US20130000855A1 - Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites - Google Patents

Method for manufacturing nanofibrillated cellulose pulp and use of the pulp in paper manufacturing or in nanofibrillated cellulose composites Download PDF

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US20130000855A1
US20130000855A1 US13/511,956 US201013511956A US2013000855A1 US 20130000855 A1 US20130000855 A1 US 20130000855A1 US 201013511956 A US201013511956 A US 201013511956A US 2013000855 A1 US2013000855 A1 US 2013000855A1
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pulp
cellulose
optical brightening
brightening agent
refining
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Markus Nuopponen
Taru Päiväläinen
Antti Laukkanen
Jouni Paltakari
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UPM Kymmene Oy
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001Modification of pulp properties
    • D21C9/002Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H11/00Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18Highly hydrated, swollen or fibrillatable fibres
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21DTREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00Methods of beating or refining; Beaters of the Hollander type
    • D21D1/20Methods of refining
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30Luminescent or fluorescent substances, e.g. for optical bleaching
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/32Bleaching agents

Definitions

  • the invention relates to a method of manufacturing nanofibrillated cellulose pulp.
  • the invention further relates to use of the pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • nanofibrillated cellulose consumes a great deal of energy due to several fibrillarion passages that are needed to achieve nano-sized material. Because the energy consumption of the manufactured pulp increases hugely when the produced pulp includes nanofibrillated cellulose, there may be an efficiency problem when the produced pulp consist at least partly of nanofibrillated cellulose. Sometimes another problem in the nanofibrillated cellulose pulp production is poor water removal due to several strong bonds between cellulose fibers and the water to be removed.
  • the new additive would preferably have features to reduce the inter-fiber bonding and, thus, increase a refining efficiency due to decreased energy consumption of the refining stage.
  • the additive would preferably have features to reduce fiber-water and fiber-fiber bonding that occurs during drying and concentrating.
  • the additive would preferably be some of those additives that are often added for another purpose on later process stages.
  • the present invention solves at least some of the above mentioned problems by providing a method for pulp manufacturing wherein the produced pulp consist at least partly of nanofibrillated cellulose.
  • the method comprises a step in which at least one type of optical brightening agent (OBA) is dosed before and/or during at least one pre-refining and/or fibrillation stage.
  • OSA optical brightening agent
  • the invention further discloses a use of the produced pulp in nanofibrillated cellulose composites or in paper or paperboard manufacturing including base paper manufacturing and finishing stages like, for example, the use in paper or paperboard coatings.
  • optical brightening agents can increase the production efficiency of the nanofibrillated cellulose pulp if the additives are dosed before or during a pre-refining stage and/or a fibrillation stage.
  • Optical brightening agents have been found to be able to create bonding with cellulose in such a way that the optical brightening agents can act as substituents in inter-fiber bonding and, thus, inhibiting hydrogen bonding of fibrils in cellulose.
  • the increased production efficiency is mainly due to decreased energy consumption of the fibrillation stage because of the substituent effect.
  • Optical brightening agents are also able to create bonding with water and, thus, to increase the efficiency of drying and concentrating processes.
  • optical brightening agents are able to enable redispersing of nanofibrillated containing cellulose. Due to the dispersive effect, an optical brightening agent can be used as a dispersing agent in nanofibrillated concentrating and/or redispersing process and, therefore, help the process. In addition, due to the dispersive effect, the quality of the nanofibrillated cellulose pulp can be increased.
  • At least one kind of optical brightening agent is added before a pulp pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is added before a pulp fibrillation stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the fibrillation stage.
  • the amount of the nanofibrillated cellulose in the produced pulp is more than 30 w-%, preferably more than 40 w-%, 50 w-%, 60 w-% or 70 w-%, and can be even up to 100 w-% measured from the dried pulp.
  • the nanofibrillated cellulose pulp that can be produced according to the invention and, thus, contains one or more optical brightening agents, may be used in various end product applications.
  • the cellulose pulp may be used, for example, in nanofibrillated cellulose composites, and/or in paper manufacturing, for example, in a base paper and/or in a finishing stage of produced paper.
  • the finishing stages of produced paper includes, for example, coating stages.
  • FIGS. 1 a - d show microscopy pictures of cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulps
  • FIG. 2 a - c show some viscosity results of experimental test together with some optical microscopy pictures taken during experimental test from Masuko grinded samples;
  • FIG. 3 a - b show optical microscopy images of some fluidisator samples taken during experimental test
  • FIG. 4 a - b show SEM (scanning electron microscope) pictures of the samples shown also in FIGS. 3 a - 3 b;
  • FIG. 5 shows some turbidity and centrifugation experimental test results of the fluidized samples.
  • cellulose raw material refers to any cellulose raw material source that can be used in a production of cellulose pulp, refined pulp, or microfibrillar cellulose.
  • the cellulose raw material can be based on any plant material that contains cellulose, for example wood material.
  • the wood material can be from softwood trees, such as spruce, pine, fir, larch, douglas-fir or hemlock, or from hardwood trees, such as birch, aspen, poplar, alder, eucalyptus or acacia, or from a mixture of softwoods and hardwoods.
  • Non-wood material can be from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
  • agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
  • cellulose pulp refers in this application to cellulose fibers, which are isolated from any cellulose raw material using chemical, mechanical, thermomechanical, or chemithermo—mechanical pulping process(es). Typically the diameter of the fibers varies between 15-25 ⁇ m and the length exceeds 500 ⁇ m, but the present invention is not intended to be limited to these parameters.
  • paper manufacturing refers to manufacturing process of any paper-like material, for example, paperboards, papers and/or paper composites.
  • At least part of the lignin that has been included in cellulose raw material is advantageously removed from the cellulose raw material when it is processed into cellulose pulp to be used in the nanofibrillated cellulose production.
  • chemical pulp may be used more preferably for nanofibrillated cellulose production than mechanical pulp.
  • the yield of the process wherein cellulose raw material is processed into cellulose pulp to be used in the nanofibrillated pulp production has been at least 50%, at least 60%, at least 70% or at least 80%.
  • the cellulose pulp used in the nanofibrillated cellulose production may be preferably unbleached or bleached chemithermo or chemical pulp, more preferably unbleached or bleached chemical pulp, and the most preferably unbleached chemical pulp, because the method of the invention may be the most advantageous compared to other processes when the used cellulose pulp is chemically produced unbleached pulp.
  • refined pulp refers to refined cellulose pulp.
  • the refining of cellulose pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator.
  • suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator.
  • suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator.
  • fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator.
  • all cellulose fibers have not been fully fibrillated; a large fraction of cellulose fibers with unchanged dimensions are still present in addition to refined cellulose material.
  • nanofibrillated cellulose refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material.
  • Microfibrils have typically high aspect ratio: the length might exceed one micrometer while the number-average diameter is typically below 200 nm.
  • the diameter of microfibril bundles can also be larger but generally less than 1 ⁇ m.
  • the smallest microfibrils are similar to the so called elementary fibrils, which are typically 2-12 nm in diameter.
  • the dimensions of the fibrils or fibril bundles are dependent on the raw material and disintegration method.
  • the nanofibrillated cellulose may also contain some hemicelluloses; the amount may be dependent on the plant source.
  • Nanofibrillated cellulose can also be any chemically or physically modified derivate of cellulose microfibrils or microfibril bundles.
  • the chemical modification could be based for example on carboxymethylation, oxidation, esterification, or etherification reaction of cellulose molecules. Modification could also be realized by physical adsorption of anionic, cationic, or non-ionic substances or any combination of these on cellulose surface.
  • the described modification can be carried out before, after, or during the production of nanofibrillated cellulose.
  • Nanofibrillated cellulose described in this application is not the same material as the so called cellulose whiskers, which are also known as: cellulose nanowhiskers, cellulose nanocrystals, cellulose nanorods, rod-like cellulose microcrystals or cellulose nanowires. In some cases, similar terminology is used for both materials, for example by Kuthcarlapati et al.
  • cellulose nanofiber amorphous segment along the fibrillar structure as microfibrillar cellulose, which leads to more rigid structure.
  • Cellulose whiskers are also shorter than microfibrillar cellulose; typically the length is less than one micrometer.
  • Nanofibrillated cellulose and normal cellulose are usually produced using different kind of refiners, because the refiners that are used conventionally in the pulp refiner production may not, at least efficiently, be used in nanofibrillated cellulose production. However, the refiners used in the conventional pulp production may be used as pre-refiners in nanofibrillated cellulose production.
  • the term “fibrillation stage” means the stage that causes more fibrillar cellulose
  • the term “pre-refiner stage” means the stage that may advantageously be used for pre-refining before a fibrillation stage in nanofibrillated cellulose production.
  • Nanofibrillated cellulose pulp differs hugely from conventional cellulose pulp due to many nano-sized particles of the nanofibrillated cellulose pulp and, thus, nanofibrillated cellulose cannot be though as a same material as conventional cellulose pulp.
  • Nanofibrillated cellulose is, for example, gel-like material even in low consistency, and its water removal rate is usually slow.
  • Paper sheets that contain a lot of nanofibrillated cellulose have special properties comparing to the sheets made from normal cellulose pulp, for example, they have usually high strength properties, their porosity is very low, and the sheets are usually (at least partly) transparent.
  • FIGS. 1 a - 1 d The differences between cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulp are illustrated in FIGS. 1 a - 1 d in optical microscopy pictures. Magnification is the same in the FIGS. 1 a - 1 c.
  • FIG. 1 a shows an optical microscopy picture of typical cellulose pulp.
  • FIG. 1 b shows an microscopy picture of typical refined cellulose pulp.
  • FIGS. 1 c and 1 d show microscopy pictures of typical nanofibrillated cellulose pulp.
  • FIG. 1 c shows the large cellulose fibers shown in FIGS. 1 a and 1 b are not anymore clearly visible.
  • FIG. 1 d shows the same situation as FIG. 1 c but with higher magnification wherein individual microfibrils and microfibril bundles with diameter less than 100 nm can be detected.
  • the present invention provides a method for manufacturing nanofibrillated cellulose pulp by pre-refining and/or fibrillating the pulp with a presence of at least one kind of optical brightening agent.
  • the present invention provides the use of the produced pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • optical brightening agents are dye-like compounds which absorb short-wave light in the ultraviolet and violet region of the electromagnetic spectrum not visible to the human eye and re-emit the light in the longer-wave blue region.
  • optical brightening agents make the material, for example paper, to look less yellow to the human eyes and, thus, human eyes interpret the blue light as a higher degree of whiteness.
  • the optical brightening agents are used to achieve better optical properties of the produced paper, for example, for a whitening effect of the produced paper.
  • Optical brightening agent types that are typically used in the pulp and paper industry are, for example, di-, tetra-, and hexasulphonated stilbene compounds.
  • the amount of sulphonated groups has an effect on the chemical properties of the optical brightening agent and, thus, the type of the used OBA may have an effect on the method according to an example embodiment of the invention.
  • the more the optical brightening agent has sulphonated groups the bigger may be the effect of the used optical brightening agent on the method accordant with the invention.
  • Some other most commercially available optical brightening agents in pulp and paper industries are based on coumarin and pyrazoline chemistries. Those mentioned optical brightening agent types are only some examples and also other types of optical brightening agents known in prior art can be used in this invention.
  • those chemical types mentioned in the application i.e stilbene, coumarin and pyrazoline, are preferred to use in the practice of this invention.
  • the anionic stilbene compounds may be the most preferably used in the invention.
  • optical brightening agents are quite expensive additives, thus, solutions provided in this invention are intended to be the most efficient if optical brightening agents are used in nanofibrillated pulp production wherein the optical brightening agent is otherwise added in a later stage to the pulp or to the end product.
  • optical brightening agents are typically added at the wet end of the papermaking process, which include, for example, the fan pulp or the machine chest.
  • optical brightening agent in accordance with some example embodiments of the invention does not necessarily increase additive costs but, quite the contrary, the retention of the optical brightening agent to the nanofibrillated pulp may be improved if the optical brightening agent is added before or during pre-refining stage or before or during a fibrillation step and, therefore, the overall costs of the used optical brightening agent may be decreased.
  • the total amount of the needed optical brightening agent dosage according to an example embodiment of the invention can be smaller if the optical brightening agent is added accordant with some example embodiments of the invention due to several fiber-optical brightening agent bondings that may be formed during nanofibrillated cellulose pre-refining and/or fibrillation stages.
  • the efficiency of the nanofibrillated cellulose production can further be increased when the optical brightening agent is added to the produced pulp before or during the refining stage, not only because of the decreased energy consumption but also because of less additive costs.
  • the optical brightening agent dosage to the nanofibrillated cellulose production according to some example embodiments of this invention may increase an ability of the nanofibrillated cellulose to carry the optical brightening agent and, therefore, a need for other optical brightening agent carriers e.g. Polyvinyl Alcohol (PVOH) may decrease.
  • PVOH Polyvinyl Alcohol
  • the method comprises a step wherein at least one type of the optical brightening agent (OBA) is dosed as a refining additive to the pulp which contains cellulose.
  • OSA optical brightening agent
  • the dosage is preferably done before a pre-refining and/or fibrillation stage.
  • one type of the optical brightening agent can be added into the pulp at the pre-refining or the fibrillation stage.
  • the pulp is fibrillated in at least one fibrillation stage after the additive addition, no matter in which stage the additive is added to the process.
  • the anionic optical brightening agent is capable of inhibiting hydrogen bonding between the cellulose fibrils in cellulose and can therefore be used to create a dispersive effect, which dispersive effect can increase the quality of the produced nanofibrillated cellulose. Due to the dispersive effect, optical brightening agent can be used as a dispersing agent in the nanofibrillated concentrating/redispersing process and, therefore, may help the process.
  • Nanofibrillated cellulose that contains optical brightening agent may improve not only the refining efficiency and the quality of the produced pulp but also both the strength and the optical properties of the end product to be produced from the pulp manufactured according to an example embodiment of the invention.
  • the improvements in strength properties are mainly due to the features of nanofibrillated cellulose and the improvements in optical properties are mainly due to the features of the optical brightening agent.
  • the novel invention can provide at least some of the following advantages:
  • the amount of nanofibrillated cellulose in the pulp manufactured according to the invention may be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 w-%, including any and all ranges and subranges therein.
  • the pulp manufacturing process according to invention has at least one fibrillation stage, possibly at least 2, 3 or 4 fibrillation stages. According to the invention at least one type of the optical brightening agent is added
  • the pulp is fibrillated after at least one additive dosage in at least one fibrillation stage in order to form some nanofibrillated cellulose material.
  • the addition of the optical brightening agent before or during the refining decreases the cellulose-cellulose bonding through hydroxyl groups by forming hydrogen bonds with the cellulose fibrils.
  • the addition of the optical brightening agent creates a dispersive effect to the pulp suspension through the repulsive forces between the anionic groups.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

A method for manufacturing pulp. The manufactured pulp includes at least 30 w-% nanofibrillated cellulose material measured from the dried pulp. A raw material is introduced to a system. The raw material includes cellulose. At least one type of an optical brightening agent is dosed as a refining additive to the system. The raw material is refined in the presence of the dosed optical brightening agent in at least one pre-refining stage or fibrillation stage to form fibrillar cellulose material.

Description

    FIELD OF THE INVENTION
  • The invention relates to a method of manufacturing nanofibrillated cellulose pulp. The invention further relates to use of the pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • BACKGROUND OF THE INVENTION
  • Many stages of pulp production, especially refining stages, consume lots of energy. Specially a production of nanofibrillated cellulose consumes a great deal of energy due to several fibrillarion passages that are needed to achieve nano-sized material. Because the energy consumption of the manufactured pulp increases hugely when the produced pulp includes nanofibrillated cellulose, there may be an efficiency problem when the produced pulp consist at least partly of nanofibrillated cellulose. Sometimes another problem in the nanofibrillated cellulose pulp production is poor water removal due to several strong bonds between cellulose fibers and the water to be removed.
  • Due to the above mentioned problems, it is beneficial to add at least one compound capable of substantially inhibiting hydrogen bonding of fibrils in cellulose, especially in a process preparing nanofibrillated cellulose. For this purpose some polyhydroxy compounds, such as sucrose, are used in prior art. However, those known compounds have some problems. For example, known additives have generally been used only for refining stages, which will cause extra additive costs. Thus, it would be more beneficial to use those kind of additives which were anyway added to the process for another purpose on later process stages instead of those known additives used only for the above mentioned purpose.
  • There is, therefore, a need for a new solution for increasing the efficiency of the nanofibrillated cellulose pulp production. There is, thus, a need for an additive that could cause a smaller energy consumption of pre-refining and/or fibrillation stages and a better water removability in the pulp production. The new additive would preferably have features to reduce the inter-fiber bonding and, thus, increase a refining efficiency due to decreased energy consumption of the refining stage. In addition, the additive would preferably have features to reduce fiber-water and fiber-fiber bonding that occurs during drying and concentrating. Moreover, the additive would preferably be some of those additives that are often added for another purpose on later process stages.
  • SUMMARY OF THE INVENTION
  • The present invention solves at least some of the above mentioned problems by providing a method for pulp manufacturing wherein the produced pulp consist at least partly of nanofibrillated cellulose. The method comprises a step in which at least one type of optical brightening agent (OBA) is dosed before and/or during at least one pre-refining and/or fibrillation stage. The invention further discloses a use of the produced pulp in nanofibrillated cellulose composites or in paper or paperboard manufacturing including base paper manufacturing and finishing stages like, for example, the use in paper or paperboard coatings.
  • Aspects of the invention are characterized by what is stated in the independent claims 1, 10 and 11. Various embodiments of the invention are disclosed in the dependent claims.
  • The inventors of the present invention have surprisingly found that optical brightening agents can increase the production efficiency of the nanofibrillated cellulose pulp if the additives are dosed before or during a pre-refining stage and/or a fibrillation stage. Optical brightening agents have been found to be able to create bonding with cellulose in such a way that the optical brightening agents can act as substituents in inter-fiber bonding and, thus, inhibiting hydrogen bonding of fibrils in cellulose. The increased production efficiency is mainly due to decreased energy consumption of the fibrillation stage because of the substituent effect. Optical brightening agents are also able to create bonding with water and, thus, to increase the efficiency of drying and concentrating processes.
  • Due to the above mentioned things, optical brightening agents are able to enable redispersing of nanofibrillated containing cellulose. Due to the dispersive effect, an optical brightening agent can be used as a dispersing agent in nanofibrillated concentrating and/or redispersing process and, therefore, help the process. In addition, due to the dispersive effect, the quality of the nanofibrillated cellulose pulp can be increased.
  • According to an embodiment of the present invention, at least one kind of optical brightening agent is added before a pulp pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is added before a pulp fibrillation stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the pre-refining stage. According to another embodiment, at least one kind of optical brightening agent is dosed into the pulp at the fibrillation stage.
  • According to an embodiment, the amount of the nanofibrillated cellulose in the produced pulp is more than 30 w-%, preferably more than 40 w-%, 50 w-%, 60 w-% or 70 w-%, and can be even up to 100 w-% measured from the dried pulp.
  • The nanofibrillated cellulose pulp that can be produced according to the invention and, thus, contains one or more optical brightening agents, may be used in various end product applications. The cellulose pulp may be used, for example, in nanofibrillated cellulose composites, and/or in paper manufacturing, for example, in a base paper and/or in a finishing stage of produced paper. The finishing stages of produced paper includes, for example, coating stages.
  • DESCRIPTION OF THE DRAWINGS
  • In the following, the invention will be illustrated by drawings in which
  • FIGS. 1 a-d show microscopy pictures of cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulps;
  • FIG. 2 a-c show some viscosity results of experimental test together with some optical microscopy pictures taken during experimental test from Masuko grinded samples;
  • FIG. 3 a-b show optical microscopy images of some fluidisator samples taken during experimental test;
  • FIG. 4 a-b show SEM (scanning electron microscope) pictures of the samples shown also in FIGS. 3 a-3 b; and
  • FIG. 5 shows some turbidity and centrifugation experimental test results of the fluidized samples.
  • DETAILED DESCRIPTION OF THE INVENTION
  • In this application, the term “cellulose raw material” refers to any cellulose raw material source that can be used in a production of cellulose pulp, refined pulp, or microfibrillar cellulose. The cellulose raw material can be based on any plant material that contains cellulose, for example wood material. The wood material can be from softwood trees, such as spruce, pine, fir, larch, douglas-fir or hemlock, or from hardwood trees, such as birch, aspen, poplar, alder, eucalyptus or acacia, or from a mixture of softwoods and hardwoods. Non-wood material can be from agricultural residues, grasses or other plant substances such as straw, leaves, bark, seeds, hulls, flowers, vegetables or fruits from cotton, corn, wheat, oat, rye, barley, rice, flax, hemp, manila hemp, sisal hemp, jute, ramie, kenaf, bagasse, bamboo or reed.
  • The term “cellulose pulp” refers in this application to cellulose fibers, which are isolated from any cellulose raw material using chemical, mechanical, thermomechanical, or chemithermo—mechanical pulping process(es). Typically the diameter of the fibers varies between 15-25 μm and the length exceeds 500 μm, but the present invention is not intended to be limited to these parameters.
  • In this application, the term “paper manufacturing” refers to manufacturing process of any paper-like material, for example, paperboards, papers and/or paper composites.
  • According to an example embodiment of the invention, at least part of the lignin that has been included in cellulose raw material is advantageously removed from the cellulose raw material when it is processed into cellulose pulp to be used in the nanofibrillated cellulose production. Thus, chemical pulp may be used more preferably for nanofibrillated cellulose production than mechanical pulp. According to an example embodiment of the invention, the yield of the process wherein cellulose raw material is processed into cellulose pulp to be used in the nanofibrillated pulp production has been at least 50%, at least 60%, at least 70% or at least 80%.
  • According to an example embodiment, the cellulose pulp used in the nanofibrillated cellulose production may be preferably unbleached or bleached chemithermo or chemical pulp, more preferably unbleached or bleached chemical pulp, and the most preferably unbleached chemical pulp, because the method of the invention may be the most advantageous compared to other processes when the used cellulose pulp is chemically produced unbleached pulp.
  • The term “refined pulp” refers to refined cellulose pulp. The refining of cellulose pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer or ultrasound sonicator. Typically, all cellulose fibers have not been fully fibrillated; a large fraction of cellulose fibers with unchanged dimensions are still present in addition to refined cellulose material. The large fibers in the refined pulp may have fibrillated surface. The finest fraction of cellulose based material in the “refined pulp” consists of nanofibrillated cellulose, i.e. cellulose microfibrils and microfibril bundles with diameter less than 200 nm.
  • The term “nanofibrillated cellulose, (NFC)” refers to a collection of isolated cellulose microfibrils or microfibril bundles derived from cellulose raw material. Microfibrils have typically high aspect ratio: the length might exceed one micrometer while the number-average diameter is typically below 200 nm. The diameter of microfibril bundles can also be larger but generally less than 1 μm. The smallest microfibrils are similar to the so called elementary fibrils, which are typically 2-12 nm in diameter. The dimensions of the fibrils or fibril bundles are dependent on the raw material and disintegration method. The nanofibrillated cellulose may also contain some hemicelluloses; the amount may be dependent on the plant source.
  • Mechanical disintegration of nanofibrillated cellulose from cellulose raw material, cellulose pulp, or refined pulp is carried out with suitable equipment such as a refiner, grinder, homogenizer, colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer, macrofluidizer or fluidizer-type homogenizer. Nanofibrillated cellulose can also be any chemically or physically modified derivate of cellulose microfibrils or microfibril bundles. The chemical modification could be based for example on carboxymethylation, oxidation, esterification, or etherification reaction of cellulose molecules. Modification could also be realized by physical adsorption of anionic, cationic, or non-ionic substances or any combination of these on cellulose surface. The described modification can be carried out before, after, or during the production of nanofibrillated cellulose.
  • There are several widely used synonyms for nanofibrillated cellulose. For example: nanocellulose, microfibrillar cellulose, nanofibrillar cellulose, cellulose nanofiber, nano-scale fibrillated cellulose, microfibrillated cellulose (MFC), or cellulose microfibrils. Nanofibrillated cellulose described in this application is not the same material as the so called cellulose whiskers, which are also known as: cellulose nanowhiskers, cellulose nanocrystals, cellulose nanorods, rod-like cellulose microcrystals or cellulose nanowires. In some cases, similar terminology is used for both materials, for example by Kuthcarlapati et al. (Metals Materials and Processes 20(3):307-314, 2008) where the studied material was called “cellulose nanofiber” although they clearly referred to cellulose nanowhiskers. Typically these materials do not have amorphous segments along the fibrillar structure as microfibrillar cellulose, which leads to more rigid structure. Cellulose whiskers are also shorter than microfibrillar cellulose; typically the length is less than one micrometer.
  • In conventional pulp production, it is usually an aim to get long, quite undamaged, fibrillated fibers, while in the nanofibrillated cellulose production an aim is to crush fibers into small pieces. Nanofibrillated cellulose and normal cellulose are usually produced using different kind of refiners, because the refiners that are used conventionally in the pulp refiner production may not, at least efficiently, be used in nanofibrillated cellulose production. However, the refiners used in the conventional pulp production may be used as pre-refiners in nanofibrillated cellulose production. In this application, the term “fibrillation stage” means the stage that causes more fibrillar cellulose, and the term “pre-refiner stage” means the stage that may advantageously be used for pre-refining before a fibrillation stage in nanofibrillated cellulose production.
  • Properties of nanofibrillated cellulose pulp differs hugely from conventional cellulose pulp due to many nano-sized particles of the nanofibrillated cellulose pulp and, thus, nanofibrillated cellulose cannot be though as a same material as conventional cellulose pulp. Nanofibrillated cellulose is, for example, gel-like material even in low consistency, and its water removal rate is usually slow. Paper sheets that contain a lot of nanofibrillated cellulose have special properties comparing to the sheets made from normal cellulose pulp, for example, they have usually high strength properties, their porosity is very low, and the sheets are usually (at least partly) transparent.
  • The differences between cellulose pulp, refined cellulose pulp and nanofibrillated cellulose pulp are illustrated in FIGS. 1 a-1 d in optical microscopy pictures. Magnification is the same in the FIGS. 1 a-1 c. FIG. 1 a shows an optical microscopy picture of typical cellulose pulp. FIG. 1 b shows an microscopy picture of typical refined cellulose pulp. FIGS. 1 c and 1 d show microscopy pictures of typical nanofibrillated cellulose pulp. As can be seen in FIG. 1 c, the large cellulose fibers shown in FIGS. 1 a and 1 b are not anymore clearly visible. FIG. 1 d shows the same situation as FIG. 1 c but with higher magnification wherein individual microfibrils and microfibril bundles with diameter less than 100 nm can be detected.
  • According to an example embodiment the present invention provides a method for manufacturing nanofibrillated cellulose pulp by pre-refining and/or fibrillating the pulp with a presence of at least one kind of optical brightening agent. In addition, according to another example embodiment, the present invention provides the use of the produced pulp in paper manufacturing or in nanofibrillated cellulose composites.
  • The optical brightening agents (OBAs) are dye-like compounds which absorb short-wave light in the ultraviolet and violet region of the electromagnetic spectrum not visible to the human eye and re-emit the light in the longer-wave blue region. In other words, optical brightening agents make the material, for example paper, to look less yellow to the human eyes and, thus, human eyes interpret the blue light as a higher degree of whiteness. In prior art the optical brightening agents are used to achieve better optical properties of the produced paper, for example, for a whitening effect of the produced paper. Optical brightening agent types that are typically used in the pulp and paper industry are, for example, di-, tetra-, and hexasulphonated stilbene compounds. The amount of sulphonated groups has an effect on the chemical properties of the optical brightening agent and, thus, the type of the used OBA may have an effect on the method according to an example embodiment of the invention. Generally, the more the optical brightening agent has sulphonated groups the bigger may be the effect of the used optical brightening agent on the method accordant with the invention. Some other most commercially available optical brightening agents in pulp and paper industries are based on coumarin and pyrazoline chemistries. Those mentioned optical brightening agent types are only some examples and also other types of optical brightening agents known in prior art can be used in this invention. However, according to an embodiment of the invention, those chemical types mentioned in the application, i.e stilbene, coumarin and pyrazoline, are preferred to use in the practice of this invention. From those chemicals, the anionic stilbene compounds may be the most preferably used in the invention.
  • Optical brightening agents are quite expensive additives, thus, solutions provided in this invention are intended to be the most efficient if optical brightening agents are used in nanofibrillated pulp production wherein the optical brightening agent is otherwise added in a later stage to the pulp or to the end product. In papermaking, optical brightening agents are typically added at the wet end of the papermaking process, which include, for example, the fan pulp or the machine chest. The use of the optical brightening agent in accordance with some example embodiments of the invention does not necessarily increase additive costs but, quite the contrary, the retention of the optical brightening agent to the nanofibrillated pulp may be improved if the optical brightening agent is added before or during pre-refining stage or before or during a fibrillation step and, therefore, the overall costs of the used optical brightening agent may be decreased. In the other words, it is possible that the total amount of the needed optical brightening agent dosage according to an example embodiment of the invention can be smaller if the optical brightening agent is added accordant with some example embodiments of the invention due to several fiber-optical brightening agent bondings that may be formed during nanofibrillated cellulose pre-refining and/or fibrillation stages.
  • Therefore, the efficiency of the nanofibrillated cellulose production can further be increased when the optical brightening agent is added to the produced pulp before or during the refining stage, not only because of the decreased energy consumption but also because of less additive costs. Moreover, the optical brightening agent dosage to the nanofibrillated cellulose production according to some example embodiments of this invention may increase an ability of the nanofibrillated cellulose to carry the optical brightening agent and, therefore, a need for other optical brightening agent carriers e.g. Polyvinyl Alcohol (PVOH) may decrease. Thus, the production efficiency can also be increased this way due to the invention.
  • According to an embodiment of the invention, the method comprises a step wherein at least one type of the optical brightening agent (OBA) is dosed as a refining additive to the pulp which contains cellulose. In the method the dosage is preferably done before a pre-refining and/or fibrillation stage. In addition or alternatively, one type of the optical brightening agent can be added into the pulp at the pre-refining or the fibrillation stage. Thus, it is possible to add the optical brightening agent to a pre-refining stage, and/or the optical brightening agent can be added to some or all of the following fibrillation stages. According to an advantageous embodiment of the invention, the pulp is fibrillated in at least one fibrillation stage after the additive addition, no matter in which stage the additive is added to the process.
  • The anionic optical brightening agent is capable of inhibiting hydrogen bonding between the cellulose fibrils in cellulose and can therefore be used to create a dispersive effect, which dispersive effect can increase the quality of the produced nanofibrillated cellulose. Due to the dispersive effect, optical brightening agent can be used as a dispersing agent in the nanofibrillated concentrating/redispersing process and, therefore, may help the process.
  • Nanofibrillated cellulose that contains optical brightening agent may improve not only the refining efficiency and the quality of the produced pulp but also both the strength and the optical properties of the end product to be produced from the pulp manufactured according to an example embodiment of the invention. The improvements in strength properties are mainly due to the features of nanofibrillated cellulose and the improvements in optical properties are mainly due to the features of the optical brightening agent.
  • The method according to an example embodiment of the invention comprises at least the following:
      • introducing raw material to a system which raw material includes cellulose,
      • dosing at least one type of an optical brightening agent as a refining additive to the system, and
      • refining the raw material in the presence of the dosed optical brightening agent in at least one pre-refining or fibrillation stage in order to form fibrillar cellulose material.
  • When compared to the pulp produced according to the invention with pulp produced according to prior art, the novel invention can provide at least some of the following advantages:
      • lower energy consumption to reach the targeted pulp fibrillation degree,
      • better quality of the produced nanofibrillated cellulose pulp,
      • better processing properties, including, for example, better water removability and better dispersing properties,
      • better strength properties compared to the same total energy consumption of refining, and
      • better optical properties compared to the same amount of the optical brightening agent (due to better retention of the optical brightening agent).
  • The amount of nanofibrillated cellulose in the pulp manufactured according to the invention may be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 w-%, including any and all ranges and subranges therein.
  • The pulp manufacturing process according to invention has at least one fibrillation stage, possibly at least 2, 3 or 4 fibrillation stages. According to the invention at least one type of the optical brightening agent is added
      • before at least one of the mentioned fibrillation stages or before the pre-refining stage, possibly before at least 2, 3, 4 or 5 of the mentioned fibrillation stages or before the pre-fibrillation stage,
        • and/or
      • to at least one of the mentioned fibrillation stages or to the pre-refining stage, possibly to at least 2, 3, 4 or 5 of the mentioned fibrillation stages or to the pre-refining stage.
  • In addition, according to the invention, the pulp is fibrillated after at least one additive dosage in at least one fibrillation stage in order to form some nanofibrillated cellulose material.
  • As it presented above, the addition of the optical brightening agent before or during the refining decreases the cellulose-cellulose bonding through hydroxyl groups by forming hydrogen bonds with the cellulose fibrils. At the same time, the addition of the optical brightening agent creates a dispersive effect to the pulp suspension through the repulsive forces between the anionic groups.
  • Experimental Tests
  • Experimental tests were carried out in processes wherein some amounts of optical brightening agents were dosed as refining additives. In addition, paper sheets were made from the produced pulps and tested afterwards.
  • 1. Used Pulp
      • A bleached birch pulp made with conventional chemical pulping process was used as raw cellulose pulp.
  • 2. Used Optical Brightening Agents
      • Two different kinds of optical brightening agents were used as the refining additive: disulphonic type of the optical brightening agent and hexasulphonic type of the optical brightening agent. In addition, reference samples without addition of the optical brightening agent were performed.
  • 3. Pre-Refining
      • The pre-refining stage was performed with Voith refiner. Addition of the used optical brightening agent was always 2 w-%. The whole amount was dosed to the pulp before the pre-refiner stage, after which the samples were refined at energy of 200 kWh/t. The pre-refinings were performed in the consistency of 4%.
      • The obtained pulps were diluted to 1.6% for fluidizer and to 2% for Masuko. The optical brightening agents were dosed to the pre-refining process in order to improve their bonding to fiber surface.
  • 4. Sample Preparation
      • 4a: Fluidizer
      • The part of the samples was fluidized with the M-700 Microfluidics Processor. Those samples were dispersed with a mixer in 1.6% consistency during 30 minutes. After dispersing, the samples were passed three times through fluidizer so that in the first pass there was only an APM chamber with diameter at 500 μm. In the second pass, the fiber suspension was passed through two sequential chambers with diameters at 500 μm and 200 μm. The third pass was carried out so that the fiber suspension passed through sequential 500 μm and 100 μm diameter chambers. The condenser of the fluidizer was switched off during all these trials, as it was found to improve fibrillation in the first part of experiments.
      • 4b: Masuko ultra-fine friction grinder.
      • The grinded samples were dispersed in 2% consistency with a mixer during 15 minutes before the treatment with Masuko. The dispersed samples were passed four times through Masuko in such a way that in the first pass the gap between the grinding stones was looser than with the following three passes. The grinder was washed after the first and third pass.
  • 5. Characterization
      • The gel-like fiber suspensions obtained from Masuko and from fluidizer were characterized by measuring viscosity (Brookfield) and turbidity of the samples and by observing optical microscope and SEM images of the samples. In addition, with centrifugation measurements the dry matter content was measured from both the liquid and the solid phase in order to determine the amount of nano-sized material in the sample.
  • 6. Preparation of Paper Sheets
      • Paper sheets were made in a laboratory from the produced pulps.
  • 7. Test Results
      • Refining result can be estimated by measuring the viscosity level of the nanofibrillated cellulose sample, because the viscosity level of the pulp material goes along with the portion of nanofibrillated cellulose in the pulp. In general, more refined, and thus, more fibrillated nanofibrillated cellulose is more gel-like material than less nanofibrillated cellulose. Therefore, more gel-like material means more nanofibrillated cellulose in the sample and this bigger part of nanofibrillate cellulose can be seen in higher viscosity level in the sample. Samples with optical brightening agent—dosage were clearly more viscous than the reference samples. The amount of unfibrillated fibers can be estimated from optical microscopy pictures.
      • Based on both the viscosity results and the optical microscope images, the optical brightening agent dosage had a clear effect on fibrillation. Some of these results can be seen in FIGS. 2 a-2 c wherein viscosity results with some optical microscopy pictures of Masuko grinded samples are shown. The FIG. 2 a presents the viscosity results of the reference sample 21, the sample with disulphonic optical brightening agent dosage 22, and the sample with hexasulphonic optical brightening agent dosage 23. FIG. 2 b shows an optical microscopy picture of the reference sample 21 and FIG. 2 c shows an optical microscopy picture of the sample 23 with hexasulphonic optical brightening agent dosage.
      • Also, preliminary redispersion tests on the fluidized samples were performed when the samples were oven dried. Differences in the disintegration of the dried films in water was detected. Reference samples did not broken into smaller pieces almost at all, but the optical brightening agent modified samples disintegrated clearly. FIGS. 3 a and 3 b show an optical microscopy images of fluidisator samples, wherein the reference sample (shown in FIG. 3 a) and the sample 32 with hexasulphonic optical brightening agent (shown in FIG. 3 b) are presented. The sample presented in FIG. 3 b with the dosage of the optical brightening agent is clearly better fibrillated than the reference sample shown in FIG. 3 a. FIGS. 4 a and 4 b show the same situation with SEM pictures (magnification: 10 000×) in which the reference sample (in FIG. 4 a) and the sample with hexasulphonated optical brightening agent addition (in FIG. 4 b) are presented. As can be seen, the samples with hexasulphonated optical brightening agent looks clearly better compared to the reference sample, as many smaller fibrils can be seen in the image.
      • Quality of the nanofibrillated cellulose can be analyzed using centrifugation of nano-sized material and measuring the turbidity of the samples. Centrifugation results are supposed to describe the degree of fibrillation so that the more the nano-sized material has more efficient fibrillation than less nano-sized material. When it comes to turbidity results, the smaller the value for turbidity is, the more there should be nano-sized material in the sample. FIG. 5 shows turbidity and centrifugation results of the fluidized samples. In this figure the reference sample 51, the sample 52 with disulphonic type of the optical brightening agent dosage, and the sample 53 with addition of hexasulphonic type of the optical brightening agent are presented. As can be seen, according to the turbidity results, the samples with OBA dosages were the most nano-sized. Also centrifugation results indicated that amount of nano-sized material increases along with OBA addition.
      • The paper sheets tested afterwards showed that internal strengths of the sheets produced according to the invention were clearly higher than the internal strength properties of the reference sheets produced without optical brightening agent addition.
  • One skilled in the art understands readily that the different embodiments of the invention may have applications in environments where optimization of a nanofibrillated cellulose pulp fibrillation is desired. Therefore, it is obvious that the present invention is not limited solely to the above-presented embodiments, but it can be modified within the scope of the appended claims.

Claims (12)

1. A method for manufacturing pulp, wherein the manufactured pulp contains at least 30 w-% nanofibrillated cellulose material measured from the dried pulp, the method comprising:
introducing raw material to a system which raw material includes cellulose,
dosing at least one type of an optical brightening agent as a refining additive to the system, and
refining the raw material in the presence of the dosed optical brightening agent in at least one pre-refining stage or fibrillation stage in order to form fibrillar cellulose material.
2. The method according to claim 1, wherein the refining is made in the presence of the dosed optical brightening agent in at least one fibrillation stage in order to form fibrillar cellulose material.
3. The method according to claim 1, wherein manufactured pulp contains at least 40 w-%, at least 50 w-%, at least 60 w-%, or at least 70 w-% nanofibrillated cellulose material measured from the dried pulp.
4. The method according to claim 1, wherein at least part of the raw material is selected from the following group:
unbleached chemical pulp,
bleached chemical pulp,
unbleached chemithermo pulp, and
bleached chemithermo pulp.
5. The method according to claim 1, wherein at least one type of the optical brightening agent is dosed before the pre-refining stage.
6. The method according to claim 1, wherein at least one type of the optical brightening agent is added to the pre-refining stage.
7. The method according to claim 1, wherein at least one type of the optical brightening agent is dosed before the fibrillation stage.
8. The method according to claim 1, wherein at least one type of the optical brightening agent is dosed to the fibrillation stage.
9. The method according to claim 1, wherein at least one dosed optical brightening agent type is selected from the group of stilbene, coumarin and pyrazoline compounds.
10. The method according to claim 1, further comprising:
using the pulp in nanofibrillated cellulose composites.
11. The method according to claim 1, further comprising:
utilizing the pulp in manufacturing of paper or paperboard including
base paper production, and
finishing stages of paper or paperboard.
12. The use according to claim 11, wherein said finishing stages comprise coatings for the paper or paperboard.
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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120043039A1 (en) * 2009-02-13 2012-02-23 Upm-Kymmene Oyj Method for producing modified cellulose
US20120316330A1 (en) * 2011-06-09 2012-12-13 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrated conversion of lignocellulosic material to sugars or biofuels and nano-cellulose
US20150041089A1 (en) * 2013-08-08 2015-02-12 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US20150191036A1 (en) * 2012-05-29 2015-07-09 De La Rue International Limited Substrate for security documents
US20150218756A1 (en) * 2012-08-21 2015-08-06 Upm-Kymmene Corporation Method for making paper product and paper product
US20150299955A1 (en) * 2012-11-03 2015-10-22 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose
US20160060814A1 (en) * 2013-04-29 2016-03-03 Blankophor Gmbh & Co., Kg Use of Micronized Cellulose and Fluorescent Whitening Agent for Surface Treatment of Cellulosic Materials
AU2013399666B2 (en) * 2013-09-04 2017-05-25 Halliburton Energy Services, Inc. Nano-carbohydrate composites as a lost circulation materials - LCM origami and other drilling fluid applications
US20170167079A1 (en) * 2014-05-21 2017-06-15 Cellucomp Ltd. Cellulose microfibrils
US9970159B2 (en) * 2014-12-31 2018-05-15 Innovatech Engineering, LLC Manufacture of hydrated nanocellulose sheets for use as a dermatological treatment
US10017624B2 (en) 2013-05-01 2018-07-10 Ecolab Usa Inc. Rheology modifying agents for slurries
US10053817B2 (en) 2010-04-27 2018-08-21 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US10087580B2 (en) 2015-05-01 2018-10-02 Fpinnovations Dry mixed re-dispersible cellulose filament/carrier product and the method of making the same
US10100232B2 (en) 2007-12-20 2018-10-16 University Of Tennessee Research Foundation Wood adhesives containing reinforced additives for structural engineering products
US10132040B2 (en) 2013-08-08 2018-11-20 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US10214859B2 (en) 2016-04-05 2019-02-26 Fiberlean Technologies Limited Paper and paperboard products
US10294371B2 (en) 2009-03-30 2019-05-21 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US10301774B2 (en) 2009-03-30 2019-05-28 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10570347B2 (en) 2015-10-15 2020-02-25 Ecolab Usa Inc. Nanocrystalline cellulose and polymer-grafted nanocrystalline cellulose as rheology modifying agents for magnesium oxide and lime slurries
US10577469B2 (en) 2015-10-14 2020-03-03 Fiberlean Technologies Limited 3D-formable sheet material
US10697116B2 (en) * 2014-03-31 2020-06-30 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose and nanofibrillar cellulose product
US10695947B2 (en) 2013-07-31 2020-06-30 University Of Maine System Board Of Trustees Composite building products bound with cellulose nanofibers
US10731298B2 (en) 2012-06-15 2020-08-04 University Of Maine System Board Of Trustees Release paper and method of manufacture
US10752741B2 (en) * 2016-05-20 2020-08-25 Stora Enso, OYJ UV blocking film and composition comprising microfibrillated cellulose, a method for producing said film and use of the composition
CN111684130A (en) * 2017-12-04 2020-09-18 芬欧汇川集团 Process for making pulp precursor materials for composite applications from chemical pulp and products thereof
US10781025B2 (en) 2013-03-20 2020-09-22 Ahlstrom-Munksjö Oyj Fibrous substrate containing fibers and nanofibrillar polysaccharide
US10822442B2 (en) 2017-07-17 2020-11-03 Ecolab Usa Inc. Rheology-modifying agents for slurries
US10865317B2 (en) 2017-08-31 2020-12-15 Kimberly-Clark Worldwide, Inc. Low-fluorine compositions with cellulose for generating superhydrophobic surfaces
US10883226B2 (en) * 2016-02-03 2021-01-05 Kemira Oyj Process for producing microfibrillated cellulose and a product thereof
US11155697B2 (en) 2010-04-27 2021-10-26 Fiberlean Technologies Limited Process for the production of gel-based composite materials
US20220064390A1 (en) * 2017-03-01 2022-03-03 Stora Enso Oyj Process for production of film comprising microfibrillated cellulose
US11846072B2 (en) 2016-04-05 2023-12-19 Fiberlean Technologies Limited Process of making paper and paperboard products

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0908401D0 (en) 2009-05-15 2009-06-24 Imerys Minerals Ltd Paper filler composition
GB201019288D0 (en) 2010-11-15 2010-12-29 Imerys Minerals Ltd Compositions
EP2665859B1 (en) 2011-01-21 2019-06-26 FPInnovations METHOD FOR THE PRODUCTION Of HIGH ASPECT RATIO CELLULOSE NANOFILAMENTS
WO2012115590A1 (en) * 2011-02-24 2012-08-30 Innventia Ab Single-step method for production of nano pulp by acceleration and disintegration of raw material
FI20115882A0 (en) * 2011-09-08 2011-09-08 Teknologian Tutkimuskeskus Vtt Oy A process for making a fiber yarn
FI126041B (en) 2011-09-12 2016-06-15 Stora Enso Oyj Method for controlling retention and intermediate used in the process
FI126457B (en) 2011-11-14 2016-12-15 Upm Kymmene Corp Process for the production of fibrill cellulose
FI126118B (en) * 2012-02-10 2016-06-30 Upm Kymmene Corp Cellulose pulp pretreatment method
FI126013B (en) * 2012-02-13 2016-05-31 Upm Kymmene Corp Process and system for the treatment of fibril cellulose, as well as fibril cellulose material
SE537517C2 (en) 2012-12-14 2015-05-26 Stora Enso Oyj Wet-laid sheet material comprising microfibrillated cellulosic process for making them
FI127014B (en) * 2013-05-15 2017-09-29 Upm Kymmene Corp A process for preparing nanofibril cellulose and a paper product
FI125942B (en) * 2013-07-26 2016-04-15 Upm Kymmene Corp Modification procedure of nanofibrillar cellulose composition
FI126688B (en) * 2014-06-30 2017-03-31 Upm Kymmene Corp Method and apparatus for controlling the quality of nanofibrillar cellulose
EP3303404A4 (en) * 2015-06-04 2019-01-23 GL&V Luxembourg S.à.r.l. PROCESS FOR PRODUCING CELLULOSE NANOFIBRILLES
SE539833C2 (en) * 2016-04-01 2017-12-12 Stora Enso Oyj Process for production of film comprising microfibrillated cellulose
BR112018069541A2 (en) * 2016-04-04 2019-01-29 Fiberlean Tech Ltd compositions and methods for providing increased strength in ceiling, floor and construction products
EP4056741A1 (en) 2016-04-22 2022-09-14 FiberLean Technologies Limited A method for preparing an aqueous suspension comprising microfibrillated cellulose
US10463205B2 (en) 2016-07-01 2019-11-05 Mercer International Inc. Process for making tissue or towel products comprising nanofilaments
US10724173B2 (en) 2016-07-01 2020-07-28 Mercer International, Inc. Multi-density tissue towel products comprising high-aspect-ratio cellulose filaments
US10570261B2 (en) 2016-07-01 2020-02-25 Mercer International Inc. Process for making tissue or towel products comprising nanofilaments
BR112019004246B1 (en) 2016-09-01 2023-12-05 Hs Manufacturing Group Llc COMPOSITION, METHOD FOR ADJUSTABLE DERIVATIZATION, A CELLULOSE-BASED MATERIAL FOR WATER RESISTANCE OR WATER AND LIPID RESISTANCE, AND PRODUCT RESULTING FROM THE PROCESS
JP7749311B2 (en) 2016-09-19 2025-10-06 マーサー インターナショナル インコーポレイテッド Absorbent paper products with unique physical strength properties
US12467206B2 (en) 2016-09-19 2025-11-11 Mercer International Inc. Absorbent paper products having unique physical strength properties
WO2019161272A1 (en) 2018-02-15 2019-08-22 North Carolina State University Synthesis of micron and nanoscale carbon spheres and structures using hydrothemal carbonization
US11352747B2 (en) 2018-04-12 2022-06-07 Mercer International Inc. Processes for improving high aspect ratio cellulose filament blends
EP3824018A1 (en) * 2018-07-19 2021-05-26 Kemira Oyj Cellulose composition
FI129352B (en) * 2019-05-03 2021-12-31 Valmet Technologies Inc Monitoring and controlling of refining of fibrous pulp

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3534912A (en) * 1967-01-11 1970-10-20 Beloit Corp Low speed refining of a papermaking pulp solution
US3591451A (en) * 1969-02-06 1971-07-06 Ethyl Corp Pretreatment of vegetable matter and delignification of the refined matter with chloring dioxide
US6224663B1 (en) * 1996-07-15 2001-05-01 Rhodia Chimie Additivation of essentially amorphous cellulose nanofibrils with carboxyl cellulose with a high degree of substitution
US20070193707A1 (en) * 2005-02-19 2007-08-23 Xuan Truong Nguyen Pulp and paper having increased brightness
US20090025895A1 (en) * 2006-02-20 2009-01-29 John Stuart Cowman Process for the Manufacture of Paper and Board
EP2042655A1 (en) * 2006-07-19 2009-04-01 Pioneer Corporation Nanofiber sheet, process for producing the same, and fiber-reinforced composite material
CA2705970A1 (en) * 2007-11-26 2009-06-04 The University Of Tokyo Cellulose nanofiber, production method of same and cellulose nanofiber dispersion
US20090205795A1 (en) * 2008-02-07 2009-08-20 Yonghao Ni Combined process of peroxide bleaching of wood pulps and addition of optical brightening agents
US20090221812A1 (en) * 2006-02-08 2009-09-03 Stfi- Packforsk Ab Method for the manufacture of microfibrillated cellulose

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0607171A2 (en) * 2005-02-19 2009-08-11 Int Paper Co method for making pulp and / or a paper substrate, pulp, pulp or paper substrate and composition
US7914646B2 (en) * 2006-07-21 2011-03-29 Nalco Company Compositions and processes for paper production
JP4831570B2 (en) 2006-03-27 2011-12-07 木村化工機株式会社 Functional cellulose material having high functional particle content and method for producing the same
EP2132381A1 (en) 2007-04-05 2009-12-16 Akzo Nobel N.V. Process for improving optical properties of paper
JP5398180B2 (en) 2007-06-11 2014-01-29 国立大学法人京都大学 Lignin-containing microfibrillated plant fiber and method for producing the same
SE0800807L (en) 2008-04-10 2009-10-11 Stfi Packforsk Ab New procedure

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3534912A (en) * 1967-01-11 1970-10-20 Beloit Corp Low speed refining of a papermaking pulp solution
US3591451A (en) * 1969-02-06 1971-07-06 Ethyl Corp Pretreatment of vegetable matter and delignification of the refined matter with chloring dioxide
US6224663B1 (en) * 1996-07-15 2001-05-01 Rhodia Chimie Additivation of essentially amorphous cellulose nanofibrils with carboxyl cellulose with a high degree of substitution
US20070193707A1 (en) * 2005-02-19 2007-08-23 Xuan Truong Nguyen Pulp and paper having increased brightness
US20090221812A1 (en) * 2006-02-08 2009-09-03 Stfi- Packforsk Ab Method for the manufacture of microfibrillated cellulose
US20090025895A1 (en) * 2006-02-20 2009-01-29 John Stuart Cowman Process for the Manufacture of Paper and Board
EP2042655A1 (en) * 2006-07-19 2009-04-01 Pioneer Corporation Nanofiber sheet, process for producing the same, and fiber-reinforced composite material
CA2705970A1 (en) * 2007-11-26 2009-06-04 The University Of Tokyo Cellulose nanofiber, production method of same and cellulose nanofiber dispersion
US20090205795A1 (en) * 2008-02-07 2009-08-20 Yonghao Ni Combined process of peroxide bleaching of wood pulps and addition of optical brightening agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
On the Manufacture and Use of Nanocelluose, Ankerfors et al., 9th International Conference on Wood & Biofiber Plastic Composites, 2007 *

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10100232B2 (en) 2007-12-20 2018-10-16 University Of Tennessee Research Foundation Wood adhesives containing reinforced additives for structural engineering products
US9181653B2 (en) 2009-02-13 2015-11-10 Upm-Kymmene Oyj Method for producing modified cellulose
US20120043039A1 (en) * 2009-02-13 2012-02-23 Upm-Kymmene Oyj Method for producing modified cellulose
US10294371B2 (en) 2009-03-30 2019-05-21 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US10301774B2 (en) 2009-03-30 2019-05-28 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10982387B2 (en) 2009-03-30 2021-04-20 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose suspensions
US10975242B2 (en) 2009-03-30 2021-04-13 Fiberlean Technologies Limited Process for the production of nano-fibrillar cellulose gels
US10053817B2 (en) 2010-04-27 2018-08-21 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US11155697B2 (en) 2010-04-27 2021-10-26 Fiberlean Technologies Limited Process for the production of gel-based composite materials
US10633796B2 (en) 2010-04-27 2020-04-28 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US10100467B2 (en) 2010-04-27 2018-10-16 Fiberlean Technologies Limited Process for the manufacture of structured materials using nano-fibrillar cellulose gels
US8835141B2 (en) * 2011-06-09 2014-09-16 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrated conversion of lignocellulosic material to sugars or biofuels and nano-cellulose
US20120316330A1 (en) * 2011-06-09 2012-12-13 The United States Of America As Represented By The Secretary Of Agriculture Methods for integrated conversion of lignocellulosic material to sugars or biofuels and nano-cellulose
US20150191036A1 (en) * 2012-05-29 2015-07-09 De La Rue International Limited Substrate for security documents
US10731298B2 (en) 2012-06-15 2020-08-04 University Of Maine System Board Of Trustees Release paper and method of manufacture
US20150218756A1 (en) * 2012-08-21 2015-08-06 Upm-Kymmene Corporation Method for making paper product and paper product
US9702085B2 (en) * 2012-08-21 2017-07-11 Upm-Kymmene Corporation Method for making paper product and paper product
US9797093B2 (en) * 2012-11-03 2017-10-24 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose
US20150299955A1 (en) * 2012-11-03 2015-10-22 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose
US10781025B2 (en) 2013-03-20 2020-09-22 Ahlstrom-Munksjö Oyj Fibrous substrate containing fibers and nanofibrillar polysaccharide
US20160060814A1 (en) * 2013-04-29 2016-03-03 Blankophor Gmbh & Co., Kg Use of Micronized Cellulose and Fluorescent Whitening Agent for Surface Treatment of Cellulosic Materials
US10017624B2 (en) 2013-05-01 2018-07-10 Ecolab Usa Inc. Rheology modifying agents for slurries
US10695947B2 (en) 2013-07-31 2020-06-30 University Of Maine System Board Of Trustees Composite building products bound with cellulose nanofibers
US9303360B2 (en) * 2013-08-08 2016-04-05 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US10132040B2 (en) 2013-08-08 2018-11-20 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US20150041089A1 (en) * 2013-08-08 2015-02-12 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
AU2013399666B2 (en) * 2013-09-04 2017-05-25 Halliburton Energy Services, Inc. Nano-carbohydrate composites as a lost circulation materials - LCM origami and other drilling fluid applications
US10697116B2 (en) * 2014-03-31 2020-06-30 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose and nanofibrillar cellulose product
US11274396B2 (en) 2014-03-31 2022-03-15 Upm-Kymmene Corporation Method for producing nanofibrillar cellulose and nanofibrillar cellulose product
US10753041B2 (en) * 2014-05-21 2020-08-25 Cellucomp Ltd. Cellulose microfibrils
US20170167079A1 (en) * 2014-05-21 2017-06-15 Cellucomp Ltd. Cellulose microfibrils
US9970159B2 (en) * 2014-12-31 2018-05-15 Innovatech Engineering, LLC Manufacture of hydrated nanocellulose sheets for use as a dermatological treatment
US10087580B2 (en) 2015-05-01 2018-10-02 Fpinnovations Dry mixed re-dispersible cellulose filament/carrier product and the method of making the same
US11932740B2 (en) 2015-10-14 2024-03-19 Fiberlean Technologies Limited 3D-formable sheet material
US10577469B2 (en) 2015-10-14 2020-03-03 Fiberlean Technologies Limited 3D-formable sheet material
US11384210B2 (en) 2015-10-14 2022-07-12 Fiberlean Technologies Limited 3-D formable sheet material
US10570347B2 (en) 2015-10-15 2020-02-25 Ecolab Usa Inc. Nanocrystalline cellulose and polymer-grafted nanocrystalline cellulose as rheology modifying agents for magnesium oxide and lime slurries
US10883226B2 (en) * 2016-02-03 2021-01-05 Kemira Oyj Process for producing microfibrillated cellulose and a product thereof
US10801162B2 (en) 2016-04-05 2020-10-13 Fiberlean Technologies Limited Paper and paperboard products
US11274399B2 (en) 2016-04-05 2022-03-15 Fiberlean Technologies Limited Paper and paperboard products
US11732421B2 (en) 2016-04-05 2023-08-22 Fiberlean Technologies Limited Method of making paper or board products
US11846072B2 (en) 2016-04-05 2023-12-19 Fiberlean Technologies Limited Process of making paper and paperboard products
US10214859B2 (en) 2016-04-05 2019-02-26 Fiberlean Technologies Limited Paper and paperboard products
US12203223B2 (en) 2016-04-05 2025-01-21 Fiberlean Technologies, Ltd. Method of making paper or board products
US10752741B2 (en) * 2016-05-20 2020-08-25 Stora Enso, OYJ UV blocking film and composition comprising microfibrillated cellulose, a method for producing said film and use of the composition
US20220064390A1 (en) * 2017-03-01 2022-03-03 Stora Enso Oyj Process for production of film comprising microfibrillated cellulose
US10822442B2 (en) 2017-07-17 2020-11-03 Ecolab Usa Inc. Rheology-modifying agents for slurries
US10865317B2 (en) 2017-08-31 2020-12-15 Kimberly-Clark Worldwide, Inc. Low-fluorine compositions with cellulose for generating superhydrophobic surfaces
CN111684130A (en) * 2017-12-04 2020-09-18 芬欧汇川集团 Process for making pulp precursor materials for composite applications from chemical pulp and products thereof

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