• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD TO PRODUCE CELLULOSE NANOFIBRILLA. In a method for the production of cellulose nanofibril, a fibrous cellulose-based material, in which internal bonds in the cellulose fiber have been weakened by chemical modification, they are supplied, separating fibrils, through various counter-rotation rotors (RI, R2 , R3 ...) and that externalize in the radial direction in relation to the rotation axis (RA) of the rotors, so that the material is repeatedly subjected to shear forces and impact by the effect of the blades (1) of the different rotors of counter-rotation, according to which it is fibrillated simultaneously.
    公开号:BR112014011501B1
    申请号:R112014011501-0
    申请日:2012-11-14
    公开日:2021-03-09
    发明作者:Juha Tamper；Markus Nuopponen
    申请人:Upm-Kymmene Corporation；
    IPC主号:
    专利说明:

    Field of invention
    [0001] The invention relates to a method for the production of nanofibrillar cellulose, in which the fibrous cellulose-based material is supplied in a refining interstice to separate fibrils. Background of the invention
    [0002] In refining fibers containing lignocellulose through, for example, a disc refiner or a conical refiner at a low consistency of about 3 to 4%, the structure of the fiber wall is loosened, and so-called fibrils or fines are separated from the fiber surface. The fines formed and flexible fibers have an advantageous effect on the properties of most types of paper. In refining pulp fibers, however, the objective is to retain the length and strength of the fibers. In the post-refining of the mechanical pulp, the objective is the partial fibrillation of the fibers, making the thick fiber wall thinner by refining, to separate the fibrils from the fiber surface.
    [0003] Fibers containing lignocellulose can also be totally disintegrated into smaller parts by separating the fibrils that act as components in the fiber walls, in which the particles obtained become significantly smaller in size. The properties of the cellulose nanofibril so called thus obtained differ significantly from the properties of the normal pulp. It is also possible to use cellulose nanofibril as an additive in the manufacture of paper and to increase the resistance of the internal bond (interlaminar resistance) and tensile strength of the paper product, as well as to increase the cohesion of the paper. Cellulose nanofibril also differs from the pulp in its appearance, because it is a gel-like material in which fibrils are present in a dispersion of water. Because of the properties of cellulose nanofibril, it has become a desired raw material, and the products that contain it would have various uses in the industry, for example, as an additive in various compositions.
    [0004] Cellulose nanofibril can be isolated as such directly from the fermentation process of some bacteria (including Acetobacter xylinus). However, in view of the large-scale production of cellulose nanofibril, the raw material with the most promising potential is the raw material derived from plants and containing cellulose fibers, particularly wood and fibrous pulp made from it. The production of cellulose nanofibril from the pulp requires the decomposition of the fibers still on the fibril scale. In processing, a cellulose fiber suspension is processed several times through a homogenization step that generates high shear forces on the material. This can be achieved by guiding the suspension under high pressure repeatedly through a narrow gap where it reaches a high speed. It is also possible to use refining discs, among which the fiber suspension is introduced several times.
    [0005] In practice, the production of cellulose nanofibril from cellulose fibers of the conventional size class can currently be implemented by laboratory scale disc refiners, which have been developed for the needs of the food industry. This technique requires several courses of refining in succession, for example 2 to 5 courses, to obtain the nanocellulose size class. The method is also poorly scalable to an industrial scale. Brief Summary of the Invention
    [0006] It is an objective of the invention to eliminate the above mentioned disadvantages and to present a method by which the cellulose nanofibril can be made with a good capacity and also a greater consistency.
    [0007] To achieve this objective, the method according to the invention is characterized mainly by the fact that the fibrous material is introduced through several counter-rotation rotors that are externalized in the radial direction in relation to the rotation axis of the rotors in such a way that the material is repeatedly subjected to shear and impact forces by the effect of different counter-rotation rotors, in which it is fibrillated simultaneously.
    [0008] As a matter of great importance, the fibrous material in the suspension is repeatedly impacted by the rotor blades or ribs hitting in opposite directions when the blades rotate at the speed of rotation and at the peripheral speed determined by the radius (distance to the axis of rotation) ) in opposite directions. Because the fibrous material is transferred outward in the radial direction, it strikes the wide surfaces of the blades, that is, ribs, proceeding one after the other at a high peripheral speed from opposite directions; in other words, it receives several successive impacts from opposite directions. In addition, on the margins of the wide surfaces of the blades, that is, ribs, whose margins form an interstice in the blade with the opposite edge of the next rotor blade, shear forces occur which contribute to fibrillation.
    [0009] The fibrous material to be processed is such cellulose in which the internal bonds of the fiber have already been weakened by chemical pretreatment. Cellulose is therefore chemically modified cellulose. Such cellulose, which has already been adequately labialized prior to its mechanical processing, can be surprisingly influenced by impacts from blades (ribs) in opposite directions and which can be produced by a series of successive rotors, and by shear forces generated on the edges of the blades (ribs) when the fibers are transferred from the radius of action of one rotor to the radius of action of the next rotor.
    [00010] In addition, fibrillation works well when the pH of the fibrous suspension is in the neutral or slightly alkaline range (pH 6 to 9, advantageously 7 to 8). A high temperature (above 30 ° C) also contributes to fibrillation. With regard to temperature, the normal operating environment for processing is generally 20 to 60 ° C. The temperature is advantageously between 35 and 50 ° C.
    [00011] At the periphery of each rotor, there are several blades that, together with several blades of the anterior and / or next rotor in the radial direction, due to their rotation movement in opposite directions, repeatedly produce several interstices or narrow spaces in the blade, where the fibers are also subjected to shear forces since the opposite edges of the blades, that is, ribs, cross at high speed when moving in opposite directions.
    [00012] It can be said that in each pair of counter-rotation rotors, a large number of narrow blade interstices and, consequently, reversals of impact directions, are generated during a single rotation of each rotor, the frequency of recurrence being proportional to the number of blades, that is, ribs on the periphery. Consequently, the direction of impacts caused by the blades, that is, ribs on the fibrous material is changed at a high frequency. The number of blade interstices during rotations and their frequency of recurrence depend on the density of the blades distributed on the periphery of each rotor, and, correspondingly, on the rotation speed of each rotor. The number of such rotor pairs is n - 1, where n is the total number of rotors, as a rotor always forms a pair with the next outer rotor in the radial direction, with the exception of the outermost rotor, through which the pulp processed leaves the refining process.
    [00013] Different rotors can have different number of blades, that is, ribs, for example, in such a way that the number of blades increases in the outermost rotors. The number of blades, that is, ribs, can also vary according to another formula.
    [00014] The density of the blades / ribs on the periphery of each rotor, as well as the angles of the blades in relation to the radial direction, as well as the rotational speeds of the rotors can be used to affect the refining efficiency (the refining intensity) , as well as the processing time of the fibrous material to be refined.
    [00015] The fibrillation method based on high frequency impacts from different directions is particularly suitable for such fibrous cellulose-based material, in which the internal bonds of the cellulose have been weakened by a chemical pretreatment, whereby the method can be used for the production of cellulose nanofibril. The pretreated cellulose can thus be carboxymethylated, oxidized (for example, N-oxyl-mediated oxidations) or cationic.
    [00016] Another advantage to be obtained by the method is the fact that it can also be used for the refining of the fibrous material in high consistencies (2 to 4%) compared to, for example, a homogenizer, because the gelation during the refining of the same material several times does not require dilution of the material. The principle makes it possible to use even higher consistencies than this, where the density of the blades / ribs can be adjusted to match the consistency currently used.
    [00017] The supply can be implemented so that the mixture to be passed through the rotors contains a certain part of the volume of a gaseous medium mixed in it, but, as a separate phase, for example, greater than 10% by volume. To intensify the separation of the fibrils, the gas content is at least 50% by volume, advantageously at least 70% and more advantageously between 80 and 99%; that is, expressed in degrees of filling (the proportion of the fiber suspension to be processed in the volume that passes through the rotor) less than 90% in volume, not exceeding 50%, not exceeding 30% and, correspondingly, between 1 and 20%. The gas is advantageously air, in which the fiber suspension to be processed can be supplied so that a given proportion of air is mixed with the fiber suspension.
    [00018] The method is also advantageous in the sense that it can be easily scaled up, for example, by increasing the number of rotors. Description of the drawings
    [00019] In the following, the invention will be described in more detail with reference to the attached drawings, in which: - Figure 1 shows the device used in the present invention in a sectional plane AA coinciding with the axis of rotation of the rotors, - Figure 2 shows the device of figure 1 in a partial horizontal section, - Figure 3 shows the device according to a second modality used in the invention in a sectional plane AA coinciding with the axis of rotation of the rotors, - Figure 4 shows the device of figure 3 in a partial horizontal section, and - Figures 5 to 7 show samples of materials refined with the device. Detailed description of the invention
    [00020] In this application, cellulose nanofibril refers to cellulose microfibrils or bundles of microfibrils separated from the fibrous cellulose-based raw material. These fibrils are characterized by a high aspect ratio (length / diameter): their length can exceed 1 μm, while the diameter typically remains less than 200 nm. The smallest fibrils are on the scale of the so-called elementary fibrils, the diameter being typically 2 to 12 nm. The dimensions and size distribution of the fibers depend on the refining method and efficiency. Cellulose nanofibril can be characterized as a cellulose-based material, in which the average particle length (fibrils or fibril bundles) is not greater than 10 μm, for example, between 0.2 and 10 μm, advantageously not more than 1 μm, and the particle diameter is less than 1 μm, suitably ranging from 2 nm to 200 nm. Cellulose nanofibril is characterized by a large specific surface area and a strong ability to form hydrogen bonds. In the dispersion of water, cellulose nanofibril typically appears either as a clear or almost colorless gel-like material. Depending on the fibrous raw material, cellulose nanofibril may also contain small amounts of other wood components, such as hemicellulose or lignin. Frequently parallel names used for cellulose nanofibril include nanofibrillated cellulose (NFC), which is often called simply nanocellulose, and microfibrillated cellulose (MFC).
    [00021] In this application, the term "refining" or "fibrillation" generally refers to material comminuted mechanically by the work applied to the particles, whose work can be grinding, crushing or shearing, or a combination of these, or other corresponding action that reduces the particle size. The energy required for refining work is usually expressed in terms of energy per amount of raw material processed in units, for example, kWh / kg, MWh / ton, or units proportional to these.
    [00022] Refining is carried out at a low consistency for the mixture of fibrous raw material and water, the fiber suspension. Hereafter, the term pulp will also be used for the mixture of fibrous raw material and water subjected to refining. The fibrous raw material submitted to refining can refer to whole fibers, separate parts of them, bundles of fibrils, or fibrils, and, typically, the pulp is a mixture of such elements, in which the proportions between the components are dependent on the refining stage.
    [00023] Particularly in the case presented in this application, "refining" or "fibrillation" occurs by means of impact energy using a series of frequently repeated impacts with varying directions of action.
    [00024] The device shown in figure 1 comprises several counter rotating rotors R1, R2, R3 ... placed concentrically within each other, so that they rotate around a common axis of rotation RA. The device comprises a series of rotors R1, R3 ... rotating in the same direction, and rotors R2, R4 ... rotating in the opposite direction, in which the rotors are arranged in pairs, so that one rotor is always followed and / or preceded in the radial direction by a counter-rotation rotor. Rotors R1, R3 ... rotating in the same direction are connected to the same mechanical rotation means 5. Rotors R2, R4 ... rotating in the opposite direction are also connected to the same mechanical rotation means 4, but rotating in a direction opposite to the direction of the means mentioned above. Both rotation means 4, 5 are connected to their own drive axes which are introduced from below. The drive axes can be located concentrically in relation to the axis of rotation RA, for example, in such a way that the external drive axis is connected to a lower means of rotation 4, and the internal drive axis placed inside and rotating freely in relation to it, it is connected to an upper means of rotation 5.
    [00025] The figure does not show the fixed housing of the device within which the rotors are placed to rotate. The housing comprises an inlet, through which the material can be supplied from the top into the innermost rotor R1, and an outlet located on the side and oriented approximately tangentially outwardly in relation to the peripheries of the rotors. The housing also comprises interstitial holes for the drive shafts below.
    [00026] In practice, the rotors consist of vanes or blades 1 placed at certain intervals on the periphery of a circle whose geometric center is the axis of rotation RA, and extending radially. In the same rotor, flow interstices 2 are formed between the vanes 1, through which the material to be refined passes can flow radially outwards. Between two successive rotors R1, R2; R2, R3; R3, R4; etc., several spaces or interstices of the blade are formed repeatedly and at a high frequency during the rotational movement of the rotors in the opposite direction. In figure 2, reference number 3 indicates such interstices of the blade between the blades 1 of the fourth and fifth rotors R4, R5 in the radial direction. The blades 1 of the same rotor form narrow interstices, that is, interstices of the blade 3, with the blades 1 of the previous rotor (having the narrowest radius at the periphery of the circle) in the radial direction and with the blades 1 of the next rotor (placed in the periphery of the circle with the largest radius) in the radial direction. In a corresponding manner, a large number of changes in the direction of impact are formed between two successive rotors when the blades of the first rotor rotate in a first direction along the periphery of the circle, and the blades of the next rotor rotate in the opposite direction along from the periphery of a concentric circle.
    [00027] The first series of rotors of R1, R3, R5 are mounted on the same axis of mechanical rotation 5 which consists of a horizontal lower disk and an upper horizontal disk, connected to each other by one of the blades of the first rotor R1, more internally in the radial direction. On the upper disk, in turn, the blades of the other rotors R3, R4 of this first series are mounted, with blades 1 extending downwards. In this series, the blades 1 of the same rotor, except for the innermost rotor R1, are still connected at their lower end by a connection ring. The second series of rotors R2, R4, R6 are mounted on the second mechanical rotation means 4, which is a horizontal disk placed under said lower disk, and to which the blades 1 of the series rotors are connected, extending to up. In this series, the blades 1 of the same rotor are connected at their upper ends by a connection ring. Said connection rings are concentric with the axis of rotation RA. The lower discs are also arranged concentrically by an annular groove and a corresponding annular protrusion on the surfaces facing the discs, also placed concentric with the axis of rotation RA and being equally spaced from it.
    [00028] Figure 1 shows that the vanes or blades 1 are elongated pieces parallel to the axis of rotation R1 and having a height greater than width I (the dimension in the radial direction). In the horizontal section, the blades are square, in figure 2 rectangular. The fibrous material is passed transversely to the longitudinal direction of the blades, from the center outward, and the margins on the sides of the surfaces facing the radial direction on the blades 1 form narrow and long interstices 3 of the blade that extend in the longitudinal direction of the blade. , with the corresponding margins of the blades 1 of the second rotor.
    [00029] The rotors of R1, R2, R3 ... are thus, in one way, flow interstitial rotors in the form of concentric bodies of revolution in relation to the axis of rotation, in which the part that processes the fibrous material it consists of elongated vanes or blades 1 extending in the direction of the axis of rotation RA, and flow interstices 2 left between them.
    [00030] Figure 1 also shows that the heights h1, h2, h3 ... of the blades of rotor 1 gradually increase from the first, that is, the innermost rotor R1 outwards. As a result, the heights of the flow interstices 2 limited by the rotor blades 1 also increase in the same direction. In practice, this means that when the cross-sectional area of the radial flow increases externally as the peripheral length of the rotors increases, the increase in height also increases this cross-sectional area. Consequently, the travel speed of a single fiber is decelerated in the external direction, if the volume flow is considered to be constant.
    [00031] Due to the centrifugal force caused by the rotational movement of the rotors, the material to be processed is passed through the rotors with a certain retention time.
    [00032] As can be easily concluded from figure 2, during a single entire rotation of a pair of rotors (from a position where the supplied blades are aligned, to the position in which the same blades 1 are aligned again), various interstices of the blades 3 are formed when the successive blades 1 in the peripheral direction encounter successive blades of a second rotor. As a result, the material transferred through the interstices 2 that are externalized in the radial direction is continuously subjected to shear forces and impact in the interstices of the blade 3 between different rotors and in the flow interstices 2 between the blades 1 on the periphery of the rotor, when the material is passed from the rotor interval to the reach of an external rotor, while the movement of the blades in the peripheral direction and the changes in the direction of movement caused by the rotors rotating in different directions prevent the flow out and very fast. material through the rotors by the effect of the centrifugal force.
    [00033] Paddle 3 interstices and, correspondingly, paddle encounters 1 and respective changes in the impact directions in two successive rotors in the radial direction are generated at a frequency of [1 / s] which is 2 x fr x n1 x n2, where n1 is the number of blades 1 on the periphery of the first rotor, n2 is the number of blades on the periphery of the second rotor, and fr is the speed of rotation in revolutions per second. Coefficient 2 is due to the fact that the rotors rotate at the same speed of rotation in opposite directions. More generally, the formula has the form (fr (1) + fr (2)) x n1 x n2, where fr (1) is the rotation speed of the first rotor and fr (2) is the rotation speed of the second rotor in the opposite direction.
    [00034] In addition, figure 2 shows how the number of blades 1 can be different in different rotors. In the figure, the number of blades per rotor increases from the most interim rotor, except for the last rotor R6 where it is smaller than in the previous rotor R5. As the rotational speeds (rpm) are the same regardless of the location and direction of rotation of the rotor, this means that the frequency at which the blades 3 pass at a given point and, correspondingly, the frequency of the interstice formation of the blade 3 increase from the inside to the outside in the radial direction of the device.
    [00035] Figures 3 and 4 show a device that has a principle and a structure similar to that represented in figures 1 and 2. The difference is that the last two rotors R5 and R6 that rotate in different directions are equipped with blades placed in a angle in the direction of radius r, while the blades on the other rotors are parallel to radius r. In the penultimate rotor R5, these paddle surfaces 1, which limit the flow interstices 2, are at an angle α1 with respect to 4 on the side of the direction of rotation; in other words, its outer margin is ahead of the inner margin in the peripheral direction. In addition, in the last rotor R6, the blades are turned at an angle α2 with respect to the radius, in the direction of rotation. The blade angles of the different rotors are the same, but they can also be different. Angles α1, α2 can be between 30 and 60 °. In figure 4, the angles α1, α2 are 45 °. Due to the angular position of the blades 1, they are shaped like a parallelogram in a horizontal cross section.
    [00036] When the blades 1 are rotated in the manner described above for the direction of rotation, they can be used to retain the fibrous material to be processed more efficiently in the range of the rotor blades, and to increase the retention time and processing efficiency. Also on other rotors, the blades can be placed at an angle to the radius, such that the angle is formed on the side of the direction of rotation. The angles can also vary in different rotors, for example, in such a way that the angle increases from the inside to the outside. In the internal rotors, the angle can be smaller than in the external rotors. The situation is, in a way, the same in figure 4 as well, because there the angle in relation to the radius r is 0 in all other rotors, except for the last two rotors.
    [00037] In figures 1 and 3, the dimension I of the blades in the direction of radius r is 15 mm, and the dimension and the interstice of the blade 3 in the same direction is 1.5 mm. Said values can vary, for example, from 10 to 20 mm and from 1.0 to 2.0 mm, respectively. The dimensions are influenced, for example, by the consistency of the material to be processed.
    [00038] The diameter d of the device, calculated from the outer margin of the outermost rotor R6, can vary according to the desired capacity. In figures 1 and 3, the diameter is 500 mm, but the diameter can also be larger, for example, greater than 800 mm. When the diameter is increased, the production capacity increases by a greater proportion than the proportion of the diameters.
    [00039] It has been revealed that a decrease in the speed of rotation of the rotors impairs fibrillation. Likewise, a decrease in flow (production) clearly improves fibrillation; in other words, the longer the retention time of the material to be processed during which it is subjected to the impact and shear forces of the blades, that is, ribs, the better the result of the fibrillation.
    [00040] In the process described above, the material to be processed to produce cellulose nanofibril is a mixture of water and fibrous cellulose-based material in which the fibers have been separated from each other in the preceding manufacturing processes of mechanical pulp or chemical pulp , where the starting material is preferably woody raw material. In the manufacture of cellulose nanofibrils, it is also possible to use cellulose fibers from other plants, in which cellulose fibrils are separable from the fiber structure. The suitable consistency of the low consistency pulp to be refined is 1.5 to 4.5%, particularly at least 2%, preferably 2 to 4% (weight / weight), in an aqueous medium. The pulp is thus sufficiently diluted so that the fibers of the starting material can be supplied uniformly and in a sufficiently swollen state to open them and separate the fibrils. It is also possible that the material is a fibrous material that has already undergone the same process one or more times, and from which the fibrils have already been separated. When the material is already partially gelled as a result of the preceding processing courses, the material can be run at the same relatively high consistency (in view of the gel-like state). However, you should note that thanks to the modification possibilities provided by the method (inter alia, blade density, rotation speeds and, correspondingly, peripheral speeds, impact frequencies, etc.), the consistency of the pulp to be processed can vary over a wide range, from 1 to 10%.
    [00041] Fibrous material in a given water consistency is supplied in the form described above through rotors R1, R2, R3 ... until it has been gelled and a typical viscosity of cellulose nanofibril has been reached. If necessary, processing is repeated once or several times by passing the material through the rotors again, or by means of another similar series of rotors, in which the device comprising two or more of the above-described sets of rotors can be coupled in series .
    [00042] Advantageously, the cellulose-based fibers of the pulp to be supplied are enzymatically or chemically pre-processed, for example, to reduce the amount of hemicellulose. Cellulose fibers are also chemically modified, where cellulose molecules have, in comparison with the original cellulose, other functional groups, and the internal bonds in cellulose fibers have thus been weakened; in other words, cellulose is stabilized. Such groups include, for example, carboxyl or quaternary ammonium (cationic pulp) groups. Carboxyl groups can be provided on cellulose molecules in a known manner, for example, by the oxidation of cellulose mediated by N-oxyl, an example being oxidation by the chemical "TEMPO". The fibrous raw material can also be carboxymethylated cellulose.
    [00043] As a final result, the cellulose nanofibril suspension obtained after several refining courses is a gel with strong pseudoplasticity properties. Typically, its viscosity is measured by a Brookfield viscometer. Complete fiber fibrillation occurs according to energy consumption, and the proportion of non-disintegrated parts of the fiber wall contained in the cellulose nanofibril is measured, for example, by the Fiberlab equipment.
    [00044] When refining by the method according to the invention, if necessary repeating the refining, that is, feeding the same fibrous material two or several times through the device or successively through devices coupled in series, it is possible to obtain cellulose nanofibril, in which the viscosity of the aqueous dispersion increases as a function of the specific energy (energy consumption), that is, as the specific energy used for refining increases. Consequently, the viscosity of the product and the specific energy used in the method have a positive correlation. It was also revealed that cellulose nanofibril can be obtained by refining, in which the turbidity and the content of fibrous particles decrease as a function of specific energy (energy consumption).
    [00045] Typically, in the method, the objective is to obtain, as a final product, cellulose nanofibril whose Brookfield viscosity, measured at a consistency of 0.8%, is at least 1000 mPa.s, advantageously at least 5000. It can be , for example, from pulp that was catalytically oxidized prior to refining (pulp containing carboxyl groups), for example, oxidized by N-oxyl mediation (such as the TEMPO catalyst), which satisfies said value. With the oxidized pulp as the starting material, the objective is to advantageously obtain cellulose nanofibril whose Brookfield viscosity measured at a consistency of 0.8% is at least 10,000 mPa.s, for example, between 10,000 and 20,000. In addition to the high viscosity, the aqueous dispersions of cellulose nanofibril obtained are also characterized by the so-called pseudoplasticity; that is, the viscosity decreases as the shear rate increases.
    [00046] In addition, the objective is to obtain a cellulose nanofibril whose turbidity is typically less than 80 NTU, advantageously from 20 to 60 NTU, in a consistency of 0.1% by weight (aqueous medium), measured by nephelometry.
    [00047] In addition, the objective is to obtain pseudoplastic cellulose nanofibril having a zero shear viscosity ("plateau" of constant viscosity at small shear stresses) in the range of 2,000 to 50,000 Pa.s, and a yield stress limit (shear stress where pseudoplasticity begins) in the range of 3 to 30 Pa, advantageously in the range of 6 to 15 Pa, measured at a consistency of 0.5% by weight (aqueous medium).
    [00048] In the definitions above, consistencies refer to consistencies, in which measurements are taken, and they are not necessarily consistencies of the product obtained by the method.
    [00049] Next, the test runs adopted for the invention will be discussed.
    [00050] The starting pulp was bleached birch pulp, oxidized by TEMPO using the standard method. The starting pulp load was determined by the conductometric titration, which was 1.2 mmol / g. Equipment: A: "Atrex" mixer, model G30, diameter 500 mm, 6 rotor peripheries, applied rotation speed 1500 rpm (counter-rotation rotors). M: Masuko Supermasscolloider, model MKZA10-15J F: Fluidizer, Microfluidics M110Y
    [00051] In the "Method" column, the letter indicating the device is followed by the refining consistency expressed in percent, as well as the number of runs, separated by a dot in the case of more than one run.
    [00052] The results are shown in the table below. The turbidity values were obtained by nephelometry of a sample with a consistency of 0.1%. Viscosity is Brookfield viscosity determined at a consistency of 0.8%, and a rotation speed of 10 rpm.

    [00053] The methods for measuring turbidity and viscosity will be briefly presented below. Turbidity:
    [00054] Turbidity can be measured quantitatively by optical methods that operate using two different physical measurement methods: by measuring the loss of light intensity in a sample (turbidimetry), and by measuring the emission of scattered light from particles of a sample (nephelometry).
    [00055] Cellulose nanofibril is substantially transparent in an aqueous medium. More fibrillated materials have a lower turbidity expressed in NTU units (nephelometric turbidity units). Consequently, the measurement of turbidity fits particularly well for the characterization of cellulose nanofibril. In measurements, HACH P2100 equipment was used. The sample was made by mixing an amount of product corresponding to a dry matter content of 0.5 g in water in such a way that the total amount became 500 g, after which the sample was divided into different containers of measurement for analysis. Viscosity:
    [00056] The viscosity of cellulose nanofibril was measured by the Brookfield RVDV-111 rotation viscometer, selecting a "reed axis" sensor (key 73). The product was diluted with water to a consistency of 0.8% by weight, and the sample was stirred for 10 minutes before measurement. The temperature was adjusted to the range of 20 ° C ± 1 ° C.
    [00057] Figures 5 to 7 show photomicroscopic images of samples 1022, 1023 and 1025 obtained from the execution of the test. As can be seen in the images, the product fibrillated by the method according to the invention (equipment A), sample 1022, does not differ in its appearance from samples 1023 and 1025 obtained by known reference methods.
    [00058] Thanks to its rheological properties, the resistance properties of the fibril, as well as the translucency of the products produced from it, the cellulose nanofibril obtained by the method can be applied in many uses, for example, as a rheological modifier and a viscosity regulator, and as elements in different structures, for example, as a reinforcement. Cellulose nanofibril can be used, among other things, in oil fields as a rheology modifier and a sealing agent. Likewise, cellulose nanofibril can be used as an additive in various medical and cosmetic products, as a reinforcement in composite materials, and as an ingredient in paper products. This list is not intended to be exhaustive, but cellulose nanofibril can also be applied for other uses, if it is found to have properties suitable for them.
    权利要求:
    Claims (17)
    [0001]
    1. Method for producing cellulose nanofibril, in which the fibrous cellulose-based material, in which internal bonds in the cellulose fiber have been weakened by chemical modification, are introduced into a refining interstice to separate fibrils, characterized by the fact that the material Fibrous is supplied by means of several counter-rotation rotors (R1, R2, R3 ...) that are externalized in the radial direction in relation to the rotation axis (RA) of the rotors so that the material is repeatedly subjected to forces of shear and impact by the effect of the blades (1) of the different counter-rotation rotors, according to which it is fibrillated simultaneously, in which the fibrillation is carried out by means of impact energy using a series of frequently repeated impacts having varying directions of action caused by several successive impacts from opposite directions, when the fiber material in suspension is repeatedly impacted by the blades (1) of the rotors hitting from different angles. opposite reactions when the blades rotate in opposite directions at a speed of rotation and at a peripheral speed determined by the distance to the rotor axis of rotation (R1, R2, R3 ...).
    [0002]
    2. Method according to claim 1, characterized by the fact that the fibrous material is provided with a consistency of at least 1%.
    [0003]
    Method according to claim 1, characterized by the fact that the fibrous material to be supplied is partially gelled.
    [0004]
    4. Method according to claim 1, characterized by the fact that cellulose is cellulose oxidized by N-oxyl-mediated oxidation.
    [0005]
    5. Method according to claim 1, characterized by the fact that cellulose is carboxymethylated cellulose.
    [0006]
    6. Method according to claim 1, characterized by the fact that cellulose is cationized cellulose.
    [0007]
    7. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached a Brookfield viscosity of at least minus 1,000 mPa.s, measured at a consistency of 0.8%.
    [0008]
    8. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached a turbidity value more lower than 80 NTU, measured at a 0.1% consistency.
    [0009]
    9. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached zero shear viscosity from 2,000 to 50,000 Pa.s, and a yield stress of 3 to 30 Pa, measured at a consistency of 0.5%.
    [0010]
    10. Method according to claim 1, characterized by the fact that it additionally comprises providing the rotors with blades (1), which are oriented in relation to the radius direction (r) at an angle (α1, α2) in the direction of rotation .
    [0011]
    11. Method according to claim 10, characterized by the fact that in at least one rotor (R5, R6), all blades are oriented in relation to the radius direction (r) at an angle (α1, α2) in the direction of rotation.
    [0012]
    12. Method according to claim 10, characterized by the fact that in at least one rotor (R5, R6), more than one of the blades are oriented in relation to the direction of the radius (r) at an angle (α1, α2) in the direction of rotation.
    [0013]
    13. Method according to claim 1, characterized by the fact that the fibrous material is supplied with a gaseous medium through the rotors.
    [0014]
    14. Method according to claim 1, characterized in that the fibrous material is supplied with a consistency of 2 to 4%.
    [0015]
    15. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached a Brookfield viscosity of at least minus 5,000 mPa.s, measured at a consistency of 0.8%.
    [0016]
    16. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached a turbidity value of 20 to 60 NTU, measured at a 0.1% consistency.
    [0017]
    17. Method according to claim 1, characterized by the fact that the fibrous cellulose-based material is processed by supplying it through the rotors (R1, R2, R3 ...) until it has reached zero shear viscosity from 2,000 to 50,000 Pa.s, and a yield stress of 6 to 15 Pa, measured at a consistency of 0.5%.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014011501B1|2021-03-09|method to produce cellulose nanofibril
    US10697116B2|2020-06-30|Method for producing nanofibrillar cellulose and nanofibrillar cellulose product
    US10808356B2|2020-10-20|Method and a device for producing nanofibrillar cellulose
    US10604893B2|2020-03-31|Method for producing fibrillated cellulose
    US10570564B2|2020-02-25|Method for preparing nanofibrillar cellulose
    BRPI0707255B1|2017-01-24|method for treating a chemical pulp for the manufacture of microfibrillated cellulose, microfibrillated cellulose and use
    US9909256B2|2018-03-06|Method for fibrillation of cellulose and fibril cellulose product
    US11274396B2|2022-03-15|Method for producing nanofibrillar cellulose and nanofibrillar cellulose product
    同族专利:
    公开号 | 公开日
    EP2794986A1|2014-10-29|
    CA2856151C|2020-03-24|
    US20140284407A1|2014-09-25|
    NO2794986T3|2017-12-23|
    EP2794986B1|2017-07-26|
    FI20116130A|2013-05-15|
    JP2015502462A|2015-01-22|
    FI126457B|2016-12-15|
    EP2794986A4|2015-10-07|
    WO2013072559A1|2013-05-23|
    BR112014011501A2|2017-05-09|
    CN103930615A|2014-07-16|
    JP6170061B2|2017-07-26|
    US9739011B2|2017-08-22|
    CN103930615B|2016-12-07|
    CA2856151A1|2013-05-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB379761A|1931-06-05|1932-09-05|Josef Otto|Improvements in or relating to comminuting machines|
    GB891152A|1957-11-21|1962-03-14|Peter Willems|A method and apparatus for continuously changing the structure of substances or mixtures of such substances|
    AT258691B|1962-03-02|1967-12-11|Jarmil Dipl Ing Pav|Disk mill for the continuous processing of paper stock or the like.|
    AT325396B|1973-07-05|1975-10-27|Patent Anst Baustoffe|DISINTEGRATOR|
    DE3034849C2|1980-09-16|1989-12-28|Hammona Immobilien-Anlagen Gmbh, 4700 Hamm, De|
    DE19523704C2|1995-06-29|2000-08-10|Voith Sulzer Stoffaufbereitung|Device for the mechanical treatment of highly consistent fiber|
    FI105112B|1997-01-03|2000-06-15|Megatrex Oy|Method and apparatus for defibrating fibrous material|
    US6602994B1|1999-02-10|2003-08-05|Hercules Incorporated|Derivatized microfibrillar polysaccharide|
    WO2000050462A1|1999-02-24|2000-08-31|Sca Hygiene Products Gmbh|Oxidized cellulose-containing fibrous materials and products made therefrom|
    FI120463B|2003-07-15|2009-10-30|Upm Kymmene Corp|Method of making paper and paper|
    FI20050538A0|2005-05-20|2005-05-20|Fractivator Oy|transmission arrangement|
    CN101952508B|2008-03-31|2013-01-23|日本制纸株式会社|Additive for papermaking and paper containing the same|
    FI120733B|2008-11-14|2010-02-15|Fractivator Oy|Method and apparatus for preparing finely divided calcium hydroxide|
    FI124724B|2009-02-13|2014-12-31|Upm Kymmene Oyj|A process for preparing modified cellulose|
    JP5528760B2|2009-09-30|2014-06-25|日本製紙株式会社|Paper made by adding cellulose nanofibers and method for producing the same|
    FI123289B|2009-11-24|2013-01-31|Upm Kymmene Corp|Process for the preparation of nanofibrillated cellulosic pulp and its use in papermaking or nanofibrillated cellulose composites|
    JP5881274B2|2010-02-05|2016-03-09|国立大学法人京都大学|Cationic microfibrillated plant fiber and method for producing the same|
    FI20105383A|2010-04-14|2011-10-15|Chemec Ab Oy|Process for making boards containing wood chips|
    WO2014045209A1|2012-09-20|2014-03-27|Stora Enso Oyj|Method and device for defibrating fibre-containing material to produce micro-fibrillated cellulose|US20130000856A1|2010-03-15|2013-01-03|Upm-Kymmene Oyj|Method for improving the properties of a paper product and forming an additive component and the corresponding paper product and additive component and use of the additive component|
    FI122889B|2010-12-31|2012-08-31|Upm Kymmene Corp|Method and apparatus for preparing nanocellulose|
    WO2014045209A1|2012-09-20|2014-03-27|Stora Enso Oyj|Method and device for defibrating fibre-containing material to produce micro-fibrillated cellulose|
    WO2015007953A1|2013-07-16|2015-01-22|Stora Enso Oyj|A method of producing oxidized or microfibrillated cellulose|
    FI127124B2|2013-12-05|2021-02-15|Upm Kymmene Corp|Method for making modified cellulose products and modified cellulose product|
    FI126042B|2014-03-31|2016-06-15|Upm Kymmene Corp|Process for the manufacture of nanofibrillar cellulose and nanofibrillar cellulose product|
    FI127716B|2014-03-31|2018-12-31|Upm Kymmene Corp|A method for producing fibrillated cellulose|
    ES2772850T3|2014-05-07|2020-07-08|Univ Maine System|High-efficiency production of nanofibrillated cellulose|
    FI126688B|2014-06-30|2017-03-31|Upm-Kymmene Corp|Method and apparatus for controlling the quality of nanofibrillar cellulose|
    FI127904B|2014-08-13|2019-05-15|Upm Kymmene Corp|Method for preparing nanofibrillar cellulose|
    US9822285B2|2015-01-28|2017-11-21|Gpcp Ip Holdings Llc|Glue-bonded multi-ply absorbent sheet|
    EP3303404A4|2015-06-04|2019-01-23|GL&V Luxembourg S.à.r.l.|Method of producing cellulose nanofibrils|
    SE540016E|2015-08-27|2020-11-13|Stora Enso Oyj|Method and apparatus for producing microfibrillated cellulose fiber|
    US10774476B2|2016-01-19|2020-09-15|Gpcp Ip Holdings Llc|Absorbent sheet tail-sealed with nanofibrillated cellulose-containing tail-seal adhesives|
    US20180243750A1|2017-02-24|2018-08-30|Greenvolt LTD|Apparatus and method for forming nanoparticles|
    US11154868B2|2017-02-24|2021-10-26|Greenvolt Nano Inc.|Apparatus and method for forming nanoparticles|
    RU2637216C1|2017-02-27|2017-12-01|федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова"|Disintegrator|
    EP3453798A1|2017-09-07|2019-03-13|Borregaard AS|Inline dilution of microfibrillated cellulose|
    WO2019132001A1|2017-12-28|2019-07-04|日本製紙株式会社|Paper containing cellulose nanofibers|
    FI20185143A1|2018-02-16|2019-08-17|Upm Kymmene Corp|A method for the treatment of calcium-containing solid side stream material|
    FI20185144A1|2018-02-16|2019-08-17|Upm Kymmene Corp|A method for the treatment of biosludge|
    RU2677168C1|2018-04-04|2019-01-16|федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова"|Disintegrator|
    RU2688409C1|2018-11-06|2019-05-21|федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова"|Disintegrator|
    US11124920B2|2019-09-16|2021-09-21|Gpcp Ip Holdings Llc|Tissue with nanofibrillar cellulose surface layer|
    CN113728138A|2019-09-17|2021-11-30|日本制纸株式会社|Method for producing chemically modified microfibrillar cellulose fiber|
    RU2727296C1|2020-01-17|2020-07-21|федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова"|Disintegrator|
    US20210348332A1|2020-05-11|2021-11-11|Suzano S.A.|Process to produce microfibrillated cellulose by impacts|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-02-17| B09A| Decision: intention to grant|
    2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20116130A|FI126457B|2011-11-14|2011-11-14|Method for producing fibril pulp|
    FI20116130|2011-11-14|
    PCT/FI2012/051116|WO2013072559A1|2011-11-14|2012-11-14|A method for producing nanofibril cellulose|
    [返回顶部]