• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    13 ABSTRACT A method for drying nanofibrillated polysaccharide to obtain a5 substantially dry nanofibrillated polysaccharide product, comprising thefollowing steps: (i) providing an aqueous suspension of nanofibrillatedpolysaccharide; (ii) increasing the solid content of said suspension, therebyforming a high solid content microfibrillated cellulose suspension; and (iii)drying said high solid content microfibrillated cellulose suspension, through a10 simultaneous heating and mixing operation.
    公开号:SE1251280A1
    申请号:SE1251280
    申请日:2012-11-09
    公开日:2014-05-10
    发明作者:Kaj Backfolk；Heidi Saxell；Isto Heiskanen；Lars Axrup；Cecilia Land Hensdal；Veikko Jokela；Ari Kotilainen；Henri Kastinen；Anna Kauppi；Esa Saukkonen
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    AWAPATENT ABKontor/HandläggareLinköping/Sofia Willquist/SZJVår referensSE-11014523Ansökningsnr1MIXING DRYING OF NANOFIBRILLATED POLYSACCHARIDETechnical fieldThe present document relates to a method of drying an aqueoussuspension of nanofibrillated polysaccharide to obtain an substantially drynanofibrillated polysaccharide product. More particularly, the presentdisclosure relates to a nanofibrillated polysaccharide product obtainable bysuch method and the uses thereof.
    BackgroundNanofibrillated polysaccharides, such as for instance microfibrillatedcellulose, have many end uses, such as in food, composites, paper, paints,plastics, cosmetics, and medical products, in which it would be good to beable to dosage nanofibrillated polysaccharide in a dry form so that the originalproperties of wet nanofibrillated polysaccharide would be retained.
    Microfibrillated cellulose which is added and used in composites istypically in a dry form.
    When microfibrillated cellulose is used in composites one shouldensure that micro fibrils are clearly separated from each other and that microfibrils are very well dispersed on the matrix.
    A low solid content dispersion of microfibrillated cellulose in water isusually a gel having pseudoplastic or thixotropic viscosity properties becausethe fibrils are very well dispersed in the matrix (water). Upon drying, however,the properties of microfibrillated cellulose are severely changed. lt”sdispersibility, hydration and rheological properties are lost or at leastsubstantially reduced or changed, depending on the severity of the drying.Typically after drying, micro and nano fibrils are bound together andsubstantially less separate micro or nano fibrils are present which henceaffects the characteristic property, for instance, as defined by a highlynanofibrillated cellulose can be found via different analysis of thenanofibrillated cellulose.
    Conventional drying techniques for drying MFC or nanofibrillatedpolysaccharides currently used today are e.g. spray drying and freeze drying.Freeze drying produces the best quality MFC in terms of preserving original2properties and in re-dispersability. However, both the operating andinvestment costs are high and the process can be difficult to scale up toindustrial processing. Spray drying, which can rather easily be scaled up, hashigh operation costs and during which process also hornification of fibrils isprone to occur.
    The term "hornification" refers to the stiffening of the polymer structurethat occurs in lignocellulosic materials when they are dried or otherwisedewatered. Because of structural changes in the wood pulp fibers upon dryingthe internal fiber shrinks. Often the fibers needs to be rewetted, or re-suspended in water for practical use and due to these structural changes theoriginal properties, i.e. being in a gel form having pseudoplastic or thixotropicviscosity, is not regained. The effect of hornification may be identified in thosephysical paper or wood pulp properties that are related to hydration orswelling, such as burst or tensile properties. (Hornification - its origin andinterpretation in wood pulps, J.M.B. Fernandes Diniz, M.H. Gil, J.A.A.M.Castro, Wood Sci Technol 37 (2004) 489-494).ln articles (e.g. LeCompte T.R. (1931), Papier (34), p.1193, Jayme, G.(1944) Papier-Fabr (42), p.187, Lyne, L. M., Gallay, W. (1954) Measurementsof wet web strength, Tappi Journal 37(12):694-697, Higgins, H.G., McKenzie,A.W. (1963) The structure and properties of paper XIV: Effects of drying oncellulose fibers and the problem of maintaining pulp strength) concerninghornification phenomenon and pulp swelling after drying and rewetting thereare suggestions made that pulp could be less hornificated if its dried in such away that fibers do not stick together during drying. According to Lyne andGallay (1950) rigorous agitation during boiling of pulp neutralizes thedehydrating effect, and that mechanical effect prevents to a large extent theloss in swelling which othen/vise occurs.lt is however impractical for pulp and papermakers to dry fibers undere.g. vigorous agitation.
    Spray-drying of fibrillated cellulose is described e.g. in WO2011/139749 A2. An aqueous suspension of nanofibrils (NFC), which areregarded as a category of MFC, is atomized in a drying chamber of a dryingapparatus. A drying gas, such as ambient air, may be used as an aid toevaporate the water present in the suspension, yielding dry NFC as theproduct. The teachings even include coating the NFC particles with sodiumsilicate prior to the atomizing step.
    WO 2011/095335 A1 describes a process, in which MFC is formed bydefibrillation of a suspension of cellulose fibers and a liquid, which is misciblewith liquid C02, and then replacing said liquid in the suspension by liquid C02,and finally removing the C02 by evaporation so as to yield dry MFC. Theprocess is claimed to overcome the MFC deterioration problems afflictingordinary oven-drying and freeze-drying processes.
    Still there is room for an improved process of drying nanofibrillatedpolysaccharide comprising composites, which is simpler to carry out whileyielding a dry MFC composite material, without loss of important re-dispersibility properties, since, if strong hornifiction or agglomeration occursduring drying the beneficial properties of cellulosic fibrils or fibrillatedaggregates are not obtained. lt it thus preferable that the dried compositemaintains its Characteristics when dispersed in aqueous systems, othersolvents or e.g. polymeric matrices. lt is also necessary to find a solution thatprevents hornification without necessary use of chemical additives, whichmight affect the properties of the final composition.
    Summarylt is an object of the present disclosure, to provide an improved oralternative method of drying microfibrillated cellulose, which eliminates oralleviates at least some of the disadvantages of the prior art.
    The invention is defined by the independent claims. Embodiments areset forth in the appended dependent claims and in the following descriptionand drawings.
    According to a first aspect, there is provided a method for dryingnanofibrillated polysaccharide to obtain a substantially dry nanofibrillatedpolysaccharide product, comprising the following steps:(i) providing an aqueous suspension of nanofibrillated polysaccharide;(ii) increasing the solid contents said suspension, thereby forming ahigh solid contents microfibrillated cellulose suspension; and(iii) drying said high solid contents microfibrillated cellulose suspension,through a simultaneous heating and mixing operation.4By “aqueous suspension of nanofibrillated polysaccharide” (NFP) ismeant that the solid contents of the suspension is in the range of 0.01wt-% to25 wt-%. This suspensiom or dispersion in water may be in a gel form. Thesaid suspension might also contain functional additives which assist in re-dispersability but they can also have another function such as providingoptical effects or improved compoundability in polymers.
    The term “nanofibrillated polysaccharide” includes nanofibrouspolysaccharides, micro or nano fibrillated cellulose (MFC/NFC), micro or nanocrystalline cellulose (MCC/NCC), regenerated cellulose, cellulose whiskers,nanofibers spun from polysacchardies such as starches, cellulosenanoparticles, porous cellulose particles, starch fibrils, or mixtures thereof ormixtures with normal pulp or fibers or with inorganic or organic syntheticfibers. The nanofibrillated polymer can also be surface modified with e.g. oneor several polymer layers.
    By “substantially dry NFP product” is meant that the water content inthe NFP product is reduced to a level where the product may be in a powderform, but still being suitable for re-dispersion in a solvent such as water. Assuch the solids content of the product may be in the range of 50-99 wt-%.
    By this method there is achieved a way of drying NFP without causinghornification problems of the micro fibrils and pulp swelling after drying andrewetting. There is further provided a way of drying the NFP in a energyefficient manner.
    By the mixing operation removal of water may be affected byevaporation or using co-solvents, such as ethanol or isopropanol. The co-solvents may be recycled during the mixing and heating operation.
    The mixing operation also provides for micro fibrils that are clearlyseparated from each other and that micro fibrils are very well dispersed in thematrix, which is normally achieved by a refining or homogenizing step a theprocess for producing e.g. MFC.
    According to one alternative of the first aspect the solid contents may,in step (ii), be increased to >15 vvt-%, or to > 20 wt-% , or to > 25 wt-% , or to> 30 wt-%.
    This solids content is based on the NFP-water ratio, but it may incertain cases contain other substances in which case the solids content maybe even higher.
    According to another embodiment step (iii) may comprise a grindingoperation.
    The grinding operation may be performed in a PVC mixer or by anysimilar method, such as a high speed mixer, where the mechanical energy isconverted into heat in the suspension whereby water is caused to evaporate.Alternativley part of the energy may be used to provide for a fibriliation or tocut fibers. Since the solid content, or the dry contents, of the suspension isrelativley high at the onset of mixing the shear forces, and friction evoived inthe suspension becomes greater thus resulting in an increased temperature.At a solids content of >15-20 wt-% the NFP solution is viscous, thus causinggreater friction.
    Step (ii) may further comprise any one of a centrifugal force operation,pressing operation and dewatering operation.
    The dewatering operation may comprise an eiectro-osmosis operationor electric field induced dewatering, electric field flow fractionation and thepressing operation may comprise a wet pressing operation.
    According to one alternative of the first aspect, the temperature of thesuspension, at step (iii) may be in the range of 75-99 °C, preferably about 80-85 °C.
    The temperature is thus kept relativley low, which is advantageous notonly in that less energy is consumed, but also in that the effect onhornification of the micro fibrils may be reduced, as hornification is prone tooccur at a higher temperature. lt may be that the temperature towards the endof the drying process is more important to control, or to keep at a low level inorder to prevent hornification of the fibrils, and that the temperature at thebeginning of the process, i.e. when the solids content is still relativley low maybe higher than the preferred temperature range. This increase in temperaturemay mainly be created through the mechanical energy provided to thesuspension by the mixing operation.
    According to an alternative embodiment the suspension may further beheated from about room temperature to the range of 75-99 °C.
    According to one embodiment of the method according to the firstaspect there may further be provided a simultaneous heating and mixingoperation in step (iii). This means that the suspension may, in step (iii) beactively heated in addition to the heat evolved during the mixing operation.6This “active heating” may for instance be used at the onset of the mixingoperation to achieve a higher starting temperature and thus a more efficientdrying. According to another embodiment this heating operation may becombined with a subsequent cooling operation to ensure the optimaltemperature of the suspension as the solid content is increased, i.e. towardsthe end of the drying operation, in order to prevent any hornification or otherharmful structural changes from occuring.
    According to another embodiment of the first aspect step (iii) may beperformed under vacuum.
    By introducing a vacuum, or performing the drying step under vacuumit is further possible to reduce both the energy needed and the dryingtemperature, which may lead to a further reduction in the hornification of themicro fibrils. lf vacuum is introduced the heat developed trough themechanical energy provided to the suspension may be lower than undernormal pressure.
    The nanofibrillated polysaccharide may, according to onel alternative ofthe first aspect of the invention, be a nanofibrillated cellulose or amicrofibrillated cellulose.
    The nano- och microfibrillated cellulose may be obtained throughconventional methos such as mechanical liberation of fibrils or by acidhydrolysis of cellulosic materials, e.g. disclosed in WO 2009021687 A1, orMFC suspension produced by enzymatic hydrolysis of Kraft pulp cellulose,e.g. disclosed in WO2011004300 A1, acid hydrolysis followed by highpressure homogenization, e.g. disclosed in US20100279019, or by any othermeans known to the skilled person. One method of producing nanofibrils is byspinning or e-spinning cellulose or polysaccharides or mixtures thereof.
    The concentration of MFC is usually about 1-6 % and the remainingpart is water or components used to promote e.g. runnability or used forgrafting of fibrillated cellulose such as Na-CMC.
    According to yet an alternative of the first aspeact there may further beprovided a drying additive in step (iii).
    By introducing a drying additive the drying process may be eventfurther improved. Such additives are disclosed in CA1208631. A dryingadditive may also be a solvent.
    According to a second aspect there is provided a substantially drynanofibrillated polysaccharide product obtainable by the method according tothe first aspect.
    By “substantially dry NFP product” is meant that the water content inthe NFP product is reduced to a level where the product may be in a powderform, but still being suitable for re-dispersion, in a solvent such as water orsolid phase.
    As such the solids content of the product may be in the range of 50-99wt-%. ln a preferred embodiment the solids content is in the range of 75-90wt-%.
    The dry NFP or MFC product obtained through the method describedabove may have very good and well separated straight individual micro fibrilswhen re-dispersed in water, i.e. the hornification problems normallyassociated with drying of NFP has been greatly reduced. The applicability ofthis dried NFP product may therefore be greatly increased for applicationssuch as composites, paints, food and pharmaceutical uses.
    According to a third aspect there is provided a use of a drynanofibrillated polysaccharide product according to the second aspect in, orfor the production of composites.
    According to a fourth aspect there is provided a use of a drynanofibrillated polysaccharide product according to the second aspect, forany one of a rheology application, fixative agent, strength enhancing agent,emulsifying agent, excipient, paper applications, film forming agent, moisturecontrol agent, and in paper or paperboard of products thereof.
    The dry product may thus be used in, for instance, textiles, food,pharmaceuticals, paints, concrete, asphalt, rubber, plastic-wood composites,inks, etc.
    Description of Embodimentsln the below, a method of drying a nanofibrillated polysaccharide, or asit may be a microfibrillated cellulose is disclosed. These definintions may beused alternately in the below, but is not intended to exclude one or the other.The definitions for nanofibrillated polysaccharide and microfibrillated cellulosemay also be found in the below description.ln a preferred embodiment, however, the method is applied to thedrying of microfibrillated cellulose or nanofibrillated cellulose, in a pure form oralternativley including additives.
    According to one embodiment the method of drying nanofibrillatedpolysaccharide (NFP), is provided through a process in which an aqueoussuspension of NFP is provided. The solid contents of this suspension may bein the range of 0.01wt-% to 25 wt-%, according to one embodiment the solidscontent is the range of 0,01 wt-% to 15 wt-% (can be 20-25%).
    The solids content or the consistency of this aqueous suspension isthen increased to at least 15 % by weight. According to one embodiment thesolids content of the suspension is raised to 30-35 %.
    This increase may be performed by a mechanical dewatering.According to one embodiment this dewatering is performed by centrifugation.According to another embodiment it is performed through pressing, such aswet pressing in a paper making machine. According to yet an alternativeembodiment the dewatering is performed through electro-osmosis combinedwith mechanical pressure. Other alternative ways to provide for an increase inthe solids content of the suspension may include, but is not limited to any oneof a decanter centrifuge, wire press, belt press,extended dewatering nips, andmagnetically induced dewatering. The dewatering may also be performed byheating to a suitable temperature, evaporation, or adsorption e.g. into felt orusing radiation such as IR, NlR or microwave. When selecting the suitablemanner to increase the solids content care must however be taken that thechosen method does not, in a negative way, influence the occurrence ofhornification, which the skilled person would readily be able to determine.
    According to the method, after the solids content has been increasedthe suspension is dried. This drying operation is performed through asimultaneous grinding and heating of the suspension, for instance in a mixingapparatus, and thereby effecting removal of water by evaporation.
    Alternatively the drying operation is performed under vacuum, i.e. thesuspension is treated under vacuum.
    According to one alternative the drying is performed through a grindingdrying operation, e.g. by PVC mixer similar method where heat andmechanical energy is introduced at the same time as water is allowed toevaporate.
    According to one embodiment, at the drying operation, the temperatureof the suspension is in the range of 75-99 °C, preferably about 80 °C. Forinstance the mixing apparatus may heat the dispersion from about roomtemperature to the range of 75-99 °C.
    The effect of the temperature in drying step of the process is critical,which was found here. An optimal temperture, particularly at the end ofdrying, prevents hornification of the fibers. By optimal temperature is thusmeant a temperature which is low enough to prevent the hornificationprocess.
    According to one embodiment the drying step can be done in presenceof different additives, such as those disclosed in CA1208631.
    According to one embodiment the suspension may be cooled or kept ata constant temperature by cooling or heating the suspension. The cooling orheating may be performed by conventional means known to the skilledperson.
    According to one alternative embodiment the temperature of thesuspension may be further increased, for instance in the mixing appartus afterthe NFP suspension has been dried to a water content of at most 10 wt-%.
    The total drying time at the drying operation step may be in the rangeof 15-40 min, preferably about 30 min, thus allowing for a fast and dryingoperation which may be incorporated into a industrial process. The dryingtime may be dependent on the initial solids content of the suspension, theenergy input, any additives and the batch size.
    Definition of nanofibrillated polvsaccharideThis definition includes bacterial cellulose or nanocellulose spun witheither traditional spinning techniques or membrane technique or then withelectrostatic spinning. ln these cases, the material is preferably apolysaccharide but not limited to solely a polysaccharide.
    Also whiskers, microcrystalline cellulose (MCC) and nanocellulosecrystals(NCC) regenerated cellulose particles or fibers is included in thisdefinition. lt can also be a mixture of e.g. MCC and MFC.
    Definition of microfibrillated celluloseThe microfibrillated cellulose (MFC) is also known as nanocellulose. ltis a material typically made from wood cellulose fibers, both from hardwood orsoftwood fibers. lt can also be made from microbial sources, agriculturalfibers such as wheat straw pulp, bamboo or other non-wood fiber sources. lnmicrofibrillated cellulose the individual microfibrils have been partly or totallydetached from each other. A microfibrillated cellulose nanofiber is normallyverythin (~20 nm) and the length is often between 100 nm to 10 pm.However, the microfibrils may also be longer, for example between 10-200pm, but lengths even 2000 pm can be found due to wide length distribution.Fibers that has been fibrillated and which have microfibrils on the surface andmicrofibrils that are separated and located in a water phase of a slurry areincluded in the definition MFC. Furthermore, whiskers are also included in thedefinition MFC.
    ExampleMicrofibrillated fibers were dewatered in paper machine type of wire sectionand subsequent wet pressing to a solids content of about 30-35 % by weight.The high solids MFC was dosaged into a PVC mixer and mixed so that thetemperature was increased to about 80°C, until the MFC was substantiallydry, after which the temperature was further incrased to about 95°C.ln this example a PVC mixer having a size of was 200/100 liters was used.The motor was of 50 kW.
    The total drying time was about 30 min and the batch size was 25 kgwet MFC dispersion, which gave about 9 kg dry MFC.
    After rewetting of micro fibrillated cellulose it was studied undermicroscope; and very good and well separated straight individual micro fibrilscould be seen. This in turn implies that little or no hornification of the microfibrils has taken place, which was confirmed with water retention valuemeasurements. This type of micro fibrills are very well suitable for compositesand other applications where dry micro fibrillated cellulose is preferred insteadof wet.
    权利要求:
    Claims (15)
    [1] 1. A method for drying nanofibrillated polysaccharide to obtain asubstantially dry nanofibrillated polysaccharide product, comprising thefollowing steps: (i) providing an aqueous suspension of nanofibrillated polysaccharide; (ii) increasing the solid content of said suspension, thereby forming ahigh solid content microfibrillated cellulose suspension; and (iii) drying said high solid content microfibrillated cellulose suspension,through a mixing operation.
    [2] 2. The method for drying as claimed in claim 1, wherein in step (ii), thesolid contents is increased to >15 wt-%, or to > 20 wt-% , or to > 25 wt-% , orto > 30 wt-% _
    [3] 3. The method of drying as claimed in any one of the preceedingclaims, wherein step (iii) comprises a flbrillation or grinding operation.
    [4] 4. The method of drying as claimed in any one of the preceding claims,wherein step (ii) comprises any one of a centrifugal force operation, pressingoperation and dewatering operation.
    [5] 5. The method as claimed in claim 4 wherein the dewatering operationcomprises an electro-osmosis operation.
    [6] 6. The method as claimed in claim 4, wherein the pressing operationcomprises a wet pressing operation.
    [7] 7. The method as claimed in any one of the preceding claims, whereinat step (iii) the temperature of the suspension is in the range of 75-99 °C,preferably about 80 °C.
    [8] 8. The method as claimed in claim 7, wherein at step (iii) thesuspension is heated from about room temperature to the range of 75-99 °C. 12
    [9] 9. The method as claimed in any one of the preceding claims, whereinin step (iii) there is further provided a simultaneous heating and mixingoperation.
    [10] 10. The method of drying as claimed in any one of claim 1-6, wherestep (iii) is performed under vacuum.
    [11] 11. The method as claimed in any one of the preceding claims,wherein the nanofibrillated polysaccharide is a nanofibrillated ceiiuiose or amicrofibrillated ceilulose.
    [12] 12. The method as claimed in any one of the preceding claims,wherein in step (iii) there is further provided a drying additive.
    [13] 13. A substantially dry nanofibrillated polysaccharide productobtainable by the method as claimed in any one of claims 1-11.
    [14] 14. Use of a dry nanofibrillated polysaccharide product as claimed inclaim 13 in, or for the procuction of composites.
    [15] 15. Use of a dry nanofibrillated polysaccharide product as claimed inclaim 13, for any one of a rheoiogy application, fixative agent, strengthenhancing agent, emulsifying agent, excipient, paper applications, and inpaper or paperboard of products thereof.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2917403B1|2018-07-04|Mixing drying of nanofibrillated polysaccharide
    US9926668B2|2018-03-27|Substantially dry composite comprising a nanofibrillated polysaccharide
    FI125941B|2016-04-15|Method and apparatus for treating fibril pulp and a fibril pulp product
    CN109415875B|2021-12-24|Microfibrillated film
    Rol et al.2017|Pilot-scale twin screw extrusion and chemical pretreatment as an energy-efficient method for the production of nanofibrillated cellulose at high solid content
    JP6886457B2|2021-06-16|A method for producing a film with good barrier properties
    CN108026696B|2021-05-04|Method for making a film comprising microfibrillated cellulose and amphoteric polymer
    KR20150082523A|2015-07-15|Dry cellulose filaments and the method of making the same
    CN104619913A|2015-05-13|Method and intermediate for the production of highly refined or microfibrillated cellulose
    Saurabh et al.2016|Effect of hydrolysis treatment on cellulose nanowhiskers from oil palm | fronds: Morphology, chemical, crystallinity, and thermal characteristics
    JP2019522123A|2019-08-08|Process for producing an intermediate product for conversion to microfibrillated cellulose
    RU2696383C2|2019-08-01|Method of producing microfibrillated cellulose and microfibrillated cellulose
    EP3423629B1|2020-12-02|Method of manufacturing 3d shaped articles
    CN111479859A|2020-07-31|Microfibrillated cellulose film
    CN111479959A|2020-07-31|Filaments of microfibrillated cellulose
    JP2021515114A|2021-06-17|Methods for Producing Compositions Containing Microfibrillated Cellulose
    US20210277265A1|2021-09-09|Cross-linkable cellulose as 3d printing material
    US20220025147A1|2022-01-27|Foam assisted drying process of nano- and microfibrillated cellulose
    Trigui et al.2022|Twin-screw extrusion for the production of nanocellulose-PVA gels with a high solid content
    同族专利:
    公开号 | 公开日
    EP2917403B1|2018-07-04|
    SE538085C2|2016-03-01|
    WO2014072886A1|2014-05-15|
    CN104903511A|2015-09-09|
    EP2917403A1|2015-09-16|
    US20150308017A1|2015-10-29|
    PL2917403T3|2018-11-30|
    EP2917403A4|2016-05-04|
    CN104903511B|2017-12-22|
    AR093320A1|2015-05-27|
    BR112015010597A2|2017-07-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB839569A|1955-10-26|1960-06-29|Wacker Chemie Gmbh|Process for removing liquids from and drying solid substances|
    US4178341A|1978-04-12|1979-12-11|Arcanum Corporation|Process for preparing agglomerates of clays|
    US4481076A|1983-03-28|1984-11-06|International Telephone And Telegraph Corporation|Redispersible microfibrillated cellulose|
    US4767848A|1985-07-22|1988-08-30|Personal Products Company|Cross-linked microfibrillated cellulose prepared from pore generating particles|
    US5094717A|1990-11-15|1992-03-10|James River Corporation Of Virginia|Synthetic fiber paper having a permanent crepe|
    KR19990037728A|1996-06-21|1999-05-25|가부시키가이샤 바이오 폴리머 리서치|How to Treat Bacterial Cellulose|
    WO1998057109A1|1997-06-09|1998-12-17|Samra Kouhen Nathan|Process and device with rotary blades for the friction drying of particles of polyethylen terephthalate and other condensation polymers|
    FR2768620B1|1997-09-22|2000-05-05|Rhodia Chimie Sa|ORAL FORMULATION COMPRISING ESSENTIALLY AMORPHOUS CELLULOSE NANOFIBRILLES|
    AUPQ741800A0|2000-05-10|2000-06-01|Commonwealth Scientific And Industrial Research Organisation|Apparatus for electrodewatering by filtration|
    JP4336275B2|2004-08-27|2009-09-30|光男 沼田|Plant organic matter grinding method and apparatus|
    FI126046B|2009-04-20|2016-06-15|Elastopoli Oy|Composite intermediate and process for its preparation|
    GB0908401D0|2009-05-15|2009-06-24|Imerys Minerals Ltd|Paper filler composition|
    EP2531643A1|2010-02-04|2012-12-12|Borregaard AS|Method and device for producing dry microfibrillated cellulose|
    CN101780160B|2010-04-07|2011-09-28|史长山|Traditional Chinese medicine preparation for treating gynecological disease and preparation method thereof|
    US8372320B2|2010-04-27|2013-02-12|University Of Maine System Board Of Trustees|Method for drying cellulose nanofibrils|
    US9856607B2|2010-05-11|2018-01-02|Fpinnovations|Cellulose nanofilaments and method to produce same|
    SE536744C2|2010-05-12|2014-07-08|Stora Enso Oyj|A process for manufacturing a composition containing fibrillated cellulose and a composition|
    GB201019288D0|2010-11-15|2010-12-29|Imerys Minerals Ltd|Compositions|
    CN102174612A|2011-01-06|2011-09-07|浙江农林大学|Biological and mechanical silk dividing method for producing nanocellulose|
    FI127301B|2011-02-10|2018-03-15|Upm Kymmene Corp|A method for treating nanocellulose and a product obtained by the method|
    FI126122B|2011-12-22|2016-06-30|Upm Kymmene Corp|Use of a stationary phase comprising fibril pulp in a separation process|WO2015007953A1|2013-07-16|2015-01-22|Stora Enso Oyj|A method of producing oxidized or microfibrillated cellulose|
    CN104562823B|2014-12-11|2017-01-18|天津科技大学|Synchronization method for preparing microfibrillated cellulose and application of microfibrillated cellulose in strengthening of paper|
    FI127918B|2015-09-03|2019-05-15|Helsingin Yliopisto|Method of dewatering water soluble polymers|
    SE539563C2|2016-02-29|2017-10-10|Stora Enso Oyj|Method of manufacturing 3d shaped articles comprising nanofibrillated polysaccharide from cellulose|
    US10865317B2|2017-08-31|2020-12-15|Kimberly-Clark Worldwide, Inc.|Low-fluorine compositions with cellulose for generating superhydrophobic surfaces|
    SE2050622A1|2020-06-01|2021-12-02|Stora Enso Oyj|A method to produce an adhesive component comprising starch and microfibrillated cellulose, an adhesive and products|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1251280A|SE538085C2|2012-11-09|2012-11-09|Drying and mixing process for microfibrillated cellulose|SE1251280A| SE538085C2|2012-11-09|2012-11-09|Drying and mixing process for microfibrillated cellulose|
    CN201380069825.2A| CN104903511B|2012-11-09|2013-10-30|The combination drying of nanometer fibrillation polysaccharide|
    US14/441,263| US20150308017A1|2012-11-09|2013-10-30|Mixing drying of nanofibrillated polysaccharide|
    PL13853497T| PL2917403T3|2012-11-09|2013-10-30|Mixing drying of nanofibrillated polysaccharide|
    EP13853497.9A| EP2917403B1|2012-11-09|2013-10-30|Mixing drying of nanofibrillated polysaccharide|
    BR112015010597A| BR112015010597A2|2012-11-09|2013-10-30|drying by mixing nanofibrillated polysaccharide ".|
    PCT/IB2013/059778| WO2014072886A1|2012-11-09|2013-10-30|Mixing drying of nanofibrillated polysaccharide|
    ARP130103992A| AR093320A1|2012-11-09|2013-11-01|DRYING WITH NANOFIBRILLED POLYACARIDE MIX|
    [返回顶部]