 120 °C. The fed liquid had a peracetic acid concentration of about 10-20 g/1. The ratio waterxhips was 6:1. Steaming was carried out after impregnation and liquid removal. The test results are given in table 4. Table 4
- peracid batches in table 5 and also table 6 below are indicated as 100% peracetic acid/chips, calculated as oven-dry chips, and the peroxide batch of peroxide bleaching is indicated as 100% hydrogen peroxide/ton of pulp, calculated as dry pulp.
- alkaline sulphonation (30 kg of 100% Na2S03/t of chips, calculated as dry) gives the pulp roughly as low or lower an extractive concentration compared to peracetic acid impregnation under acidic conditions and subsequent refining under neutral conditions.
- the bleached pulp received a lower extractive concentration compared to the reference pulps, i.e. alkaline sulphonation-impregnated refined pulp further bleached with alkaline peroxide, or water-impregnated, refined pulp further bleached with alkaline peroxide.
- the refined pulps were washed before peroxide bleaching, so that residual chemicals from impregnation did not reach the peroxide-bleaching step.
- Peroxide bleaching was performed by using NaOH for pH regulation and water glas as a stabiliser at a rate of 30 kg of product/ton of pulp, calculated as dry pulp.
- Table 6 indicates that the examined peracid batches did not show as high a brightness of peracid-impregnated pulps before alkaline peroxide bleaching compared to the brightness of the sulphonation-impregnated CTMP reference or the water- impregnated TMP reference. This is due to the formation of chromophore groups during peracid impregnation and the chromophore groups formed with refiners under oxidising conditions, resulting in decreased brightness of the pulp. During reducing sulphonation or subsequent refining, oxidising conditions are avoided and chromophore groups do not form as readily as under oxidising conditions at high temperature during refining after equilibrium peracid impregnation.
- Alkaline peroxide bleaching after peracid impregnation enhances pulp brightness appreciably.
- the brightening potential for peroxide bleaching of coloured chromophore groups formed in the pulp during peracid impregnation and subsequent refining is not obvious to those skilled in the art.
- Table 6 also shows that neutralisation of peracid-impregnated pulps for refining is advantageous.
- a low neutralising pH of 3.5 after peracid impregnation yields a clearly poorer strength of the refined pulp than does neutralisation to a pH range of 6-7.
- Assumedly peracid impregnation at a very low pH value (pH ⁇ 3.5) impairs the quality of refined fibres unless neutralisation is performed after the impregnation.
- alkaline peroxide bleaching improves the strength of impregnated and refined pulps.
- the brightness and the strength of peracid-impregnated pulps further refined at a pH level of 6-7 improved during peroxide bleaching to values above those of the reference sulphonation pulp. Raising the peracid batch of peracid impregnation above 7 kg PAA/t did not yield better results.
- Peracid impregnation dissolves the organic substances.
- equilibrium peracid contains acetic acid and acetic acid is released from peracid during the reactions, and hence it is advantageous to avoid excessive peracid batches.
Landscapes
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20031937A FI121381B (en) | 2003-12-31 | 2003-12-31 | A method for removing extractives in the manufacture of a mechanical pulp and a method for producing a mechanical pulp |
| PCT/FI2004/000813 WO2005064074A2 (en) | 2003-12-31 | 2004-12-31 | Process for removing interfering substances in the production of mechanical pulp and process for producing mechanical pulp |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1702100A2 true EP1702100A2 (en) | 2006-09-20 |
| EP1702100B1 EP1702100B1 (en) | 2009-03-25 |
Family
ID=29763624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04805208A Expired - Lifetime EP1702100B1 (en) | 2003-12-31 | 2004-12-31 | Process for removing interfering substances in the production of mechanical pulp and process for producing mechanical pulp |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1702100B1 (en) |
| CA (1) | CA2549834C (en) |
| FI (1) | FI121381B (en) |
| WO (1) | WO2005064074A2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2467532T3 (en) * | 2009-08-24 | 2014-11-28 | Abengoa Bioenergy New Tech Llc | Method for producing ethanol and co-products from cellulosic biomass |
| US9745504B2 (en) * | 2013-03-21 | 2017-08-29 | Halliburton Energy Services, Inc. | Wellbore servicing compositions and methods of making and using same |
| US9512348B2 (en) | 2013-03-28 | 2016-12-06 | Halliburton Energy Services, Inc. | Removal of inorganic deposition from high temperature formations with non-corrosive acidic pH fluids |
| SE541198C2 (en) * | 2016-11-02 | 2019-04-30 | Winnington Ab | Defibrated tobacco raw material |
| WO2019048698A1 (en) * | 2017-09-11 | 2019-03-14 | Kemira Oyj | Process for treating pulp |
| US11877590B2 (en) | 2019-03-27 | 2024-01-23 | Fiedler & Lundgren Ab | Smokeless tobacco composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3428520A (en) * | 1965-08-12 | 1969-02-18 | Scott Paper Co | Pulping process with lignin recovery |
| US6364999B1 (en) * | 1995-12-27 | 2002-04-02 | Weyerhaeuser Company | Process for producing a wood pulp having reduced pitch content and process and reduced VOC-emissions |
-
2003
- 2003-12-31 FI FI20031937A patent/FI121381B/en active IP Right Grant
-
2004
- 2004-12-31 WO PCT/FI2004/000813 patent/WO2005064074A2/en not_active Ceased
- 2004-12-31 EP EP04805208A patent/EP1702100B1/en not_active Expired - Lifetime
- 2004-12-31 CA CA2549834A patent/CA2549834C/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005064074A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FI121381B (en) | 2010-10-29 |
| WO2005064074A3 (en) | 2005-11-03 |
| CA2549834A1 (en) | 2005-07-14 |
| CA2549834C (en) | 2013-03-19 |
| EP1702100B1 (en) | 2009-03-25 |
| FI20031937A0 (en) | 2003-12-31 |
| WO2005064074A2 (en) | 2005-07-14 |
| FI20031937L (en) | 2005-07-01 |
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