• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    PROCESS FOR PRODUCING MICROFIBRILLATED CELLULOSE The present invention is related to a process for treating cellulosic fibers, which process comprises a mechanical pretreatment of the fibers, followed by treating the fibers with an enzyme and, after that, mixing the fibers with a solution comprising a hydroxide alkali metal, with subsequent mechanical treatment of the fibers, to form microfibrillated cellulose. In this way, it is possible to produce microfibrillated cellulose (MFC) in an improved and energy-efficient way.
    公开号:BR112012000142B1
    申请号:R112012000142-6
    申请日:2010-07-02
    公开日:2021-05-18
    发明作者:Maarit Peltola；Pertti Nousiainen；Marianna Vehvilãinen；Taina Kamppuri；Ali Harlin
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    Field of Invention
    [001] The present invention relates to a process to produce microfibrillated cellulose by treating cellulosic fibers. Background of the Invention
    [002] Cellulosic fibers are multi-component structures made of cellulose polymers, that is, cellulose chains. Lignin, pentosans and other components known in the art may also be present. The cellulose chains in the fibers are fixed together to form elementary fibrils. Several elementary fibrils are linked together to form microfibrils and several microfibrils form aggregates. The bonds between the cellulose chains, elementary fibrils and microfibrils are hydrogen bonds.
    [003] Mycofibrillated cellulose (MFC) (also known as nanocellulose) is a material made of wood cellulose fibers, where the individual microfibrils have been detached from each other. MFC is usually very thin (~20 nm) and the range is usually between 100 nm to 1 µm.
    [004] MFC can be produced in a number of different modes. It is possible to mechanically treat the cellulosic fibers so that microfibrils are formed. However, this method is very energy-consuming, for, for example, fibrillating or refining the fibres, and therefore it is normally not used.
    [005] The production of nanocellulose or microfibrillated cellulose using bacteria is another option. Contrary to the above, this is a biosynthetic process, which starts from a raw material other than wood fibers. Also, it is a very expensive and time-consuming process.
    [006] Also, it is possible to produce microfibrils from cellulose, with the help of different chemicals, which will break or dissolve the fibers. However, it is difficult to control the extent of the fibrils formed, and the fibrils are usually remarkably short.
    [007] An example of MFC production is described in patent document WO 2007/091942. In the method described in this document, MFC is produced with the help of refining, in combination with the addition of an enzyme.
    [008] However, there is still a need for an improved process for the production of microfibrillated cellulose. Invention Summary
    [009] It is an objective of the present invention to provide a process for producing microfibrillated cellulose in an improved manner and that is efficient in energy consumption.
    [0010] These objectives and other advantages are achieved by the process according to claim 1. By mechanically making the previous treatment of cellulosic fibers, followed by enzymatic treatment and addition of a solution comprising an alkali metal hydroxide and, finally, an additional mechanical treatment, it is possible to produce microfibrillated cellulose (MFC) in a very efficient and energy-efficient way. This is achieved as described in the independent claim and preferred embodiments of the process are defined by the dependent claims.
    [0011] The invention relates to a process for treating cellulosic fibers, which process comprises a prior mechanical treatment of the fibers, followed by treating the fibers with an enzyme, and after that, mixing the fibers with a solution comprising a metal hydroxide alkaline in order to make the fibers expand. The expanded fibers are then mechanically treated to form microfibrillated cellulose. In this way, it is possible to produce MFC in an improved and energy-efficient way.
    [0012] The concentration of the alkali metal hydroxide may be between 4-18% by weight, preferably between 5-9% by weight. The alkali metal hydroxide concentration regulates the expansion of the fibers before the final mechanical treatment. The alkali metal hydroxide is preferably sodium hydroxide.
    [0013] The solution comprising alkali metal hydroxide may also comprise a zinc salt. The combination of alkali metal hydroxide and zinc salt has been shown to improve fiber expansion. The zinc salt is preferably zinc oxide. The concentration of the zinc salt may be between 0.1-2% by weight, preferably between 0.5-1.3% by weight.
    [0014] The pretreatment is preferably done by fibrillating or refining the fibers.
    [0015] The pretreatment opens the fiber structure before treatment with the enzyme and with the solution comprising alkali metal hydroxide. In this way, the enzymatic treatment as well as the treatment with the solution comprising alkali metal hydroxide and zinc salt will be more effective and the expansion of the fibers will be improved, as well as the production of MFC.
    [0016] The consistency of the fibers during refining is preferably between 2.5-30% by weight.
    [0017] Also, it is possible to add an enzyme before or during the pretreatment, in order to decompose the fiber structure. An enzyme that reacts with or breaks down hemicellulose is preferably used, for example xylanase, but cellulase, for example, endogulcanase, can also be used.
    [0018] The temperature during treatment with the solution can be between 0-15°C. Lower temperatures have been shown to increase fiber expansion.
    [0019] The enzyme used in the process, preferably, is cellulase, which will decompose the cellulosic fibers and increase the access capacity and activity of the fibers, and thus, also, the production of microfibrillated cellulose.
    [0020] Cellulosic fibers are preferably Kraft pulp fibers. Detailed Description of the Invention
    [0021] The invention relates to a process for producing mycofibrillated cellulose in an improved and energy-efficient manner.
    [0022] It has been shown that the combination of mechanical pretreatment followed by enzymatic treatment and addition of a solution comprising alkali metal hydroxide enables the expansion of the fibers in a smooth and controlled manner. Furthermore, it has been shown that an additional mechanical treatment of the expanded fibers can be done in order to produce the microfibrillated cellulose. Through this process it has been shown to be possible to produce MFC in a very controlled and energy efficient way.
    [0023] The enzymatic treatment followed by the addition of the solution comprising alkali metal hydroxide expands the fibers, and through this treatment it is possible to control the expansion of the fibers. By using enzyme and the mentioned chemical(s), it is possible to make some small adjustments, for example, in the concentrations and, thus, it becomes possible to control and regulate the degree of expansion of the fibers of a quite accurate way. Fibers expand due to the fact that the hydrogen bonds between the cellulose chains are weakened. Even though the hydrogen bonds are weakened by the treatment, the fibers are not affected in any way. Thus, the strength of the fibers is not reduced as when after a purely mechanical treatment, which is used in order to receive the same fiber length.
    [0024] The enzyme will decompose the primary layer of fibers and thus increase the access capacity of the fibers, then it will penetrate the fiber structure and insert itself between the fibrils. The solution comprising the alkali metal hydroxide will then be able to affect the fiber structure more efficiently as the primary layer of fibers is weakened. Some of the fibers will dissolve during treatment with the solution comprising the alkali metal hydroxide. When the alkali metal hydroxide content decreases after this stage, the dissolved fibrils will return to a solid state. When the fibrils return to a solid state, they will act as a glue and thereby increase the bond strength between the fibers and the fibrils. Consequently, the MFC produced will have satisfactory film-forming properties.
    [0025] Cellulosic fibers are pretreated before treatment with the enzyme and solution comprising alkali metal hydroxide. The fibers are preferably defibrated or refined in order to increase the specific surface area of the fibers, prior to the enzymatic treatment, thereby facilitating and improving the effect of the enzymatic treatment. The shredding or refining can be done with a fiber consistency between 240% by weight, with respect to the total weight. However, a high consistency, preferably between 15-40% by weight, with respect to the total weight, is normally preferred. A low consistency, for example, of 2-6% by weight, with respect to the total weight, or a medium consistency, for example, of 10-20% by weight, with respect to the total weight, can also be used.
    [0026] Also, it is possible to add enzymes during pretreatment. Usually, the use of enzymes which break the hemicellulose chain, such as, for example, xylanase, is preferred, but other enzymes, such as, cellulase, for example, endoglucanase, can also be used. Enzymes can be added in order to further improve the pretreatment and also to be able to decrease the degree of mechanical treatment, thereby saving fiber strength and energy required.
    [0027] Other mechanical pretreatments, in addition to refining and defibration, such as beating, steam explosion, defibration, homogenization, ultrasonic treatment, dry cutting or other known mechanical fiber treatments, in order to soften the fibers and make them more active and reactive before the following treatments can be used.
    [0028] After pretreatment, the enzyme is added to the fibers that are in the form of a slurry, which has a concentration of approximately 4-5%. The enzyme is added during agitation, both at the beginning of the treatment and during the entire reaction time. The purpose of the enzymatic treatment is to break the hydrogen bonds between the microfibrils present in the slurry and, thus, allow the fibers to expand. The enzyme increases the access capacity and activity of the fibers and improves the following treatment using the solution.
    The enzymes used can be any wood decomposition enzymes that break down cellulosic fibers. Cellulase is preferably used, but other examples of enzymes that can be used include xylanase and mannanase. The enzyme is usually an enzyme preparation, which may contain small parts of other enzyme activities, different from the main enzyme in the preparation. The temperature used for the enzyme treatment can be between 3085°C. However, the temperature depends on the enzyme used and the optimum working temperature for the specific enzyme, as well as other treatment parameters such as time and pH. If cellulase is used, the temperature during treatment can be approximately 500°C.
    [0030] Enzyme activity can last for 30 minutes to 5 hours. The time required depends on the cellulosic fibers being treated and enzyme activity, as well as the temperature and pH of the treatment. The enzyme activity can be from 10-1000 nkat/g.
    [0031] Enzyme treatment can be terminated by raising the temperature or pH in order to denature the enzymes. Alternatively, the solution comprising alkali metal hydroxide is added directly to the treated fibers and it is not necessary to denature the enzymes separately since the pH of the alkali metal hydroxide solution is high enough to terminate the enzymatic treatment. The pH during enzyme treatment is preferably between 4-6.
    [0032] The solution comprising alkali metal hydroxide is thereafter added to the enzyme treated fibers to form a slurry. Preferably, the slurry has a concentration between 1-7% by weight, relative to the total weight. The concentration of the alkali metal hydroxide can be between 4-18% by weight, with respect to the total weight, preferably between 5-9% by weight, with respect to the total weight. The term total weight means the total weight of the sludge, that is, the total weight of the solution and the pulp.
    [0033] The solution may also contain a zinc salt. The combination of an alkali metal hydroxide and a zinc salt has been shown to be very efficient when expanding the fibers. The concentration of the zinc salt can be between 0.1-2% by weight, with respect to the total weight, preferably between 0.5-1.3% by weight, with respect to the total weight.
    [0034] If the solution comprises the two components, ie alkali metal hydroxide and a zinc salt, the alkali metal hydroxide concentration and the zinc salt concentration will be dependent on each other. Thus, for example, when a high concentration of alkali metal hydroxide occurs, a lower concentration of zinc salt is required. The amount of alkali metal hydroxide and zinc salt should be adjusted in a staggered way, within their determined limits, so that optimal results can be obtained. The alkali metal hydroxide concentration and the zinc salt concentration are thus dependent on each other with respect to the expansion efficiency of cellulosic fibers.
    [0035] The temperature during treatment with the solution can be between 0-150C. Lower temperatures have been shown to increase fiber expansion. However, it is important not to decrease the temperature too much, as fiber dissolution increases with decreasing temperature. Thus, it is not desirable that there is dissolution of the fibers, so that the temperature, as well as other parameters, must be controlled, in order to only expand the fibers, and not promote their dissolution.
    The alkali metal hydroxide is preferably sodium hydroxide, but other alkali metal hydroxides such as potassium hydroxide or a mixture of sodium hydroxide and potassium hydroxide or other alkali metal hydroxides can be used. The zinc salt is preferably zinc oxide, but other zinc salts such as, for example, zinc chloride or mixtures between different zinc salts can be used.
    [0037] The pH during treatment with the solution comprising alkali metal hydroxide or alkali metal hydroxide and zinc salt is preferably above 13. Treatment of the fibers with the solution comprising alkali metal hydroxide may take between 5 minutes to 2 hours, depending on whether or not the mud is mixed during the treatment. When treatment with the solution is complete, the solution can be washed with water or an acid. Before the addition of water or acid, a low concentration of sodium hydroxide or other alkali metal hydroxide can be added in order to remove the part with dissolved cellulose (if any) so that it can be used later.
    [0038] When the alkali metal hydroxide content decreases, the dissolved fibrils or particles will return to the solid state (as described above). This regeneration of fibrils or dissolved particles occurs when the alkali metal hydroxide content is decreased. The reduction can be achieved by adding water or acid, or the produced sludge comprising the produced MFC can be mixed with another pulp sludge, for example, at the wet end of a paper or paperboard making machine.
    [0039] Dissolved cellulose is a clear or slightly turbid solution, containing the dissolved cellulosic material and nanoparticles. Solid particles in the solution that are called dissolved particles must, however, be of a size that cannot be seen under an optical microscope. Thus, the dissolved part also contains nano-sized fibers and therefore must also be recovered and used.
    [0040] The solid part received by the process according to the invention and the dissolved part can be further treated, together or separately.
    [0041] A drawback with the addition of water or acid is that the fibers tend to partially shrink, being advantageous to avoid this shrinkage. This shrinkage can be avoided by defibrating the fibers before adding water or acid, or through mechanical means, producing nanocellulose before adding water or acid. Also, it is possible to add chemicals that can prevent shrinkage. The choice of chemical is correlated with the end use of the expanded fibers. So, for example, surface active components, mechanical prevention by adding bentonite or TiO2, adding CMC or starch or surfactants in order to “freeze” the fiber structure, before adding water or acid.
    [0042] Then, the fibers are mechanically treated in order to form the microfibrillated cellulose. The time and temperature during this treatment varies, depending on the fibers treated, as well as the previous treatments, these parameters being controlled in order to receive fibers with the desired extension. Mechanical treatment can be done by means of a refining device, shredder, beater, friction polisher, high shear fibrillator (such as Cavitron rotor/stator system), disperser, homogenizer (such as micro fluidizer) or other devices known fiber treatment mechanics.
    The cellulosic fibers used in the process according to the invention are preferably Kraft pulp fibers, i.e. they have been treated according to the Kraft process. It has been shown that the primary wall of fibers in Kraft pulp normally prevents the fibers from expanding. Thus, it is necessary to remove the primary wall before the expansion treatment. The primary fiber wall can be removed by intensifying fiber pretreatment. Thus, an intensive refining procedure, preferably a high consistency refining, has been shown to be quite effective. Also, enzymes that react with hemicellulose can be used, alone or in combination with a refining procedure, preferably high consistency refining. Also, it is possible to treat the fibers with enzymes before refining the fibers. However, other chemical pulps, mechanical pulps, or chemical-mechanical pulps can also be used, an example being sulfite pulp. Fibers can be bleached or unbleached, although bleached is preferred as the lignin content is reduced and the fibers expand more easily.
    [0044] Cellulosic fibers can be hardwood or softwood fibers. It has been shown that pine kraft and sulphite pulps disintegrate into smaller fractions when treated in accordance with the invention, compared to eucalyptus and birch kraft pulps. Therefore, it is preferred to treat softwood fibers with the process according to the invention. The cellulosic material produced according to the invention can be used for film production. Microfibrillated cellulose (MFC) produced from softwood Kraft pulps according to the process as described herein have been shown to obtain very satisfactory film-forming properties.
    [0045] Microfibrillated cellulose (MFC) is commonly also referred to as nanocellulose. 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. Example
    [0046] A birch kraft pulp had the following treatment: - mechanical shredding for 5 hours with a pulp consistency of 20%; - enzymatic treatment with cellulase, 250nkat/g, pH 5, 500C, 3 hours.
    [0047] The pulp was then subjected to a NaOH solution with a concentration of 9% by weight, at a temperature of 100C, without intermediate drying to study its expansion capacity. The wet pulp (20% consistency) was added in NaOH at a temperature of 100°C, with the final blend content being 5% by weight pulp and 9% by weight NaOH. The mixture was stirred for 15 minutes at 1000 rpm, then left stable for 1 hour and 45 minutes, under the same temperature. The sample was then studied under an optical microscope and the soluble cellulose portion was measured.
    [0048] The expanded sample was purified by adding 4% NaOH, centrifuging the mixture and separating the clear/slightly turbid supernatant. The supernatant was treated with 10% H2SO4 to precipitate the dissolved cellulose. Then, the undissolved purified part and the dissolved precipitated part were further washed with water in a dialysis procedure. It was concluded that 42% of the fibers were dissolved.
    [0049] Then, the undissolved part and the precipitated dissolved part were subjected to a high shear mixture, with a consistency of 1.5%, for 10 minutes, in order to produce the MFC.
    [0050] The total energy consumption when producing the MFC, as described in this Example, was approximately 0.3 MWh/t.
    [0051] Studies related to the state of the art have shown that the production of MFC with the help of mechanical treatment is approximately 2-3 MWh/t.
    [0052] Consequently, the energy consumption of the Example of the invention was markedly reduced.
    权利要求:
    Claims (12)
    [0001]
    1. Process to treat cellulosic fibers, which process is characterized by the fact that it comprises the steps of: - mechanically pre-treating the fibers; - treat the fibers with an enzyme; - mixing the fibers with a solution comprising an alkali metal hydroxide in a concentration between 4 to 18% by total weight, in order to make the fibers expand; and finally - mechanically treating the expanded fibers to form microfibrillated cellulose.
    [0002]
    2. Process according to claim 1, characterized in that the concentration of alkali metal hydroxide is between 5 and 9% by total weight.
    [0003]
    3. Process according to claim 1, characterized in that the solution comprises a zinc salt.
    [0004]
    4. Process according to claim 3, characterized in that the concentration of the zinc salt is between 0.1 and 2% by total weight, preferably between 0.5 and 1.3% by weight.
    [0005]
    5. Process according to any one of the preceding claims, characterized in that the fibers are pre-treated through shredding or refining.
    [0006]
    6. Process according to claim 5, characterized in that the fibers are treated with a consistency of 2.5-40% by weight, with respect to the total weight, during the defibration or refining procedures.
    [0007]
    7. Process according to any of the preceding claims, characterized in that the temperature during treatment with the solution is between 0 and 15°C.
    [0008]
    8. Process according to any of the preceding claims, characterized in that the alkali metal hydroxide is sodium hydroxide.
    [0009]
    9. Process according to any one of claims 3 to 8, characterized in that the zinc salt is zinc oxide.
    [0010]
    10. Process according to any one of the preceding claims, characterized by the fact that the enzyme is cellulase.
    [0011]
    11. Process according to any one of the preceding claims, characterized in that the enzyme that reacts with hemicellulose, such as xylanase, or an enzyme that reacts with cellulose, such as cellulase, is added before or during the mechanical pretreatment of the fibers.
    [0012]
    12. Process according to any one of the preceding claims, characterized in that the fibers are Kraft pulp fibers.
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    法律状态:
    2020-11-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-11-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/07/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF |
    优先权:
    申请号 | 申请日 | 专利标题
    SE0950534A|SE533510C2|2009-07-07|2009-07-07|Method for producing microfibrillar cellulose|
    SE0950534-8|2009-07-07|
    PCT/IB2010/053043|WO2011004300A1|2009-07-07|2010-07-02|Process for producing microfibrillated cellulose|
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