• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    The present invention relates to a method for manufacturing an intermediate product that can be stored and transported and efficiently converted into microfibrillated cellulose with limited energy input at the time of conversion. More specifically, the invention involves the use of dewatered carboxymethylcellulose or carboxylated cellulose fiber having a low degree of substitution and a high amount of additives.
    公开号:SE1651027A1
    申请号:SE1651027
    申请日:2016-07-11
    公开日:2018-01-12
    发明作者:Backfolk Kaj；Heiskanen Isto；Saukkonen Esa；Lyytikaeinen Katja；Saxell Heidi
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    METHOD FOR MANUFACTURING INTERMEDIATE PRODUCT FORCONVERSION INTO MICROFIBRILLATED CELLULOSE Technical field The present invention relates to a method for manufacturing an intermediateproduct that can be stored and transported and efficiently converted intomicrofibrillated cellulose with limited energy input at the time of conversion.More specifically, the invention involves the use of dewateredcarboxymethylcellulose or carboxylated cellulose fiber having a low degree ofsubstitution and a high amount of additives.
    Background The manufacturing of intermediate products for microfibrillated cellulose ornanofibrillar cellulose is known from the prior art. The functionalization ofcellulose fiber with small amounts of charged groups promote swelling andfurther the fibrillation, i.e. liberation of individual fibrils or fibril aggregates. Atthe same time as fiber is able to swell and at the same time well suited forfibrillation, the intermediate product becomes much more difficult to dewater.
    US6602994 is directed to a method for producing derivatized microfibrillarpolysaccharide. ln a derivatizing step, a non-microfibrillar polysaccharide iscontacted with a swelling agent, such as an anionic reagent under alkalineconditions. Microfibrillation is then accomplished by applying energy to thenon-microfibrillar polysaccharide.
    US20130053454 is directed to a method wherein cellulosic fibers are pre- treated by mechanical, chemical and/or enzymatic treatment and mixed with 2 pigments to form a dispersion and then dispersing the dispersion of pre-treated cellulosic fibers and pigments whereby a composition comprisingmicrofibrillated cellulose is formed.
    JP2015000977 is directed to a method for producing carboxymethyl cellulosenanofibers from carboxymethyl cellulose in an aqueous medium byjet treatment at a high pressure of 100 to 245 MPa.
    WO2016024046A1 presents an intermediate product that is partly ge|ed orfibrillated. The product is preferably modified with carboxylic groups anddewatering is preferably made at low pH. lt further emphasize that the pulpconsistency is 20-30% after a washing step.
    There is still a need for more efficient methods for producing microfibrillatedcellulose efficiently and with limited use of energy both in respect ofdewatering/drying and fibrillation/mixing, but also when considering theefficient mixing of functional chemicals into the ge|ed product. ln addition,there is a need to be able to efficiently provide intermediate products that canreadily be stored, transported and converted into microfibrillated cellulose on-site and shortly before use in a process for manufacturing a paper or boardproduct. For such intermediate products, it is essential that the intermediateproducts can be converted into microfibrillated cellulose with limited energyinput and ideally without the use of complex fiber activation, wetting agents, enzymatic treatments or expensive equipment.
    Summary of the invention lt has surprisingly been found that addition of certain functional additives cansignificantly influence the ability to form an intermediate product comprisingcarboxymethylcellulose or carboxylated fiber having a low degree ofsubstitution, which can then efficiently be converted into microfibrillated 3 cellulose in a process step wherein said intermediate product is refined,fluidized or homogenized. More specifically, it has been found that by usingcertain additives or combination of additives when preparing the intermediateproduct, microfibrillated cellulose can subsequently be obtained from saidintermediate product with a limited use of energy and avoiding the use of expensive equipment.
    Thus, one embodiment of the present invention is a method for manufacturingan intermediate product which can subsequently be converted into microfibrillated cellulose, comprising the steps of a) providing an aqueous suspension comprising carboxymethy|ce|u|oseor carboxylated cellulose fiber having a degree of substitution less than0.4; and b) dewatering the suspension of step a) on a wire to achieve anintermediate product in the form of a sheet or web having at least 30%dry content; wherein said suspension has a concentration of at least one additive of at least 1% by weight of the solids of the suspension.
    The intermediate product obtained in step b) typically has an average fiberlength of at least 1 mm. ln one embodiment of the present invention, the carboxymethy|ce|u|ose usedin step a) has been purified prior to step a).
    The additive used in step a) is, in one embodiment, a retention aid,dewatering aid, a salt or a combination of any of these additives. Retentionand dewatering aids can be either one component, two component or multi-component retention systems. Retention chemicals can also be combinedwith dewatering aids (there is some overlap between these types ofchemicals). Examples of retention chemicals are: polyethylene imines,polyamideamines, polyDADMAC, polyamines, polyaluminum chlorides, 4 polyaluminum sulphates, polyacrylamides, cationic starches, bentonite,montmorollinite, alum, silica or modified silicas such cationic silicas, nanosizecationic minerals such as calcium carbonate, clays, etc. ln addition, surfaceactive chemicals like tensides may influence the dewatering rate (e.g. SDS)and re-dispersion but also the re-dispersion and fibrillation in steps c) and d) _Also other chemicals that are known to either charge neutralize or flocculatethe fibers can be used. The use of co-solvent such as ethanol or isopropanolalcohol or isopropanyl alcohol (IPA) can be used as an additive or co-additiveto enhance the dewatering.
    A retention or dewatering system is typically comprising a cationic polymer,preferably highly charged, but of course not limited to other functionalizedpolymers or particles that might positively influence the dewatering such as hydrophobic grafted cationic polymers or pH sensitive polymers, etc.
    The retention system may comprise one or several of the above chemicals oranalogues of the listed chemicals. ln one embodiment, the product of step a) may be subjected to washing priorto step b). ln one embodiment, the additive in the suspension that is being dewatered instep b) is present in the suspension in step a). ln one embodiment, theadditive has been added to the suspension in step a). ln one embodiment, theadditive is added to the suspension in step b), for example by spraying. lnone embodiment, the additive is added to the suspension both in step a) andin step b).
    The intermediate product obtained in step b), which is in the form of a sheetor web, can readily be stored and transported. lt may also be shredded intopieces to facilitate storage and transportation. Said intermediate productobtained in step b) can then be treated as follows: c) dissolving the intermediate product of step b) in water to obtain adispersion, optionally with addition of additives and/or fibers and/orminerals; and d) mechanically fibrillating the dispersion of step c) to obtain microfibrillated cellulose.
    The product of step d) may then be dosed to a papermaking process. Theproduct of step d) typically functions as an efficient dewatering, strength orretention aid in such a papermaking process. The obtained product can alsobe used as component in surface sizing, pigmentation, or coating. ln one embodiment of the present invention, the degree of substitution of thecarboxymethylcellulose or carboxylated fiber used in step a) is from 0.01 to0.4, such as from 0.15 to 0.3. ln one embodiment of the present invention, the dewatering in step b) is performed on a wire or porous fabric. ln one embodiment of the present invention, the suspension that is beingdewatered in step b) also contains unmodified microfibrillated cellulose and/oroxidized microfibrillated cellulose.
    The grammage of the intermediate product according to present invention istypically at least 10 gsm, such as at least 20 gsm, at least 50 gsm or at least100 gsm. ln one ombodiment or the present invention, the concentration of additives ofthe suspension that is being dewatered in step b) is at least 1% by weight,preferably at least 5% by weight and more preferably 10% by weight. ln oneembodiment, the additive is a salt, optionally in combination with one or moreretention aid and/or dewatering aid. The salt or salts are typically monovalent 6 or divalent or multivalent metal salts. Examples of such salts are sodiumchloride, calcium chloride, sodium sulphate, calcium sulphate, lithiumchloride, potassium chloride, sodium bromide, potassium bromide, sodiumiodide, potassium iodide, potassium nitride, sodium acetate, potassiumhydroxide, sodium citrate, zinc phosphate and iron phosphate. The salt maybe added to the suspension in step a) or may be present in the suspension asa product from any previous derivatization step. ln one embodiment of the present invention, the concentration ofcarboxymethylcellulose or carboxylated cellulose fiber having a degree ofsubstitution less than 0.4 in the suspension in step a) is at least 0.5% byweight of the so|ids of the suspension, preferably at least 3% by weight of theso|ids of the suspension, more preferably at least 5% by weight of the so|ids of the suspension. ln one embodiment of the present invention, the intermediate productobtained in step b) of the present invention has a SR >38, more preferably>40 or >42. SR denotes the Schopper Riegler number which can be determined using methods known in the art. ln one embodiment of the present invention, the microfibrillated celluloseobtained in step d) of the present invention has a SR >90, more preferably>92 or >95. SR denotes the Schopper Riegler number which can be determined using methods known in the art. ln one embodiment of the present invention, additives selected from lowmolecular weight CMC, optical brightening agents, dyes, polyacrylic-baseddispersants, wet strength chemicals, starch, surface active polymers orsurfactants, nanopigments, minerals, latexes, biocides, hydrophobicchemicals (rosin resin, AKD, ASA, SMA, etc) and cationic polymers areadded in step c). 7 The microfibrillated cellulose obtained in step d) can for example be used asretention and/or dewatering aid, strength enhancing agent, flocculation aid,adhesive, surface sizing chemical, rheology modifier, barrier, foaming agent,dispersant for e.g. filler, filler, formation agent, OBA carrier agent, spraysuspension (e.g. glue), coating additive (e.g. co-binder or thickener), surface sizing additive, printability enhances, gloss enhancer. ln one embodiment of the present invention, the carboxylated cellulose fibersused in step a) may contain up to 15% by weight hemicellulose, such as 5-15% by weight hemicellulose. ln one embodiment of the present invention, the intermediate productobtained in step b) has a dry content of at least 30%, such as at least 40%, atleast 50%, at least 60%, at least 70% or at least 80%.
    Detailed description ln one embodiment of the present invention, the dewatering in step b) iscarried out on a wire. The dewatering on wire may, according to oneembodiment of the present invention be performed by using knowntechniques with single wire or twin wire system, pressure dewatering,frictionless dewatering, membrane-assisted dewatering, vacuum- orultrasound assisted dewatering, etc. The dewatering can optionally be madeby using IR, hot air, UV, EB and dryers simultaneously as dewatering or afterthe dewatering section. According to one embodiment of the presentinvention the wet web is dewatered by vacuum, i.e. water, and other liquids, issucked from the furnish when it is placed on the wire. ln one embodiment ofthe present invention, not only water is removed during the dewatering in stepb), but also other liquids such as alcohols. After the dewatering, it is possibleto dewater further with filter press fabrics or cloths. 8 The temperature of the web should normally not exceed 85°C or 95°C.
    The dry content of the dispersion in step c) to be treated by mechanicalfibrillation in step d) is preferably between 0.5-30% by weight of fibers.
    The dry content of the dispersion after it has been treated by the mechanicalfibrillation in step d) is preferably above 50% by weight of fibers. The dispersion is preferably dewatered after the mechanical fibrillation in order toincrease the dry content. By increasing the dry content, transportation of the dispersion to other sites can be done a more efficient way.
    The process may further comprise washing of the dispersion after themechanical fibrillation in step d).
    The mechanical fibrillation in step d) can be done in many different kinds ofmechanical treatment apparatus, for example refiners or grinders such asMasuko grinders or conventional refiners or grinders used in pulp and paperindustry or those disc|osed in prior art to make microfibri|ated ce|u|ose.However, it is preferred to use a pressure homogenizer which in a veryefficient way will produce microfibri|ated ce|u|ose. A high pressure is typicallyused during mechanical fibrillation, and the pressure is preferably between500-4000 Bar, more preferably between 1000-2000 Bar. The optimalpressure is often around 1500 Bar. The pressure needed depends on thematerial being treated. However, too high pressures are often not beneficial touse since the wear of the equipment will be too high. One example of aspecific pressure homogenizer is the so called microfluidizer. ln one embodiment of the present invention, foam forming is used in step a).ln this embodiment, a tenside or other agent that is useful to create foam, isadded to the suspension in step a). ln this embodiment, the intermediateproduct obtained in step b) is more bulky than the intermediate product obtained in embodiments where foam forming is not used in step a).
    Microfibrillated cellulose (MFC) shall in the context of the patent applicationmean a nano scale cellulose particle fiber or fibril with at least one dimensionless than 100 nm. MFC comprises partly or totally fibrillated cellulose orlignocellulose fibers. The liberated fibrils have a diameter less than 100 nm,whereas the actual fibril diameter or particle size distribution and/or aspectratio (length/width) depends on the source and the manufacturing methods.
    The smallest fibril is called elementary fibril and has a diameter ofapproximately 2-4 nm (see e. g. Chinga-Carrasco, G., Cellulose fibres,nanofibrils and microfibrils,: The morphological sequence of MFCcomponents from a plant physiology and fibre technology point of view,Nanoscale research letters 2011, 6:417), while it is common that theaggregated form of the elementary fibrils, also defined as microfibril (Fengel,D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970,Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. byusing an extended refining process or pressure-drop disintegration process. Depending on the source and the manufacturing process, the lengthof the fibrils can vary from around 1 to more than 10 micrometers. A coarseMFC grade might contain a substantial fraction of fibrillated fibers, i.e.protruding fibrils from the tracheid (cellulose fiber), and with a certain amountof fibrils liberated from the tracheid (cellulose fiber).
    There are different acronyms for MFC such as cellulose microfibrils, fibrillatedcellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulosefibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers,cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulosemicrofibril aggregates. MFC can also be characterized by various physical orphysical-chemical properties such as large surface area or its ability to form agel-like material at low solids (1-5 wt%) when dispersed in water. Thecellulose fiber is preferably fibrillated to such an extent that the final specificsurface area of the formed MFC is from about 1 to about 300 m2/g, such as from 1 to 200 m2/g or more preferably 50-200 m2/g when determined for a freeze-dried material with the BET method.
    Various methods exist to make MFC, such as single or multiple pass refining,pre-hydrolysis followed by refining or high shear disintegration or liberation offibrils. One or several pre-treatment step is usually required in order to makeMFC manufacturing both energy efficient and sustainable. The cellulosefibers of the pulp to be supplied may thus be pre-treated enzymatically orchemically, for example to reduce the quantity of hemicellulose or lignin. Thecellulose fibers may be chemically modified before fibrillation, wherein thecellulose molecules contain functional groups other (or more) than found inthe original cellulose. Such groups include, among others, carboxymethyl(CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxylmediated oxydation, for example "TEMPO"), or quaternary ammonium(cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC ornanofibrillar size fibrils.
    The nanofibrillar cellulose may contain some hemicelluloses; the amount isdependent on the plant source. Mechanical disintegration of the pre-treatedfibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material iscarried out with suitable equipment such as a refiner, grinder, homogenizer,colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer,macrofluidizer or fluidizer-type homogenizer. Depending on the MFCmanufacturing method, the product might also contain fines, ornanocrystalline cellulose or e.g. other chemicals present in wood fibers or inpapermaking process. The product might also contain various amounts ofmicron size fiber particles that have not been efficiently fibrillated.
    MFC is produced from wood cellulose fibers, both from hardwood or softwoodfibers. lt can also be made from microbial sources, agricultural fibers such aswheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. lt ispreferably made from pulp including pulp from virgin fiber, e.g. mechanical, 11 chemical and/or thermomechanical pulps. lt can also be made from broke or recycled paper.
    The above described definition of MFC includes, but is not limited to, the newproposed TAPPI standard W13021 on cellulose nanofibril (CMF) defining acellulose nanofiber material containing multiple elementary fibrils with bothcrystalline and amorphous regions.
    According to another embodiment, the suspension or dispersion maycomprise a mixture of different types of fibers, such as microfibrillatedcellulose, and an amount of other types of fiber, such as kraft fibers, fines,reinforcement fibers, synthetic fibers, dissolving pulp, TMP or CTMP, PGW,etc.
    The suspension or dispersion may also comprise other process or functionaladditives, such as fillers, pigments, wet strength chemicals, dry strengthchemicals, retention chemicals, cross-linkers, softeners or plasticizers,adhesion primers, wetting agents, biocides, optical dyes, fluorescentwhitening agents, de-foaming chemicals, hydrophobizing chemicals such as AKD, ASA, waxes, resins etc. Additives can also be added using a size press. ln view of the above detailed description of the present invention, othermodifications and variations will become apparent to those skilled in the art.However, it should be apparent that such other modifications and variations may be effected without departing from the spirit and scope of the invention.
    权利要求:
    Claims (1)
    [1] 1. _ A process for preparing an intermediate product suitable for subsequent Conversion into microfibrillated cellulose comprising the steps of a) providing an aqueous suspension comprisingcarboxymethylcellulose or carboxylated cellulose fiber having adegree of substitution less than 0.4; and b) dewatering the suspension of step a) on a wire to achieve anintermediate product in the form of a sheet or web having at least30% dry content wherein said suspension has a concentration of atleast one additive of at least 1% by weight of the solids of the suspension. _ A process according to claim 1, wherein the degree of substitution of the carboxymethylcellulose or carboxylated fiber used in step a) is from0.01 to 0.4. _ A process according to claim 2, wherein the degree of substitution of the carboxymethylcellulose or carboxylated fiber used in step a) is from0.15 to 0.3. _ A process according to any one of claims 1-3, wherein the concentration of additive in the suspension that is being dewatered instep b) is at least 5% by weight of the solids of the suspension. _ A process according to claim 4, wherein the concentration of the additive in the suspension in that is being dewatered in step b) is atleast 10% by weight of the solids of the suspension. 13 6. A process according to any one of claims 1-5, wherein the additive isselected from a retention aid, a dewatering aid and a salt or a combination thereof.7. A process according to claim 6, wherein at least one additive is a salt. 8. A process according to claim 7, wherein the salt is a monovalent ordivalent metal salt selected from sodium chloride, calcium chloride,sodium sulphate, calcium sulphate, lithium chloride, potassiumchloride, sodium bromide, potassium bromide, sodium iodide,potassium iodide, potassium nitride, sodium acetate, potassium hydroxide, sodium citrate, zinc phosphate and iron phosphate. 9. A process according to any one of claims 1-8, wherein the additive is present in the suspension in step a). 10.A process according to claim 9, wherein the additive has been addedto the suspension in step a). 11.A process according to any one of claims 1-8, wherein the additive isadded to the suspension in step b). 12.A process according to claim 11, wherein the additive is added in stepb) by spraying. 13.A process according to any one of claim 1-12, whereincarboxymethylcellulose is used in step a). 14.A process according to any one of claim 1-12, wherein carboxylatedcellulose fiber is used in step a). 15.A process according to claim 13, wherein said carboxylated fibercontains 5-15% by weight hemicellulose. 14 16.An intermediate product suitable for subsequent Conversion intomicrofibrillated ce|u|ose obtainable or obtained by a process accordingto any one of claims 1-15. 17. Process for preparing microfibrillated ce|u|ose comprising the steps of any one of claims 1-15 and also comprising the subsequent steps of c) dissolving the intermediate product obtained in step b) in water toobtain a dispersion, optiona|y with addition of additives and/orfibers and/or minerals; and d) mechanicaiiy fibrillating the dispersion of step c) to obtainmicrofibrillated ce|u|ose. 18.Microfibri|ated ce|u|ose obtainable by the process of claim 17. 19.A paper or board product comprising microfibrillated ce|u|oseaccording to claim 18.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1651027A|SE540103C2|2016-07-11|2016-07-11|Method of manufacturing intermediate product for conversioninto microfibrillated cellulose|SE1651027A| SE540103C2|2016-07-11|2016-07-11|Method of manufacturing intermediate product for conversioninto microfibrillated cellulose|
    EP17827082.3A| EP3481995A4|2016-07-11|2017-07-03|Method for manufacturing intermediate product for conversion into microfibrillated cellulose|
    US16/316,864| US20190292727A1|2016-07-11|2017-07-03|Method for manufacturing intermediate product for conversion into microfibrillated cellulose|
    PCT/IB2017/054007| WO2018011669A1|2016-07-11|2017-07-03|Method for manufacturing intermediate product for conversion into microfibrillated cellulose|
    CN201780042481.4A| CN109661492A|2016-07-11|2017-07-03|Manufacture the method for being converted into the midbody product of microfibrillated cellulose|
    JP2019500790A| JP2019522123A|2016-07-11|2017-07-03|Process for producing an intermediate product for conversion to microfibrillated cellulose|
    BR112019000110-7A| BR112019000110A2|2016-07-11|2017-07-03|method for manufacturing intermediate product for conversion to microfibrillated cellulose|
    CA3030090A| CA3030090A1|2016-07-11|2017-07-03|Method for manufacturing intermediate product for conversion into microfibrillated cellulose|
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