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    • 专利摘要:
    PROCESS FOR THE TREATMENT OF CELLULOSE AND CELLULOSE PROCESSED ACCORDING TO THE PROCESS The present invention relates to a process for purifying a cellulose-containing sludge, such as microfibrillated cellulose, wherein the process comprises the following steps: - provision of a sludge comprises cellulose and a liquid; - subjecting the mud to an electric field, which induces the mud liquid to circulate; - separating the liquid from the cellulose, thereby obtaining a liquid-depleted slurry; - adding a washing liquid, such as an organic solvent, to the liquid exhausted slurry; - subjecting the exhausted liquid sludge to an electric field, which induces the sludge washing liquid to circulate; and - separating the washing liquid from the cellulose, thereby obtaining a purified cellulose. The invention also relates to cellulose, such as microfibrillated cellulose, which can be obtained from said process.
    公开号:BR112013029109B1
    申请号:R112013029109-5
    申请日:2012-05-11
    公开日:2021-04-20
    发明作者:Isto Heiskanen；Kaj Backfolk；Ari Kotilainen；Valentas Gaidelis；Jonas Sidaravicius
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    Field of Invention
    [001] The present invention relates to a process for purification, such as salt/ion reduction and/or free sugar reduction, preferably, through the use of dehydration, of a slurry comprising cellulose, such as microfibrillated cellulose , by submitting the mud to an electric field. Background of the Invention
    [002] Microfibrillated cellulose (MFC), also known as nanocellulose, is a material typically made from wood cellulose fibers. Also, it can be made from microbial sources, agricultural fibers, cellulose or dissolved CMC etc. In microfibrillated cellulose the individual microfibrils were partially or completely separated from each other.
    [003] Microfibrillated cellulose has a capacity to bind to water quite large, thus, it becomes difficult to reduce the water content of a slurry containing microfibrillated cellulose and, consequently, it becomes difficult to purify. The high water content of a slurry containing microfibrillated cellulose also prevents the use of said MFC in many different applications where a high solids MFC is required.
    [004] Currently, there are several and different methods to remove water from a slurry containing cellulose, such as microfibrillated cellulose. Thus, it is possible to use, for example, different drying techniques. Examples of different drying techniques include: freeze drying, spray drying and supercritical drying. However, these techniques are very energy-consuming and therefore not cost-effective for use in large-scale processes. Also, “keratinization” or an over-formation of keratin in microfibrillated cellulose fibers normally tends to occur when water is removed using different drying techniques. Keratinization occurs when irreversible bonds are formed between fibers. When this occurs, expansion and expansion of the fibers in water is not possible, so the original capacity to bind the fibers to water is then lost. Keratinization can be prevented by adding chemicals that physically impede or modify the fibers in such a way that the formation of bonds between the cellulose fibers is limited or prevented. Canadian patent document CA 1208631A describes a process for re-dispersing dry microfibrillated cellulose by adding additives that will prevent the fibrils from binding together, thereby also preventing keratinization of the fibres.
    [005] Furthermore, it is disclosed by Luchache et al., in the Annals of Craiova University, Electric Engineering Series, No. 32, 2008; ISSN 1842-4805, the dehydration of waste sludge from pulp and paper.
    [006] Mechanical treatments aimed at removing water from a slurry comprising microfibrillated cellulose can also be used. However, these treatments are usually not very successful due to the small fiber size and size distribution of microfibrillated cellulose. Furthermore, filtration of a slurry comprising cellulose, such as microfibrillated cellulose, is difficult due to the dense fabric formed by the slurry. Furthermore, the bonds between the microfibrillated cellulose fibers are also quite strong, which will contribute to making mechanical dewatering less efficient.
    [007] The inefficiency or limitations that occur in drying, for example, in pressurized dehydration, will later provide problems regarding the removal of ions from the constituents of the cellulose. Since a filter cake is formed during dehydration, greater resistance to dehydration will be obtained. At the same time, it is more difficult to remove, for example, ions or other dissolved species as these can accumulate in the filter cake. Therefore, the dehydrated filter cake obtained from MFC must, in fact, contain the initial amount of ions or even substantially larger amounts of ions.
    [008] When using a normal drying method, ions and residual chemicals remain in the fiber concentrate suspensions and finally in the dry microfibrillated cellulose (MFC) or cellulose sample.
    [009] Therefore, there is a need for an improved process for purification, such as salt/ion reduction and/or free sugar reduction, from a cellulose-containing slurry, such as microfibrillated cellulose, without causing keratinization or super formation of keratin (super-keratinization). Invention Summary
    [0010] The present invention solves one or more of the problems mentioned above by providing, according to a first aspect, a process for purification, such as salt/ion reduction and/or free sugar reduction, preferably using dehydrating, a cellulose-containing slurry, such as microfibrillated cellulose, the process comprising the following steps: - providing a slurry comprising cellulose and a liquid; - subjecting the mud to an electric field, which induces the liquid in the mud to circulate; - separating the liquid from the cellulose, thereby obtaining a liquid exhausted slurry; - adding a washing liquid, such as an organic solvent, to the liquid exhausted slurry; - subjecting the liquid exhausted slurry to an electric field, which induces the sludge washing liquid to circulate; e - separating the washing liquid from the cellulose, thereby obtaining a purified cellulose.
    The present invention, according to a second aspect, also provides a cellulose such as purified microfibrillated cellulose as mentioned in the first aspect.
    [0012] The present invention also provides, according to a third aspect, cellulose, such as microfibrillated cellulose, which can be obtained by the process mentioned according to the first aspect.
    [0013] The present invention also provides, according to a fourth aspect, the use of cellulose, such as microfibrillated cellulose, as mentioned in the second or third aspect, in a reinforcing additive, in a thickening agent, in a viscosity modifier, in a rheology modifier, in a cleaning powder, in a washing powder, in a detergent, in a foaming composition, in a barrier, in a film, in a food product, in a pharmaceutical composition, in a product cosmetic, in a paper or cardboard product, in a coating, in a hygiene/absorbent product, in an emulsifying/dispersing agent, in a drilling mud, in a composite material, and even used in water purification, in a filter , in a solar cell, in a battery, in an electronic circuit (which can be flexible, printed or coated) or even to increase the reactivity of cellulose in the manufacture of regenerated cellulose or cellulose derivatives.
    [0014] The aim of the present invention, therefore, is to provide a process for purification, such as salt/ion reduction and/or free sugar reduction, preferably using dehydration, of a slurry containing cellulose, such as cellulose microfibrillated, in an improved manner.
    [0015] Another objective of the present invention is to provide a dehydrated cellulose, such as a microfibrillated cellulose, having improved properties.
    [0016] These objectives, as well as other objectives and advantages, are obtained through the process according to the first mentioned aspect of the invention. It has been shown that the use of an electric field will markedly improve purification, such as salt/ion reduction and/or free sugar (carbohydrate) reduction, preferably, through the use of dehydration, of a slurry comprising cellulose, such as like, microfibrillated cellulose.
    [0017] Purification, such as salt/ion reduction and/or free sugar reduction, preferably can be done by using dehydration, through electroosmosis (or capillary electrophoresis). Such dehydration may additionally also involve stimulation from other external sources, such as mechanical or optical sources, or a magnetic field. An example is an ultrasound treatment. Purification may also be accomplished by any one or a combination of the methods described below for further drying of the material: 1) Evaporative drying methods; 2) Freeze drying, due to increased solids; 3) Addition of additives to eliminate keratinization can also be used in drying dehydrated material; 4) The dehydrated material can also be partially dried, after obtaining material that behaves like solid particles and, thus, is more easily used in commercial applications, while it is easily mixed and dispersed in other components (the fibers individual are substantially maintained) or easily used as such.
    [0018] It is preferred that an electric field with a voltage of 10 to 100V is used. Increasing the voltage typically increases the speed of water extraction. The optimal value is obtained when the current intensity of the generated electric field and the voltage gradient are at the maximum permissible levels.
    [0019] A pressure and/or heat can also be applied to the sludge, in order to further improve the purification, such as salt/ion reduction and/or free sugar reduction, of said sludge, preferably, when in use of dehydration. Pressure can be applied after the electric field has been applied and dewatering of the sludge has started. This is because it is preferred to increase the dryness content of the mud before pressure is applied. Another possibility is to have a weak dehydration in the field (E), simultaneously with the mechanical pressure being applied. However, this logically depends on the dryness content of the sludge being treated.
    [0020] The applied pressure is preferably a mechanical pressure, such as compression, carried out through the use, for example, of a pinch roller or a felt pinch device.
    [0021] The dryness content of the slurry comprising cellulose, such as microfibrillated cellulose, before purification, such as salt/ion reduction and/or free sugar reduction, preferably by use of dehydration is preferably of about 1 to 10% by weight. After treatment in accordance with the process, it is preferred that the dryness content of the purified material, such as the salt/ion depleted material and/or free sugar depleted material, preferably, through the use of dehydration, of the sludge comprising cellulose, such as microfibrillated cellulose, is about 5 to 50% by weight.
    [0022] The temperature of the sludge during purification, preferably involving dehydration, is preferably above 30°C, preferably being below 100°C.
    [0023] The slurry can also comprise nanoparticles (such as absorbents), salts and/or surfactants, which are stimulated by the electric field and improve the circulation of the liquid. Thereby, purification, such as salt/ion reduction and/or free sugar reduction, preferably involving dehydration of the sludge, is enhanced. Furthermore, flavoring agents can be reduced.
    [0024] The present invention is also related to cellulose, such as microfibrillated cellulose, which is being subjected to a purification process, such as salt/ion reduction and/or free sugar reduction, preferably through the use of dehydration , according to the process described above. It has been shown that through purification, such as salt/ion reduction and/or free sugar reduction, by using dehydration of a cellulose-containing slurry, such as microfibrillated cellulose, with the help of an electric field, none or a Very limited keratinization of microfibrillated cellulosic fibers will occur. Detailed Description of the Invention
    [0025] The present invention relates to a process for purification such as salt/ion reduction and/or free sugar reduction, preferably through the use of dewatering a cellulose containing slurry such as microfibrillated cellulose. Due to the characteristics of microfibrillated cellulose fibers, for example their size, size distribution and fiber bonding, it usually becomes quite difficult to purify, such as reducing salt/ion and/or reducing free sugar, a slurry comprising cellulose microfibrillated, through the use of dehydration.
    [0026] The term "cellulose" is intended throughout this description to include any type of cellulose, such as, for example, cellulose fibers (cellulose material). Cellulose can also be a microfibrillated cellulose (MFC). Cellulose can be bleached or unbleached. Cellulose can also be a crystalline cellulose, microcrystalline cellulose (MCC - which has a high purity due to its potential use in pharmaceutical compositions or other medical uses), BNC, (NCC - nanocrystalline cellulose, which can be used in electrical applications and which exhibits magnetic properties), CNC, CMC (carboxymethylcellulose or carboxymethylated cellulose), or synthetic polymer fibers and fibers made from pulp dissolution. Cellulose can be present in the form of a pulp, which can be a chemical pulp, mechanical pulp, thermomechanical pulp or chemo-thermomechanical pulp (CMP or CTMP). Said chemical pulp is preferably a sulfite pulp or a Kraft pulp.
    [0027] The pulp may consist of hardwood pulp, softwood or both types. The pulp may, for example, contain a mixture of pine and spruce woods or a mixture of birch and spruce woods. Chemical pulps that can be used in the present invention include all types of wood-based chemical pulps, including bleached, semi-bleached, and unbleached sulfite pulps, Kraft and soda-based pulps, and mixtures thereof. The pulp can be of the dissolved type. The pulp can also comprise textile fibers and also come from agriculture (eg potato, bamboo or carrots).
    [0028] It is intended throughout the present description that the term "free sugar" includes not only sugars in monomeric forms, but also smaller polymers. The term also includes carbohydrates.
    [0029] It has been demonstrated that by subjecting a slurry comprising cellulose, such as microfibrillated cellulose fibers, to an electric field, purification, such as salt/ion reduction and/or free sugar reduction, preferably by means of use of dehydration, can be markedly improved. One theory that explains how this fact works satisfactorily is that the electric field induces the liquids in the mud to circulate and thus pull water molecules out of the microfibrillated cellulose fibers, rather than pushing the microfibrillated fibers, as happens in the case of mechanical treatment. By pulling the water molecules, it will also be possible to remove the water molecules that are being absorbed by the microfibrillated fibers in a very efficient way. In this way, it is quite easy to purify the cellulose fibers contained in the sludge.
    [0030] It has been shown that upon purification, such as salt/ion reduction and/or free sugar reduction, preferably through the use of dehydration, a slurry comprising cellulose, such as microfibrillated cellulose, and following submission of the slurry to an electric field, no substantial keratinization of the microfibrillated fibers will occur. Thus, it is possible for the microfibrillated cellulose obtained according to the process mentioned in the first aspect of the invention to expand again when the microfibrillated cellulose comes into contact with water. This is of great importance when microfibrillated cellulose is used, for example, as a reinforcing additive, a thickening agent, or a viscosity modifier. Furthermore, the binding capacity of the dehydrated microfibrillated cellulose is also quite satisfactory, i.e. no substantial decrease in the binding capacity is observed.
    [0031] When correlated with the reduction of salt/ion, this effect may be due to the fact that the voltage gradient induces a migration of different ions from the filtrate. This causes a decrease in product specific conductivity and a decrease in sample conductivity.
    [0032] Dehydration is preferably done using electroosmosis. Electroosmotic flow is usually abbreviated by (EOF), which is synonymous with electroosmosis or electroendosmosis. Another electroosmosis process also includes the FFF process. Electroosmosis is the movement of liquid, such as water, induced by a potential or electric field applied through a porous material, a capillary tube, a membrane, micro-channel, or any other type of fluid conduit. The voltage generated by the electric field is preferably between 10-100V.
    [0033] The liquid containing salt/ion and/or free sugars from the sludge is separated from cellulose, such as microfibrillated cellulose, by removing it. This can preferably be done through different filtration techniques.
    The slurry comprises cellulose, such as microfibrillated cellulose, and a liquid. The liquid can be water, a solvent and mixtures of different solvents and/or liquids. The solvent can be an alcohol such as isopropanol, polyethylene glycol, glycol or ethanol. Also, it can be an acid or a base. Solvents such as isopropanol can change the surface tension of the sludge and this will promote dehydration. Certain solvents, such as isopropanol, can change the surface tension of the sludge, and this will promote dehydration. The solvent can also be a solvent having at least one ketone group, this preferably being acetone. Also, it is possible that the liquid is an ionic liquid. The slurry can also comprise nanoparticles, polymers, pigments, salts and/or surfactants, which are stimulated by the electric field and which will improve the migration and movement of the liquid, i.e., the flow, in the electric field and thus also the dehydration.
    [0035] According to a further preferred embodiment of the present invention, the washing liquid is water and/or an organic solvent. The organic solvent is preferably acetone. In the case of drying, it is desirable as a process procedure according to the above-mentioned first aspect, that water (more preferred, distilled water) is preferred as the washing liquid in case the cellulose is MFC, NCC, NFC or other derivative of cellulose, in a more efficient way to avoid keratinization (solvents should be avoided).
    [0036] Mud may also, as indicated above, comprise fibers of regular size. Also, it is possible that the slurry comprises fillers such as nanoclays, polymeric absorbents, PCC, kaolin or calcium carbonate. The amount of microfibrillated cellulose in the slurry can range between 20-90% by weight and the amount of regular size fibers such as Kraft pulp, hardwood and/or softwood fibers can be 10-80% in Weight. If a greater amount of filler and longer fibers are present in the sludge, it is possible to obtain a sludge with a rather high dryness content by using the dewatering process according to the invention. A dryness content of up to 90% by weight is achievable, as the presence of long fibers and/or fillers will make dewatering of the sludge easier.
    [0037] However, it is preferred to use a slurry comprising high amounts of microfibrillated cellulose. A slurry comprising microfibrillated cellulose in an amount of 80 to 100% by weight, or 80 to 90% by weight, is usually preferred. In many cases, it is preferred that the slurry comprises 100% microfibrillated cellulose, i.e. that no long sized fibers are present. The amount of microfibrillated cellulose to be produced depends on the end use of said microfibrillated cellulose.
    [0038] It may also be advantageous to subject the slurry to an increase in pressure, in combination with submission to the electric field. It has been shown that the combination of electric field and pressure will markedly improve the purification, preferably through the use of dehydration, of a slurry comprising cellulose, such as microfibrillated cellulose. It is preferred that pressure is applied after dehydration with the electric field has started, i.e. when the solids content of the slurry has been increased, preferably to about 4% by weight. If the solids content of the slurry is too low when pressure is applied, the microfibrillated cellulose is pressed through the openings of the dewatering device, along with the water, and no purification (such as such as salt/ion reduction and/or or sugar free reduction) of the microfibrillated cellulose will occur. When the solids content of the slurry is increased, the viscosity is also increased, and it is possible to apply pressure to the slurry, thereby increasing its dehydration.
    [0039] The pressure is preferably a mechanical pressure, being applied in any way possible. Thus, for example, it is possible to use a pinch roller or felt device to apply mechanical pressure to the slurry during dewatering. It is also possible to combine the electric field treatment with other types of treatment in order to increase dehydration. Examples of treatments other than pressure build-up include acoustic treatment and vacuum-based systems.
    [0040] The dryness content of the sludge comprising cellulose, such as microfibrillated cellulose, before purification, such as salt/ion reduction and/or free sugar reduction, preferably by use of dehydration, is about 1-50% by weight. Also, it can have a content of about 1-30% by weight or about 1-10% by weight.
    [0041] After treatment according to the process according to the first aspect of the invention, it is preferred that the dryness content of the dewatered sludge comprising cellulose such as microfibrillated cellulose is about 5-50% by weight plus preferably above 20% by weight. Therefore, it is possible to receive a slurry comprising microfibrillated cellulose with a very high dryness content in a very energy efficient way. Even though the dryness content is increased, the properties of the microfibrillated cellulose after water dilution are maintained, i.e. the properties of swelling in water and strength.
    [0042] The slurry temperature can be lower than 30°C before dewatering and be increased during the dewatering process, but always kept at a temperature lower than 100°C. However, lower temperatures, such as ambient temperature, are also possible. The temperature, preferably, should be kept below the boiling point. Increasing temperature can improve dehydration. This is because the viscosity of water is lowered.
    The present invention also relates to a cellulose, such as microfibrillated cellulose, which is purified according to a first aspect of the invention as mentioned above. It has been shown that through a purification process, of the salt/ion reduction and/or free sugar reduction type, preferably by using dehydration of a slurry comprising cellulose, such as microfibrillated cellulose, and which relies on the With the help of an electric field, no or only a very limited keratinization of the microfibrillated cellulosic fibers will occur. Thus, it is possible to produce a microfibrillated cellulose with improved properties, in a fast and very energy efficient way, compared to the use, for example, of conventional drying techniques.
    [0044] A microfibrillated cellulose fiber is usually quite fine (~20 nm) and its length is usually between 100 nm and 10 µm. However, microfibrils can be larger, for example, between 10-200 μm, but lengths of up to 200 μm can be found, due to the wide distribution of lengths. Fibers that have been fibrillated and that have microfibrils on the surface and microfibrils that are separated and located in an aqueous phase of a slurry are included in the definition of MFC. In addition, "whisker filaments" type fibers are also included in the definition of MFC.
    [0045] Microfibrillated cellulose is typically made from wood cellulose fibers, being possible to use hardwood fibers and softwood. Also, microfibrillated cellulose can be made from microbial sources, agricultural fibers such as wheat straw pulp or other non-wood fiber sources. Furthermore, microfibrillated cellulose can be produced by bacteria or made from carboxymethylcellulose (CMC).
    [0046] By using the electric field mentioned in the first aspect of the invention, the number of bacteria will also be reduced, as their cell walls will expand. The process according to the first aspect of the invention, by removing ions, will also remove ions and water from the microbes as well. This means that this removal of ions and water will eliminate the antimicrobial effect.
    [0047] According to a further preferred embodiment of the present invention, the process according to the first aspect may be accompanied by one or more modification steps, such as changing the ion charge, as will be described below.
    [0048] According to an additional preferred embodiment of the present invention, the cellulose according to the second and third aspect, can be further processed by using ion exchange, for example, as disclosed in patent document WO 2009126106, which discloses a method of modifying cellulose fibers. It will be possible to modify the cellulose to different forms of counter-charged ion, to obtain, for example, CMC adsorbed/absorbed in the fibers. Thus, it would be possible to have a counter-charged sodium ion modification to enhance the production of microfibrillated cellulose (MFC). Also, it would be possible, for example, to move from the Ca form to the Na form, and vice versa.
    [0049] According to a further preferred embodiment of the present invention, the counter-charge ion change, which preferably follows after the process steps of the first aspect of the invention, can be carried out by a process comprising the following steps: 1) washing the ions not contained in the pulp by means of electroosmosis (until the conductivity of the filtrate is sufficiently low), optionally followed by the addition of liquid, preferably distilled water; 2) washing the "clean" pulp with a sodium carbonate such as NaHCO3 and a basic agent such as NaOH (to raise the pH to about 9.0), preferably this can be done by addition of NaHC03 and NaOH into the washing liquid of the electroosmosis device. 3) washing the pulp with distilled water in the electroosmosis apparatus to remove excess Na ions.
    [0050] The change of oppositely charged ions as indicated above may be desirable in several applications: - to make more homogeneous pulps for chemical reactions, which allows different chemical reactions; - to improve the reactivity of the pulp; - to improve drying; or - to improve a new dispersibility of the dry pulp of each of the ions.
    [0051] In barrier-type applications, which may consist of multiple layers, as set forth in the fourth aspect of the present invention, the use of cellulose according to the second and third aspects may be especially desirable in the packaging of electronic equipment, or when manufacturing solar cells or cellulosic batteries, due to purity.
    [0052] The cellulose purified according to the second and third aspects can be present in the form of low metal content pulps. As such, they can be useful in the production of paper with low conductivity (due to dielectric properties), in pulp treatments with enzymes or as a pulp for chemical modifications.
    [0053] The cellulose purified according to the second and third aspects, in the form of microfibrillated cellulose, can be especially useful in the following applications or uses: - barrier type application, due to the improved film-forming properties; - washing powders, due to improved removal of Ca2+ (absorber/adsorber) or in other similar applications, where hard water is a cleaning problem in drinking water, as improved metal removal is possible. heavy drinking water (this is still a big problem in some regions of the world); - through oxidation and different additives it is possible to improve the metal absorption properties; - metallic absorbents, which are biodegradable.
    The preferred features of each aspect of the invention are also for each of the other aspects, "mutatis mutandis", i.e. modified in what has to be modified. The prior art documents mentioned herein are incorporated to the greatest possible extent permitted by law. The invention is further described with the help of the following examples, together with the attached figures, the sole purpose of which is to illustrate the invention, in no way conceived as limiting its scope. Description of Figures
    [0055] Figure 1 discloses the scheme of the dehydration installation (on the left) and the cathode plate with holes.
    [0056] Figure 2 discloses functions of current and mass of water collected, over time, under constant applied voltage of 20V.
    [0057] Figure 3 discloses the dehydration of microfibrillated cellulose (MFC) of low conductivity.
    [0058] Figure 4 discloses as a function of time, the mass of water collected during the dehydration of low conductivity MFC, under different voltages. Examples 1. Experimental Installation
    [0059] To investigate the dehydration of MFC dispersion, an experimental installation was set up, whose diagram is shown in Figure 1. The installation consists of a plastic tube with an internal diameter of 46 mm, fitted inside a stainless steel funnel. At the lower end of the tube, a plate with holes is arranged, also made of stainless steel, which functions as a lower electrode, usually the cathode. A paper filter is placed on the plate and the MFC dispersion is introduced into the filter. In the upper part of the MFC column there is another paper filter, and after this the upper electrode (anode) is placed.
    [0060] The best results were obtained with platinum electrode (no process change due to corrosion or contamination of the electrode was observed).
    [0061] The installation of figure 1 consisted of a battery with the researched MFC; a direct current (DC) voltage was applied inside said battery from the current source. The water, which comes out of the funnel, was placed in a beaker, located on top of a scale; the mass of water extracted from the MFC was recorded during the experiments. The experiments were usually carried out in two modes: with a voltage (U) constant or with a current (i) constant.
    [0062] Values of current functions and mass of water collected over time, under constant applied voltage of 20V are shown in Figure 2. An increase in pressure causes an increase in current and an increase in collected water.
    [0063] Surprisingly, it has been found that dehydration by electroosmosis can be used if: - at first (more or less) only electroosmosis is used; - due to dehydration, the viscosity will increase sufficiently (so that mechanical pressure can be applied) as illustrated in figure 2.
    [0064] Figure 3 shows the dehydration of MFC under low conductivity.
    [0065] Figure 4 discloses as a function of time, the mass of water collected during the dehydration of MFC under low conductivity, under different voltages. The increase in voltage causes an increase in the speed of dehydration (initial slope) and in the saturation value of the process. Example 2
    [0066] Reference MFC (initial MFC) - Dryness content (RI): 1.7%
    [0067] Salt/Metal contents based on dry matter: - Al: 9.5 mg/g; - Fe: 16 mg/g; - Ca: 1200 mg/kg; - Cu: 5.5 mg/kg; - K: 310 mg/kg; - Mg: 210 mg/kg; - Mn: 1.1 mg/kg; - Na: 1400 mg/kg; - Ni: 1.6 mg/kg; - Pb: 1.1 mg/kg; - Si: 76 mg/kg; - Zn: 5.9 mg/kg. Dehydration Procedure 1 - Water Removal Only.
    [0068] A filter paper was placed on the cathode, then the MFC and then a second filter paper. After these procedures, the anode was placed on top of them. The pressure (of anode weight) was 750 kPa. After a short time (2 minutes), additional weight was added (pressure was to 2400 Pa). The voltage during dehydration was 100 V and the time was 640 seconds. The procedure was repeated 3 times and the pressure was increased (last time to 4.6* 105 Pa). - Dehydrated MFC (MFC obtained by electroosmosis) - Results presented below.
    [0069] Salt/Metal contents based on Dry Matter: 30.5% - Al: 8.5 mg/kg; - Fe: 11 mg/kg; - Ca: 30 mg/kg; - Cu: 0.69 mg/kg; - K: 85 mg/kg; - Mg: 5.7 mg/kg; - Mn: 0.24 mg/kg; - Na: 12 mg/kg; - Ni: 0.68 mg/kg; - Pb: <0.4 mg/kg; - Si: 13 mg/kg; - Zn: 1.5 mg/kg; Example 3
    [0070] Reference MFC (initial MFC) - Dryness content (RI): 1.7%
    [0071] Salt/Metal contents based on dry matter: - Al: 9.5 mg/g; - Fe: 16 mg/g; - Ca: 1200 mg/kg; - Cu: 5.5 mg/kg; - K: 310 mg/kg; - Mg: 210 mg/kg; - Mn: 1.1 mg/kg; - Na: 1400 mg/kg; - Ni: 1.6 mg/kg; - Pb: 1.1 mg/kg; - Si: 76 mg/kg; - Zn: 5.9 mg/kg. Dehydration Procedure 2 - Water Removal and Acetone Wash
    [0072] MFC was dehydrated for 5 minutes (as in procedure 1 above, ie Example 2). After this procedure, the power was turned off and acetone was added (approximately the same amount as the water removed in the previous step). Then dehydration was started and continued for about 10 minutes. - Dehydrated MFC (MFC obtained by electroosmosis with acetone); Results presented below.
    [0073] Salt/Metal contents based on Dry Matter: 23.5% - Al: 4.6 mg/kg; - Fe: 10 mg/kg; - Ca: 10 mg/kg; - Cu: 0.68 mg/kg; - K: 40 mg/kg; - Mg: 7.1 mg/kg; - Mn: 0.13 mg/kg; - Na: 14 mg/kg; - Ni: 0.50 mg/kg; - Pb: <0.4 mg/kg; - Si: 13 mg/kg; - Zn: 1.5 mg/kg. Example 4 - Temperature Test
    [0074] Using the same installation mentioned above, temperature tests were performed.
    [0075] Temperature from 90 to 95°C - dehydration in 60 seconds - provided about 16 g of water.
    [0076] Temperature of 21°C - dehydration in 60 seconds - provided about 13.5 g of water.
    [0077] Consequently, it was advantageous to use a higher temperature to improve dehydration. Thus, the energy requirement for dehydration is much lower at elevated temperatures. Example 5
    [0078] A further experiment was carried out in which even more ions were removed (especially Ca+2 ions. At startup, the total amount was 20 g of wet MFC. 1. Approximately 11 g of water was removed by electroosmosis. a ) metallic content of water: i) Ca: 14 mg/L ii) K: 2.7 mg/L iii) Na: 26 mg/L iv)) Si: 1.3 mg/L 2. About 10 g of distilled water were added. 3. About 10g of water was removed. a) metallic content of water: i) Ca: 14 mg/L ii) K: 0.56 mg/L'iii) Na: 0.78 mg/L iv)) Si: 0.22 mg/L 4. About 10 g of distilled water was added. 5. About 9 g of water was removed. a) metallic content of water: i) Ca: 7.4 mg/L ii) K: 0.56 mg/L iii) Na: 0 mg/L (below detection limit) iv)) Si: 0.076 mg/L 6 . Distilled water (as reference) a) metallic content of water: i) Ca: 0.079 mg/L ii) K: 0 mg/L (below detection limit) iii) Na: 0 mg/L (below limit of detection) iv)) Si: 0 mg/L (below detection limit).
    [0079] In view of the above detailed description of the present invention, other modifications and variations will become apparent to those skilled in the art. However, it should be noted that these other modifications and variations can only be made as long as there is no departure from the spirit and scope of the invention.
    权利要求:
    Claims (12)
    [0001]
    1. Process for purification, such as saline/ionic depletion and/or free sugar depletion, preferably using dehydration, of a cellulose-containing slurry, such as microfibrillated cellulose, characterized in that it comprises the following steps: - providing a slurry comprising cellulose and a liquid; - subjecting the mud to an electric field, inducing the liquid in the mud to flow; - separating the liquid from the cellulose, thereby obtaining a liquid exhausted slurry; - adding a washing liquid, such as an organic solvent, to the liquid exhausted slurry; - subjecting the liquid exhausted slurry to an electric field, inducing the slurry washing liquid to flow; and - separating the washing liquid from the cellulose, thereby obtaining a purified cellulose.
    [0002]
    2. Process according to claim 1, characterized in that dehydration is done by electroosmosis.
    [0003]
    3. Process according to any one of the preceding claims, characterized in that an electric field with a voltage of 10 to 100V is used.
    [0004]
    Process according to any one of the preceding claims, characterized in that pressure is also applied in order to dehydrate the sludge.
    [0005]
    5. Process according to claim 4, characterized in that pressure is applied after the electric field has been applied and dehydration has started.
    [0006]
    Process according to any one of claims 4 and 5, characterized in that the pressure is a mechanical pressure.
    [0007]
    Process according to any one of the preceding claims, characterized in that the dry content of the sludge comprising cellulose, such as microfibrillated cellulose, before dehydration and/or saline/ionic depletion and/or free sugar depletion, is from 1 to 50 % by weight.
    [0008]
    Process according to any one of the preceding claims, characterized in that the dry content of the dewatered sludge comprising cellulose, such as microfibrillated cellulose, is from 5 to 50% by weight.
    [0009]
    Process according to any one of the preceding claims, characterized in that the temperature of the sludge during dewatering is above 30°C and below 100°C.
    [0010]
    10. Process according to any one of the preceding claims, characterized in that the slurry comprises nanoparticles, absorbents, salts, free sugars and/or surface-active agents, which are stimulated by the electric field.
    [0011]
    Process according to any one of the preceding claims, characterized in that the washing liquid is water and/or an organic solvent.
    [0012]
    Process according to any one of the preceding claims, characterized in that it is followed by an exchange of counterions and/or one or more additional washing steps.
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    同族专利:
    公开号 | 公开日
    ES2596216T3|2017-01-05|
    NZ617117A|2016-04-29|
    BR112013029110B1|2021-07-27|
    EP2707541A4|2014-11-19|
    DK2707540T3|2016-10-24|
    AU2012257465B2|2017-05-04|
    EP2707541A1|2014-03-19|
    JP6430830B2|2018-11-28|
    US9447541B2|2016-09-20|
    ZA201308335B|2014-11-26|
    CN103534409B|2017-02-15|
    ES2596227T3|2017-01-05|
    AU2012257467B2|2017-05-11|
    AU2012257465A1|2013-11-14|
    CA2834460A1|2012-11-22|
    CN103534408A|2014-01-22|
    US20140088301A1|2014-03-27|
    CL2013003258A1|2014-08-22|
    US9447540B2|2016-09-20|
    JP2014514427A|2014-06-19|
    RU2603957C2|2016-12-10|
    CA2835302C|2019-10-22|
    WO2012156880A1|2012-11-22|
    BR112013029109A2|2017-02-07|
    AU2012257467A1|2013-11-14|
    EP2707540B1|2016-07-13|
    PL2707541T3|2017-01-31|
    RU2013155201A|2015-06-20|
    PL2707540T3|2016-12-30|
    CN103534409A|2014-01-22|
    CA2835302A1|2012-11-15|
    DK2707541T3|2016-10-24|
    CN103534408B|2016-04-06|
    ZA201308337B|2014-12-23|
    RU2603956C2|2016-12-10|
    JP6165715B2|2017-07-19|
    US20140073774A1|2014-03-13|
    EP2707541B1|2016-07-13|
    WO2012156882A1|2012-11-22|
    RU2013155187A|2015-06-20|
    BR112013029110A2|2017-02-07|
    EP2707540A1|2014-03-19|
    CL2013003259A1|2014-08-18|
    JP2014519560A|2014-08-14|
    EP2707540A4|2014-11-19|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    SE1150436-2|2011-05-13|
    SE1150436|2011-05-13|
    PCT/IB2012/052353|WO2012156882A1|2011-05-13|2012-05-11|Process for treating cellulose and cellulose treated according to the process|
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