WO2007091942A1 - Method for the manufacturing of microfibrillated cellulose - Google Patents

Method for the manufacturing of microfibrillated cellulose Download PDF

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Publication number
WO2007091942A1
WO2007091942A1 PCT/SE2007/000082 SE2007000082W WO2007091942A1 WO 2007091942 A1 WO2007091942 A1 WO 2007091942A1 SE 2007000082 W SE2007000082 W SE 2007000082W WO 2007091942 A1 WO2007091942 A1 WO 2007091942A1
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WIPO (PCT)
Prior art keywords
pulp
microfibrillated cellulose
refining
enzyme
fibres
Prior art date
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Ceased
Application number
PCT/SE2007/000082
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French (fr)
Inventor
Tom Lindström
Mikael Ankerfors
Gunnar Henriksson
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STFI Packforsk AB
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STFI Packforsk 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
Priority to DE07709298.9T priority Critical patent/DE07709298T1/en
Priority to JP2008554183A priority patent/JP2009526140A/en
Priority to ES07709298.9T priority patent/ES2436636T1/en
Priority to EP07709298.9A priority patent/EP1984561B1/en
Priority to US12/161,463 priority patent/US8546558B2/en
Priority to PL07709298T priority patent/PL1984561T3/en
Application filed by STFI Packforsk AB filed Critical STFI Packforsk AB
Priority to AU2007212781A priority patent/AU2007212781B2/en
Priority to CA2641607A priority patent/CA2641607C/en
Priority to BRPI0707255A priority patent/BRPI0707255B1/en
Publication of WO2007091942A1 publication Critical patent/WO2007091942A1/en
Anticipated expiration legal-status Critical
Priority to NO20083546A priority patent/NO341867B1/en
Ceased legal-status Critical Current

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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
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres

Definitions

  • This invention concerns the technical field of pulp treatment for the manufacturing of microfibrillated cellulose. Also disclosed is a microf ibrillated cellulose manufactured in accordance with said method and uses of said cellulose.
  • a problem when manufacturing microfibrillated cellulose from pulp is the clogging of the pulp, when the pulp is pumped through high pressure fluidizers/homogenizers. Thus there is a need for a process wherein this clogging problem can be alleviated and/or avoided.
  • a further problem when manufacturing microfibrillated cellulose from pulp is the high energy consumption and accordingly there is a need for a process wherein high energy consumption can be avoided.
  • the present invention solves the above problems by providing according to a first aspect of the invention a method for treatment of chemical pulp for the manufacturing of microfibrillated cellulose comprising the following steps: a) providing a hemicellulose containing pulp, b) refining said pulp in at least one step and treating said pulp with one or more wood degrading enzymes at a relatively low enzyme dosage, and c) homogenizing said pulp thus providing s aid microfibrillated cellulose.
  • a microfibrillated cellulose obtainable by the method according to the first aspect is provided .
  • use of said microfibrillated cellulose according to the second aspect in food products, paper products, composite materials, coatings or in rheology modifiers (e.g. drilling muds) is provided.
  • beating apparatus embraces any apparatus capable of refining (beating) chemical pulp.
  • beating apparatuses are beaters and refiners optionally equipped either with refining discs (disc refiners) or a refining plug in a conical housing (conical refiner), ball mills, rod mills, kneader pulper, edger runner and drop work.
  • a beating apparatus may operate continuously or discontinuously.
  • the homogenization of said pulp of step c) may be performed using any apparatus, known for a person skilled in the art, suitable for homogenization of a pulp. For instance a high-pressure fluidizer/homogenizer may be used for the homogenization of said pulp of step c).
  • the chemical pulps that may be used in the present invention include all types of chemical wood-based pulps, such as bleached, half-bleached and unbleached sulphite, sulphate and soda pulps, kraft pulps together with unbleached, half-bleached and bleached chemical pulps, and mixtures of these.
  • said pulp contains from about 5 to 20 % of hemicellulose.
  • the consistency of the pulp during manufacture of microfibrillated cellulose may be any consistency, ranging from low consistency through medium consistency to high consistency. The consistency is preferably from 0.4 to 10 %, most preferred from 1 to 4 %.
  • said pulp is a s ulphite pulp.
  • the pulp may consist of pulp from hardwood, softwood or both types.
  • Preferably said pulp contains pulp from softwood.
  • the pulp may also contain softwood of one kind only or a mixture of different softwood types.
  • the pulp may e.g. contain a mixture of pine and spruce.
  • said enzyme is used at a concentration of from 0.1 to 500 ECU/ g fibres, preferably from 0.5 to 150 ECU/ g fibres, most preferred 0.6 to 100 ECU/ g fibres, especially preferred from 0.75 to 10 ECU/ g fibres.
  • said enzyme is a hemicellulase or a cellulase or a mixture thereof, preferably a mixture of culture filtrate type.
  • said enzyme is a cellulase, preferably a cellulase of endoglucanase type, most preferred a mono-component endoglucanase.
  • step b) comprises refining said pulp both before and after said enzyme treatment.
  • step b) comprises refining said pulp (only) before said enzyme treatment.
  • step b) comprises refining said pulp (only) after said enzyme treatment.
  • the first refining provides a pulp with a drainage resistance of from about 20 to about 35 0 SR and said second refining provides a pulp with a drainage resistance of above 70 0 SR.
  • a further advantage of the method according to the first aspect of the present invention is that the energy consumption is lowered when manufacturing microfibrillated cellulose from pulp.
  • Figure 1 shows a picture emanating from when doing Cryo-TEM measurements of the thickness of the microfibrills.
  • the cell wall delamination was carried out by treating the sulphite pulp in four separate steps.
  • a 4 % w/w cellulose suspension (ECO Bright, from Domsj ⁇ Fabriker AB) was mechanically refined using an Escher-Wyss refiner (Angle Refiner R1L, Escher- Wyss) with 33 kWh/tonne at a specific edge load of 2 Ws/m to 28 0 SR.
  • the pulp was a softwood pulp from a mixture of Norwegian Spruce and Scottish Pine (respectively 60% / 40%). The pulp had been TCF-bleached in a closed loop bleach plant.
  • the material was passed through a high-pressure fluidizer/homogenizer (Microfluidizer M-110EH, Microfluidics Corp.).
  • the 2 % w/w concentration pulp fibre slurry was passed through two differently sized chamber pairs (each pair connected in series). First, the slurry passed three times through a chamber pair with a diameter of 400 ⁇ m and 200 ⁇ m (the first chamber and the second chamber, respectively), and then, 5 times through a chamber pair with a diameter of 200 ⁇ m and 100 ⁇ m.
  • the operating pressures were 105 MPa and 170
  • the material was also produced using different chambers and different number of passes through the chambers showing that, if the pre-treatment was done in a good fashion, these parameters (chamber type and number of passes) did essentially not matter.
  • Two cases were tried (Cases E and F). In both these cases the production method was done according to Case C, with the exception of the choice of chambers and the number of passes.
  • Case E the material was passed one time through a chamber pair with a diameter of 200 ⁇ m and 100 ⁇ m.
  • the operating pressure was 170 MPa.
  • Case F the material was passed one time through a chamber pair with a diameter of 400 ⁇ m and 200 ⁇ m.
  • the operating pressure was 105 MPa.
  • microfibrillated cellulose according to the second aspect of the present invention differs from the one described in US 4,341 ,807 mentioned above.
  • the microfibrillated cellulose according to the second aspect of the present invention has a much higher specific surface in comparison with the one described in US 4,341 ,807, which is described in Journal of Applied Polymer Science (JAPS) below (ref. 1 and 2) and is therefore more reactive and more interesting for most of the practical applications thereof.
  • JAPS Journal of Applied Polymer Science
  • the microfibrillated cellulose according to the second aspect of the present invention has according to NMR-measurements an average thickness of 17.3 +/- 0.7 nm with CP/MAS 13C-NMR.
  • the method for determining the thickness of the microfibrills is described in the publications 3 and 4 below.
  • Cryo-TEM measurements (see Figure 1 ) of the thickness, of the microfibrillated cellulose according to the second aspect of the present invention give a range on this thickness of between 3.5 nm to 18 nm in comparison with 25- 100 nm for the microfibrillated cellulose produced in accordance with US 4,341 ,807.
  • the electron microscope methods are directly comparable whereas NMR primarily appears to detect the big aggregates.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The present invention provides a method for treatment of chemical pulp for the manufacturing of microfibrillated cellulose comprising the following steps: a) providing a hemicellulose containing pulp, b) refining said pulp in at least one step and treating said pulp with one or more wood degrading enzymes at a relatively low enzyme dosage, and c) homogenizing said pulp thus providing s aid microfibrillated cellulose. According to a second aspect of the invention a microfibrillated cellulose obtainable by the method according to the first aspect is provided . According to a third aspect of the invention, use of said microfibrillated cellulose according to the second aspect in food products, paper products, composite materials, coatings or in rheology modifiers (e.g. drilling muds) is provided .

Description

Method for the manufacturing of microfibrillated cellulose
This invention concerns the technical field of pulp treatment for the manufacturing of microfibrillated cellulose. Also disclosed is a microf ibrillated cellulose manufactured in accordance with said method and uses of said cellulose.
Background
Through US 4,341 ,807 a method for manufacturing a microfibrillated cellulose is disclosed by using homogenization. The method is facilitated by adding a hydrophilic polymer.
A problem when manufacturing microfibrillated cellulose from pulp is the clogging of the pulp, when the pulp is pumped through high pressure fluidizers/homogenizers. Thus there is a need for a process wherein this clogging problem can be alleviated and/or avoided. A further problem when manufacturing microfibrillated cellulose from pulp is the high energy consumption and accordingly there is a need for a process wherein high energy consumption can be avoided.
Summary of the invention The present invention solves the above problems by providing according to a first aspect of the invention a method for treatment of chemical pulp for the manufacturing of microfibrillated cellulose comprising the following steps: a) providing a hemicellulose containing pulp, b) refining said pulp in at least one step and treating said pulp with one or more wood degrading enzymes at a relatively low enzyme dosage, and c) homogenizing said pulp thus providing s aid microfibrillated cellulose.
According to a second aspect of the invention a microfibrillated cellulose obtainable by the method according to the first aspect is provided . According to a third aspect of the invention, use of said microfibrillated cellulose according to the second aspect in food products, paper products, composite materials, coatings or in rheology modifiers (e.g. drilling muds) is provided.
Detailed description of the invention It is intended throughout the present description that the expression "refiner" embraces any apparatus capable of refining (beating) chemical pulp. Examples of beating apparatuses are beaters and refiners optionally equipped either with refining discs (disc refiners) or a refining plug in a conical housing (conical refiner), ball mills, rod mills, kneader pulper, edger runner and drop work. A beating apparatus may operate continuously or discontinuously. The homogenization of said pulp of step c) may be performed using any apparatus, known for a person skilled in the art, suitable for homogenization of a pulp. For instance a high-pressure fluidizer/homogenizer may be used for the homogenization of said pulp of step c).
The chemical pulps that may be used in the present invention include all types of chemical wood-based pulps, such as bleached, half-bleached and unbleached sulphite, sulphate and soda pulps, kraft pulps together with unbleached, half-bleached and bleached chemical pulps, and mixtures of these. Preferably said pulp contains from about 5 to 20 % of hemicellulose. The consistency of the pulp during manufacture of microfibrillated cellulose may be any consistency, ranging from low consistency through medium consistency to high consistency. The consistency is preferably from 0.4 to 10 %, most preferred from 1 to 4 %.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said pulp is a s ulphite pulp. The pulp may consist of pulp from hardwood, softwood or both types. Preferably said pulp contains pulp from softwood. The pulp may also contain softwood of one kind only or a mixture of different softwood types. The pulp may e.g. contain a mixture of pine and spruce.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said enzyme is used at a concentration of from 0.1 to 500 ECU/ g fibres, preferably from 0.5 to 150 ECU/ g fibres, most preferred 0.6 to 100 ECU/ g fibres, especially preferred from 0.75 to 10 ECU/ g fibres. According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said enzyme is a hemicellulase or a cellulase or a mixture thereof, preferably a mixture of culture filtrate type.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said enzyme is a cellulase, preferably a cellulase of endoglucanase type, most preferred a mono-component endoglucanase.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein step b) comprises refining said pulp both before and after said enzyme treatment.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein step b) comprises refining said pulp (only) before said enzyme treatment. According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein step b) comprises refining said pulp (only) after said enzyme treatment.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein the first refining provides a pulp with a drainage resistance of from about 20 to about 35 0SR and said second refining provides a pulp with a drainage resistance of above 70 0SR.
As said above a further advantage of the method according to the first aspect of the present invention is that the energy consumption is lowered when manufacturing microfibrillated cellulose from pulp.
Preferred features of each aspect of the invention are as for each of the other aspects mutatis mutandis. The prior art document mentioned herein are incorporated to the fullest extent permitted by law. The invention is further described in the following examples in conjunction with the appended figure which do not limit the scope of the invention in any way. Embodiments of the present invention are described in more detail with the aid of examples of embodiments and the figure, the only purpose of which is to illustrate the invention and are in no way intended to limit its extent.
Figures
Figure 1 shows a picture emanating from when doing Cryo-TEM measurements of the thickness of the microfibrills.
Examples
Example 1 :
Treatment of sulphite pulp with enzyme and refining said pulp
The cell wall delamination was carried out by treating the sulphite pulp in four separate steps.
1. A 4 % w/w cellulose suspension (ECO Bright, from Domsjό Fabriker AB) was mechanically refined using an Escher-Wyss refiner (Angle Refiner R1L, Escher- Wyss) with 33 kWh/tonne at a specific edge load of 2 Ws/m to 28 0SR. The pulp was a softwood pulp from a mixture of Norwegian Spruce and Scottish Pine (respectively 60% / 40%). The pulp had been TCF-bleached in a closed loop bleach plant.
2. Four different amounts of monocomponent endoglucanase were added (Cases A, B, C and D) (Novozym 476, a cellulase preparation, from Novozymes A/S). In
Case A no enzyme was added (0 ECU/g fibres). In case B, C and D, 100 grams
(calculated as dry fibres) of refined pulp was dispersed in 2.5 litres of phosphate buffer (pH 7, final pulp concentration 4 % w/w) with different amounts of enzymes
(Case B=0.65 ECU/g fibres, Case C=0.85 ECU/g fibres, Case D=150 ECU/g fibres) and incubated at 50 0C for 2 hours. The samples were mixed manually every 30 minutes. Then the samples were washed with de-ionized water and the enzymes were then denaturated at 80 0C for 30 minutes. At the end, the pulp sample was washed with de-ionized water again.
3. The pre-treated pulps were refined once again with the Escher-Wyss refiner, to
°SR-values (Shopper - Riegler) between 90 and 95 (average refining energy 90 kWh/tonne, specific edge load 1 Ws/m).
4. Subsequently, the material was passed through a high-pressure fluidizer/homogenizer (Microfluidizer M-110EH, Microfluidics Corp.). The 2 % w/w concentration pulp fibre slurry was passed through two differently sized chamber pairs (each pair connected in series). First, the slurry passed three times through a chamber pair with a diameter of 400 μm and 200 μm (the first chamber and the second chamber, respectively), and then, 5 times through a chamber pair with a diameter of 200 μm and 100 μm. The operating pressures were 105 MPa and 170
MPa, respectively.
The material was also produced using different chambers and different number of passes through the chambers showing that, if the pre-treatment was done in a good fashion, these parameters (chamber type and number of passes) did essentially not matter. Two cases were tried (Cases E and F). In both these cases the production method was done according to Case C, with the exception of the choice of chambers and the number of passes.
In Case E the material was passed one time through a chamber pair with a diameter of 200 μm and 100 μm. The operating pressure was 170 MPa. In Case F the material was passed one time through a chamber pair with a diameter of 400 μm and 200 μm. The operating pressure was 105 MPa.
Table 1.
Figure imgf000006_0001
Further measurements were done which clearly indicates that the microfibrillated cellulose according to the second aspect of the present invention differs from the one described in US 4,341 ,807 mentioned above. The microfibrillated cellulose according to the second aspect of the present invention has a much higher specific surface in comparison with the one described in US 4,341 ,807, which is described in Journal of Applied Polymer Science (JAPS) below (ref. 1 and 2) and is therefore more reactive and more interesting for most of the practical applications thereof. In JAPS the size (=the thickness of the microfibrills) is indicated to be between 25-
100 nm (ref. 1 and 2). The microfibrillated cellulose according to the second aspect of the present invention has according to NMR-measurements an average thickness of 17.3 +/- 0.7 nm with CP/MAS 13C-NMR. The method for determining the thickness of the microfibrills is described in the publications 3 and 4 below. Cryo-TEM measurements (see Figure 1 ) of the thickness, of the microfibrillated cellulose according to the second aspect of the present invention, give a range on this thickness of between 3.5 nm to 18 nm in comparison with 25- 100 nm for the microfibrillated cellulose produced in accordance with US 4,341 ,807. The electron microscope methods are directly comparable whereas NMR primarily appears to detect the big aggregates.
Various embodiments of the present invention have been described above but a person skilled in the art realizes further minor alterations, which would fall into the scope of the present invention. The breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. For example, any of the above- noted methods can be combined with other known methods. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
List of documents appearing in the description
1. Herrick, F. W., R. R. Casebier, et al. (1983). "Microfibrillated Cellulose:
Morphology and Accessibility." Journal of Applied Polymer Science: Applied Polymer Svmposium(37): 797-813. o ...fibrils appear as rope-like bundles of partially embedded microfibrills having diametres of 25 to 100 nm .... (page 803)
2. Turbak, A. F., F. W. Snyder, et al. (1983). "Microfibrillated Cellulose: A new Cellulose Product: Properties, Uses, and Commercial Potential." Journal of Applied Polymer Science: Applied Polymer Svmposium(37): 815-827. o ...At x 10,000 magnification, the predominant net-like structure of the product, after carbon dioxide critical point drying, contains microfibrils having diameters of 25-100 nm .... (page 820) o Refers to US 4,341 ,807, US 4,374,702 and US 4,378,381
3. Larsson, P.; Wickholm, K.; Iversen, T. Carbohydr. Res. 1997, 302, 19-25.
4. Wickholm, K.; Larsson, P.; Iversen, T. Carbohydr. Res. 1998, 312, 123-129, and
US 4,341 ,807

Claims

Claims
1. A method for treatment of chemical pulp for the manufacturing of microfibrillated cellulose comprising the following steps: a) providing a hemicellulose containing pulp, b) refining said pulp in at least one step and treating said pulp with one or more wood degrading enzymes at a relatively low enzyme dosage, and c) homogenizing said pulp thus providing s aid microfibrillated cellulose.
2. A method according to claim 1 wherein said pulp is a sulphite pulp, preferably containing pulp from softwood.
3. A method according to claim 1 wherein said enzyme is used at a concentration of from 0.1 to 500 ECU/ g fibres, preferably from 0.5 to 150
ECU/ g fibres, most preferred 0.6 to 100 ECU/ g fibres, especially preferred from 0.75 to 10 ECU/ g fibres.
4. A method according to claim 1 wherein said enzyme is a hemicellulase or a cellulase or a mixture thereof, preferably a mixture of culture filtrate type.
5. A method according to claim 4 wherein said enzyme is a cellulase, preferably a cellulase of endoglucanase type, most preferred a mono-component endoglucanase.
6. A method according to claim 1 wherein step b) comprises refining said pulp both before and after said enzyme treatment.
7. A method according to claim 1 wherein step b) comprises refining said pulp before said enzyme treatment.
8. A method according to claim 1 wherein step b) comprises refining said pulp after said enzyme treatment.
9. A method according to claim 6 wherein the first refining provides a pulp with a drainage resistance of from 20 to 35 0SR and said second refining provides a pulp with a drainage resistance of above 70 °SR.
10. A microfibrillated cellulose obtainable by a method according to any one of claims 1-9.
11. Use of said microfibrillated cellulose according to claim 10 in food products, paper products, composite materials, coatings or in rheology modifiers.
12. Use of said microfibrillated cellulose according to claim 10 in cosmetic products.
13. Use of said microfibrillated cellulose according to claim 10 in pharmaceutical products.
PCT/SE2007/000082 2006-02-08 2007-01-31 Method for the manufacturing of microfibrillated cellulose Ceased WO2007091942A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AU2007212781A AU2007212781B2 (en) 2006-02-08 2007-01-31 Method for the manufacturing of microfibrillated cellulose
JP2008554183A JP2009526140A (en) 2006-02-08 2007-01-31 Process for producing microfibrillated cellulose
ES07709298.9T ES2436636T1 (en) 2006-02-08 2007-01-31  Microfibrillated cellulose manufacturing process
EP07709298.9A EP1984561B1 (en) 2006-02-08 2007-01-31 Method for the manufacturing of microfibrillated cellulose
US12/161,463 US8546558B2 (en) 2006-02-08 2007-01-31 Method for the manufacture of microfibrillated cellulose
DE07709298.9T DE07709298T1 (en) 2006-02-08 2007-01-31 Process for the preparation of microfibrillated cellulose
BRPI0707255A BRPI0707255B1 (en) 2006-02-08 2007-01-31 method for treating a chemical pulp for the manufacture of microfibrillated cellulose, microfibrillated cellulose and use
PL07709298T PL1984561T3 (en) 2006-02-08 2007-01-31 Method for the manufacturing of microfibrillated cellulose
CA2641607A CA2641607C (en) 2006-02-08 2007-01-31 Method for the manufacturing of microfibrillated cellulose
NO20083546A NO341867B1 (en) 2006-02-08 2008-08-14 Process for the preparation of microfibrillated cellulose

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0600272 2006-02-08
SE0600272-9 2006-02-08

Publications (1)

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WO2007091942A1 true WO2007091942A1 (en) 2007-08-16

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Country Status (11)

Country Link
US (1) US8546558B2 (en)
EP (1) EP1984561B1 (en)
JP (2) JP2009526140A (en)
AU (1) AU2007212781B2 (en)
BR (1) BRPI0707255B1 (en)
CA (1) CA2641607C (en)
DE (1) DE07709298T1 (en)
ES (1) ES2436636T1 (en)
NO (1) NO341867B1 (en)
PL (1) PL1984561T3 (en)
WO (1) WO2007091942A1 (en)

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WO2010102802A1 (en) 2009-03-11 2010-09-16 Borregaard Industries Limited, Norge Method for drying microfibrilated cellulose
WO2010105847A1 (en) 2009-03-20 2010-09-23 Borregaard Industries Limited, Norge Cellulose microfibrils as air release agent
WO2010142846A1 (en) 2009-06-08 2010-12-16 Upm-Kymmene Corporation Method of manufacturing paper and products obtained by the method
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WO2011095335A1 (en) 2010-02-04 2011-08-11 Borregaard Industries Limited, Norge Method and device for producing dry microfibrillated cellulose
WO2011141876A1 (en) * 2010-05-12 2011-11-17 Stora Enso Oyj A composition comprising microfibrillated cellulose and a process for the production of a composition
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US8231764B2 (en) 2009-05-15 2012-07-31 Imerys Minerals, Limited Paper filler method
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