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    • 专利摘要:
    METHOD TO PRODUCE HIGH ASPECT ASPECT CELLULOSE NANOFILAMENTS, COMPOSITION, REINFORCEMENT AGENT, SUBSTRATE, FILM OR COATING, AND USE OF A MASS. An unprecedented method is described to produce, on a commercial scale, high-aspect ratio (CNF) cellulose nanofilaments from natural lignocellulosic fibers. The method consists of a high consistency multi-pass refining (HCR) of chemical or mechanical fibers using specific combinations of refining intensity and specific energy. The CNF produced by this invention represents a mixture of thin filaments with sub-micron widths and lengths of tens of micrometers to a few millimeters. The resulting product is made from a population of free filaments and filaments attached to the fiber core from which they were produced. The proportion of free and bonded filaments is governed, in large part, by the total specific energy applied to the pulp at the refinery. These CNF products differ from other fibrillar cellulose materials due to their higher aspect ratio and the conserved degree of polymerization (DP) of cellulose. The CNF products made by this invention are excellent additives for the reinforcement of paper, fabric, cardboard and packaging products, plastic composite materials and formulations of (...).
    公开号:BR112013018408B1
    申请号:R112013018408-6
    申请日:2012-01-19
    公开日:2020-12-29
    发明作者:Xujun Hua；Makhlouf Laleg；Keith Miles；Reza Amiri；Lahoucine Ettaleb；Gilles Dorris
    申请人:Fpinnovations；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] This invention relates to an unprecedented method of producing, on a commercial scale, high aspect ratio cellulose nanofilaments from natural fibers, such as wood or agricultural fibers using high consistency refining (HCR). TECHNICAL FUNDAMENTALS
    [0002] Chemical pulp fibers subjected to bleaching and not subjected to bleaching processed from resistant wood and coniferous wood have traditionally been used to manufacture paper, cardboard, fabric and molded pulp products. In order to reduce the production cost of publication paper grades, such as newsprint, supercalendered paper or light weight coated paper, chemical pulp has been progressively replaced in recent decades by mechanical wood pulps or recovered paper. With the decline in paper grades in the publication, in North America in particular, the amount of mechanical pulp produced and used in paper has decreased substantially, while the proportion of chemical pulp from coniferous wood in many grades of paper continues to fall equally because modern paper machines are designed to process weaker pulps and require less chemical coniferous wood pulp, which is the cheapest component of a paper load. However, mechanical and chemical pulp fibers have unique properties that find more and more uses in areas other than papermaking. Environmental and climatic changes make the use of natural wood fiber, a significantly planet friendly choice over materials based on traditional fossils and other non-renewable materials. Although the green movement is expected to increase consumer demand for fiber-based materials and products, these products must at least meet the performance of existing non-renewable products at a competitive price. Recently, some manufacturers have used wood and plant fibers to replace artificial fibers, such as glass fibers as reinforcement material for plastic composites because they have desirable attributes, such as low density and abrasiveness, high specific strength and hardness and a high aspect ratio (length / diameter).
    [0003] A single fiber is made up of long straight polymer chains of cellulose embedded in a matrix of lignin and hemicellulose. The cellulose content depends on the source of the fiber, as well as the pulping process used to extract fibers, ranging from 40 to almost 100% for wood fiber fibers and some plants such as sisal, hemp and cotton. Cellulose molecule that forms the backbone of micro and nanofibrils is a straight polydispersed homopolymer of β (1, 4) -D glucose. The strength properties of natural fibers are strongly related to the higher degree of polymerization (DP) of cellulose. For example, the DP of native cellulose can be up to 10,000 for cotton and 5,000 for wood. Depending on the severity of the thermochemical cooking and thermomechanical pre-treatment during the defibrillation process, the cellulose DP values in papermaking fibers typically vary between 1500 and 2000, while the DP for cotton is around 3000. Cellulose in the dissolution of pulps (used to prepare regenerated cellulose fiber) have an average DP of 600 to 1200. The caustic treatment in the subsequent dissolution process still reduces the DP to about 200. Nanocrystalline cellulose has a DP of 100-200 due to acid hydrolysis in the process of variation of the crystalline portion of the cellulose.
    [0004] Although the intrinsic strength of the fibers is important, as discussed earlier, basic fiber physics prescribes that a high aspect ratio is one of the key criteria for reinforcement purposes by virtue of promoting the connectivity or degree of bonding of a sheet continuous percolation which, in turn, improves its mechanical properties. Plant fibers such as hemp, flax, sisal, jute and cotton are long and have aspect ratios that typically range from 100 to 2000. On the other hand, wood fibers tend to be shorter than these plant fibers and have a minor aspect ratio. For example, the dimensions of the wood fibers commonly used to manufacture paper products are: 0.5 mm <length <5 mm and 8 pm <width <45 pm Thus, even longer coniferous wood fibers have a very high aspect ratio smaller compared to these plant fibers, but superior to the resistant wood fibers. It is well known that short wood fibers, such as resistant wood fibers, produce lower reinforcing strength in a continuous sheet of paper than wood fibers or long flax or hemp plant fibers. In addition, the strength of reinforcement of ordinary wood fibers including coniferous wood fibers is less than fibers for the reinforcement of plastic composites.
    [0005] The reinforcing performance of wood and other plant fibers for the manufacture of paper products and plastic composites can be substantially better when their aspect ratio (length / diameter) is increased while the degree of polymerization (DP) of its cellulose chain is minimally altered during treatment. Thus, fibers should ideally be processed in such a way that their diameter is reduced as much as possible during treatment, but with minimal breakage along the fiber axis and concurrently preventing cellulose chain degradation at the molecular level. Reduction in the fiber diameter is possible because the cellulose fiber morphology represents a well-organized architecture of very thin fibrillar elements that is formed by long strands of cellulose chains stabilized laterally by hydrogen bonds between adjacent molecules. Elementary fibrils aggregate to produce micro and nanofibrils that make up the majority of the fiber cell wall (A.P. Shchniewind in Concise Encyclopedia of Wood & Wood-Based Materials, Pergamon, Oxford, p.63 (1989)). Microfibrils are defined as thin cellulose fibers of 0.1 -1 μm in diameter, while nanofibrils have a dimension on the nanometer scale (<100 nm). Cellulose structure with a high aspect ratio is obtained from the hydrogen bonds between these fibrils and can be selectively destroyed to release micro and nanofibrils without shortening them. It will be shown that current methods of extracting cellulose superstructures do not allow to achieve these objectives.
    [0006] Various methods have been described to produce valuable cellulose or agricultural supramolecular cellulose structures. The variety of acronyms for these structures, as well as their description, production method and applications were described and analyzed in the previous patent application (US 201 1 -0277947, published on November 17, 2011). The various families of cellulosic materials differ from each other by the relative quantity of free and bonded fibrillar elements in the resulting products, their composition in terms of cellulose, lignin and hemicellulose, the distribution of length, width, aspect ratio, surface load, area specific surface, degree of polymerization and crystallinity. The structures twisted from the original fiber under the smallest and strongest element of the natural fibers, nanocrystalline cellulose (NCC). Due to their market potential, several methods have been proposed to produce fibrillar cellulose elements of intermediate sizes between precursor fibers and NCC (US 4,374,702, US 6,183,596 & US 6,214,163, US 7,381,294 & WO 2004/009902 , US 5,964,983, WO2007 / 091942, US 7,191,694, US 2008/0057307, US 7,566,014). Various names have been used to describe fibrillated fibers, namely microfibrillated cellulose, super-microfibrillated cellulose, cellulose microfibrils, cellulose nanofibrils, nanofibers, nanocellulose. They involve most mechanical treatments with or without the help of enzymes or chemicals. Chemicals used before mechanical treatment are claimed to help reduce energy consumption (WO2010 / 092239A1, WO201 / 064441 A1).
    [0007] Mechanical methods of producing cellulose nanofibrils are generally carried out using high shear homogenizers, low consistency refineries or a combination of both. There are two main problems with existing methods: the relatively low aspect ratio after treatment limits the benefits associated with the use of such fibrillar structures in some matrices. In addition, production methods are not amenable to an easy and economical increase. Of particular relevance to the present patent application is the work of Turbak (US 4,374,702) for the production of microfibrillated cellulose using a homogenizer. Homogenizers require pre-cutting the fiber to pass through the small hole, which reduces the length of the fiber and thus the aspect ratio. In addition, repeated passes of the pre-cut fibers through one or a series of homogenizers inevitably promote additional fiber cutting, thus preventing high aspect ratio cellulose fibrils from being produced by this approach. Suzuki et al. (US 7,381,294) avoided the use of homogenizers to produce microfibrillated cellulose, but used instead, low consistency refining of multiple passages of resistant wood kraft pulp. The resulting microfibrilated cellulose consists of shortened fibers with a dense continuous sheet of fibrils still attached to the fiber core. Again, as homogenizers, refineries operated at low consistency cause severe fiber cutting, which prevents the formation of high aspect ratio fibrils. To reduce energy consumption, Lindstrom et al. (WO2007 / 091942), proposed an enzymatic treatment before homogenization, but this treatment attacks the macromolecular cellulose chains and also decreases the length of the fibril. The resulting fibril material, called nanocellulose or nanofibrils, had a width of 2-30 nm and a length of 100 nm at 1 pm, for an aspect ratio of less than 100. In general, observations made on a laboratory and pilot scale, as well as results from the literature all indicate that the treatment of the pulp fibers with enzymes before any mechanical action accentuates the fiber cut and reduces the degree of polymerization of the cellulose chains.
    [0008] In summary, the products mentioned above, MFC, nanocellulose or nanofibrils, are relatively short particles of low aspect ratio and degree of polymerization (DP) compared to the original pulp fibers from which they were produced. They are usually much shorter than 100 pm and some may be even shorter than 1 pm. Thus, in all the methods proposed to date to produce microfibrils or nanofibrils, the pulp fibers have to be cut to be processable through a small hole in a homogenizer or inevitably shortened by mechanical, enzymatic or chemical actions.
    [0009] More recently, Koslow and Suthar (US 7,566,014) described a method of producing fibrillated fibers using open channel refining in low consistency pulps (i.e., 3.5% solid, by weight). They claim that the open channel refining preserves the length of the fiber, while the closed channel refining, such as a disc refinery, shortens the fibers. In their subsequent patent application (US 2008/0057307), the same inventors even described a method for producing nanofibrils with a diameter of 50-500 nm. The method consists of two steps: first using open channel refining to generate fibrillated fibers without shortening, followed by closed channel refining to release the individual fibrils. Although the claimed length of the released fibrils is still the same as the starting fibers (0.1-6 mm), this is an unrealistic claim because the closed channel refining inevitably shortens the fibers and fibrils as indicated by the inventors in itself and by other descriptions (US 6,231,657, US 7,381,294). The closed refining of the inventors by Koslow et al refers to the commercial mixer, disc refining and homogenizers. These devices were used to generate microfibrillated cellulose and nanocellulose in other earlier technologies mentioned above. None of these methods generate detached nanofibrils with such a high length (above 100 micrometers). Koslow et al. recognize in US 2008/0057307 that a closed channel refining leads to both fibrillation and reduction in fiber length and generates a significant amount of fines (short fibers). Thus, the aspect ratio of these nanofibrils should be similar to those in the prior art and thus relatively low. In addition, the method by Koslow et al. is that fibrillated fibers entering the second stage have a freedom of 50 - 0 ml of CSF, while the resulting nanofibers still have a freedom of zero after refining the closed channel or homogenization. A freedom of zero indicates that the nanofibrils are much larger than the screen size of the freedom tester and cannot pass through the holes in the screen, thus quickly forming a fibrous screen in the screen that prevents water from passing through the screen (the amount of past water is proportional to the value of freedom). Due to the screen size of a freedom tester it has a diameter of 510 micrometers, it is obvious that the nanofibers must have a width greater than 500 nm.
    [00010] Previously it was found that (US 2011 -0277947) long fibril cellulose chains with a high aspect ratio can be generated by a nanofilament device that involves peeling the fibrils from the plant fibers with a set of pointed knives that rotate in very high speed. This approach generates high quality cellulose nanofilaments (CNF) of very high aspect ratios (up to 1000). Unlike Koslow's nanofibrils, the CNF in an aqueous suspension has a very high freedom value, typically greater than 700 mL of CSF, due to the CNF's narrow width and shorter length in relation to the precursor fibers. However, a disadvantage of the rotary knife method is that the resulting CNF is too diluted (ie less than 2% on a weight basis) to be transported right after processing. In addition, a very diluted suspension of CNF limits its incorporation into products as composites that require little or no water during manufacture. Thus, a drying step may be required with this approach, which makes economizing the method difficult.
    [00011] The novel method of the present invention is based on the high consistency refining of the pulp fibers. High consistency here refers to a discharge consistency greater than 20%. High consistency refining is widely used for the production of mechanical pulps. Refineries for the production of mechanical pulp consist of both a combination of a rotating-stationary disc (single disc) and two opposing rotating discs (double disc), operated in atmospheric conditions (ie, open discharge) or pressure (closed discharge). The surface of the discs is covered by plates with a particular pattern of bars and notches. The wood chips are fed into the center of the refinery. Refining not only separates the fibers, but also causes a variety of simultaneous changes in the fiber structure, such as internal and external fibrillation, fiber waviness, fiber shortening and generation of fines. External fibrillation is defined as the breaking and stripping of the fiber surface leading to the generation of fibrils that are still attached to the surface of the fiber core. Fiber fibrillation increases its surface area, thus improving its bonding potential in papermaking.
    [00012] Mechanical refineries can also be used to improve the properties of chemical pulp fibers, such as kraft fibers. The conventional refining of the chemical pulp is carried out at a low consistency. Low-consistency refining promotes fiber cutting in the early stages of production. Moderate fiber cutting improves the uniformity of the paper made from it, but is undesirable for the manufacture of high-aspect cellulose superstructures. High consistency refining is used in some kraft pulp applications, for example, for the production of sack paper. In such applications of kraft pulp refining, the applied energy is limited to a few hundred kWh per ton of pulp because the application of energy above this level can drastically reduce the length of the fiber and make the fibers unsuitable for the applications. Kraft fibers have never been refined to an energy level above 1000 kWh / t in the past.
    [00013] Miles described that, in addition to the high consistency, a low refining intensity still conserves the fiber length and produces high quality mechanical pulps (US 6,336,602). The lowest refining intensity is achieved by decreasing the speed of rotation of the disc. Ettaleb et al. (US 7,240,863) described a method of improving pulp quality by increasing the consistency of incoming pulp in a conical refinery. The superior inlet consistency also reduces the refining intensity, so it helps to reduce the fiber cut. The products of both methods are fiber materials for papermaking. There has never been any attempt to produce cellulose microfibers, microfibrillated cellulose, cellulose fibrils, nanocellulose or cellulose nanofilaments using high consistency and / or low intensity refining. DESCRIPTION OF THE INVENTION
    [00014] This invention seeks to provide high-aspect ratio (CNF) cellulose nanofilaments.
    [00015] This invention also seeks to provide a method of producing high-aspect ratio (CNF) cellulose nanofilaments.
    [00016] Still this invention seeks to supply products based on or containing the high aspect ratio (CNF) cellulose nanofilaments.
    [00017] In one aspect of the invention, a method is provided for producing high-aspect ratio (CNF) cellulose nanofilaments, comprising: refining the pulp fibers at a high total specific refining energy under conditions of high consistency. In a particular mode, refining is at a low refining intensity.
    [00018] In another aspect of the invention, a mass of refined cellulose nanofilaments per high-aspect ratio (CNF) disc is provided, comprising cellulose nanofilaments (CNF) having an aspect ratio of at least 200 to a few thousand and one width from 30 nm to 500 nm.
    [00019] Yet another aspect of the invention is provided with a film formed from the mass of high aspect ratio (CNF) cellulose nanofilaments of the invention.
    [00020] Yet another aspect of the invention provides a substrate reinforced with the mass of the high aspect ratio (CNF) cellulose nanofilaments of the invention.
    [00021] In a further aspect of the invention there is provided a composition comprising a mass of high-aspect ratio (CNF) disc-refined cellulose nanofilaments, wherein said cellulose nanofilaments (CNF) comprise uncut filaments that retain the length of the filaments in the non-disc refined precursor fibers.
    [00022] In a further aspect of the invention, a reinforcing agent comprising the mass or composition of the invention is provided.
    [00023] Yet a further aspect of the invention is provided a film or coating formed from the mass or composition of the invention.
    [00024] In this specification the term CNF "refined to disk" refers to CNF made by refining on disk to a refining on disk; and the term "non-disc refined" refers to precursor fibers prior to disc refining in a disc refining to produce CNF.
    [00025] The CNF aspect ratio in this invention will be up to 5,000, that is, 200 to 5,000 and typically 400 to 1,000. DETAILED DESCRIPTION OF THE INVENTION
    [00026] An unprecedented method of producing high-aspect ratio (CNF) cellulose nanofilaments has been developed. It consists of refining cellulose fibers at a very high level of specific energy using disc refines that operate at a high consistency. In a particular mode, refining is at a low refining intensity.
    [00027] The key element of this invention is a unique combination of refining technologies, high consistency refining and preferably low intensity refining to apply the energy required for the production of high aspect ratio CNF using commercially available refining chips. A plurality, preferably several steps, are necessary to achieve the required energy level. The high consistency refining can be atmospheric or pressurized refining.
    [00028] Thus the present invention provides an unprecedented method for preparing a family of fibrils or cellulose filaments that have superior characteristics compared to all other cellulosic materials, such as MFC, nanocellulose or nanofibrils described in the previous technologies mentioned above, in terms of aspect ratio and degree of polymerization. The cellulosic structures produced by this invention, namely cellulose nanofilaments (CNF), consist of a distribution of fibrillary elements of very high length (up to millimeters) compared to materials denoted as microfibrillated cellulose, microfibril celluloses, nanofibrils or nanocellulose. Their widths vary from nano size (30 to 100 nm) to micro size (100 to 500 nm).
    [00029] The present invention also provides an unprecedented method that can generate cellulose nanofilaments in a high consistency, at least 20% by weight and typically 20% to 65%.
    [00030] The present invention further provides an unprecedented method of producing CNF that can be easily represented up to mass production. Furthermore, the unprecedented method of producing CNF according to the present invention can use the existing commercially available industrial equipment in such a way that the capital cost can be reduced substantially when the method is commercialized.
    [00031] The CNF manufacturing process according to the present invention has a much less negative effect on the length of DP fibril and cellulose than the methods proposed to date. The unprecedented method described here differs from all other methods in that it identifies the unique set of process conditions and refining equipment in order to avoid cutting the fiber despite the high energy given to the wood pulps during the process. The method consists of refining pulp fibers at a very high level of specific energy using high consistency refineries and preferably operating at low refining intensity. The total energy required to produce CNF varies between 2,000 and 20,000 kWh / t, preferably 5,000 to 20,000 kWh / t and more preferably 5,000 to 12,000 kWh / t, depending on the fiber source, percentage of CNF and the targeted fineness of CNF in the final product . As the applied energy is increased, the percentage of CNF increases, the filaments become progressively thinner. Typically, several steps are required to achieve the required energy level. In addition to the target energy level, the number of passes also depends on the refining conditions, such as consistency, speed of rotation of the disc, clearance and the size of the refining used, etc., but is usually greater than two but less than fifteen for atmospheric refining. and less than 50 for pressurized refining. The specific energy per step is adjusted by controlling the gap in the plate. The maximum energy per pass is imposed by the type of refinery used in order to achieve operating stability and achieve the required quality of CNF. For example, experiments carried out using a 36 ”double disk refining that runs at 900 RPM and 30% consistency demonstrated that it was possible to apply energy in excess of 15,000 KWh / ton in less than 10 passes.
    [00032] CNF production on a commercial scale can be continuous across a series of refineries aligned in series to allow multiple pass refining or can be performed in batch mode using one or two refines in series with the refined material being recirculated many times to reach the target energy.
    [00033] Low intensity refining is achieved by controlling two parameters: increasing the refining consistency and reducing the rotation speed of the disc. Changing the speed of rotation of the refining disc (RPM) is by far the most effective and practical approach. The range of RPM to achieve low intensity refining is described in the previous U.S. patent (US 6,336,602). In the present invention, use of double disc refiners requires that one or both discs be rotated at less than 1200 RPM, usually 600 to 1200RPM and preferably at 900 RPM or less. For single disc refining, the disc is rotated at less than the conventional 1800 RPM, usually 1200 to 1800 RPM, preferably at 1500 or less RPM.
    [00034] High discharge consistency can be achieved in both atmospheric and pressurized refining. Pressurized refining increases the temperature and pressure in the refining zone and is used to soften the lignin in the chips, which facilitates the separation of the fiber in the first stage when wood chips are used as raw material. When the raw material is chemical kraft fibers, pressurized refining is generally not necessary because the fibers are already very flexible and separated. The inability to apply a sufficient amount of energy to the kraft pulp is a major limitation to using a pressurized refining. In the present pilot plant, experiments to prepare CNF with a pressurized refining were conducted and the specific energy per maximum pass that it was possible to apply to the kraft fibers before the run in the operation instability was around 200kWh T only. On the other hand, it was possible to reach 1500kWh / T and above with low intensity atmospheric refining. Consequently, the use of pressurized refining to produce CNF can lead to a greater number of passes than atmospheric refining to achieve the specific target refining energy. However, pressurized refining allows the recovery of steam energy generated during the process.
    [00035] High consistency here refers to a discharge consistency that is greater than 20%. The consistency will depend on the type and size of the refinery used. Small double disc refiners operate in the lower range of high consistency, while in large modern refineries the discharge consistency can exceed 60%.
    [00036] Wood cellulose fibers and other plants represent raw material for the production of CNF according to the present invention. The method of the present invention allows CNF to be produced directly from all types of wood pulp without pre-treatment: kraft, sulfite, mechanical pulps, chemothermo-mechanical pulps, whether they are subjected to bleaching, semi-bleached or not subjected to bleaching. Wood chips can also be used as starting material. This method can be applied to other plant fibers as well. Whatever the source of natural fibers, the resulting product is made up of a population of free filaments and filaments attached to the fiber core from which they were produced. The proportion of free and bonded filaments is governed in large part by the total specific energy applied to the pulp in the refining. Both free and bonded filaments have an aspect ratio superior to the microfibrillated cellulose or nanocellulose described in the prior art. The lengths of the present CNF are typically over 10 micrometers, for example, over 100 micrometers and even millimeters, yet they can have very narrow widths, around 30 - 500 nanometers. In addition, the method of the present invention does not significantly reduce the DP of the cellulose source. For example, the DP of a CNF sample produced in accordance with this invention was almost identical to that of the starting coniferous wood kraft fibers which was around 1700. As will be shown in the subsequent examples, the CNF produced according to this invention it is extraordinarily efficient for reinforcing paper, fabric, cardboard, packaging, plastic composite products and coating films. This reinforcing force is superior to the many commercially available water-soluble or aqueous emulsions of polymeric reinforcing agents including starches, carboxymethyl cellulose and synthetic polymers or resins. In particular, the improvement in resistance induced by the incorporation of high aspect ratio filaments in continuous sheets of paper is never accentuated.
    [00037] The CNF materials produced in accordance with this invention represent a population of cellulose filaments with a wide range of diameters and lengths as previously described. The average length and width can be changed by the appropriate control of the specific energy applied. The described method allows the pulp to pass more than 10 times at more than 1500 kWh / t per pass in high consistency refining without experiencing severe cutting of the fiber that is associated with low consistency refineries, crushers or homogenizers. The CNF product can be shipped as is in a semi-dry form or used on the spot after simple dispersion without any further treatment.
    [00038] The CNF product made in accordance with this invention can be dried before being distributed to customers to save the cost of transportation. The dry product must be redispersed with a constitution system before use. If desired, CNF can also be treated or impregnated with chemicals, such as bases, acids, enzymes, solvents, plasticizers, viscosity modifiers, surfactants or reagents to promote additional properties. Chemical treatment of CNF can also include chemical modifications to surfaces to charge certain functional groups or change the hydrophobicity of the surface. This chemical modification can be carried out either by chemical bonding or by adsorption of functional groups or molecules. The chemical bond can be introduced by existing methods known to those skilled in the art or by proprietary methods, such as those described by Antal et al. (US 6,455,661 and 7,431,799).
    [00039] A decisive advantage of this invention is finally the possibility of achieving a much higher production rate of CNF than with the equipment and devices described in the section of the prior art to produce microfibrillated or nanofibrillary cellulose materials. Although the manufacture of CNF can be carried out in an unprecedented shredder designed for this purpose, the present method offers a unique opportunity to recover countless lines of mechanical pulp in shredders that have been inactive due to the sharp decline of the publication's paper grades market, such as newsprint. Production on a commercial scale can be done using existing high consistency refineries in both atmospheric and pressurized modes.
    [00040] Although it is not intended to be bound by any particular theory with respect to the present invention, the mechanism for generating CNF using the present method should be summarized as follows:
    [00041] Although low consistency refining is the conventional method of developing the properties of kraft pulp, this process limits the amount of energy that can be applied and adversely affects the length of the fiber. In high consistency the mass and, thus, the amount of fiber in the refining zone is much greater. For a given motor load, the shear force is distributed over a much larger surface area of the fiber. The shear stress in the individual fibers is thus very reduced with much less risk of damage to the fiber. Thus, much more energy can be applied. Since the energy requirements for the production of CNF are extremely high and the preservation of the fiber length is essential, high consistency refining is necessary.
    [00042] As mentioned earlier, pressurized refining limits the amount of energy that can be applied in a single pass when compared to atmospheric refining. This is due to the fact that the pressurized refining leads to a much greater gap in the plate, a consequence of the thermal softening of the material at a temperature above which it is exposed in the pressurized process. What's more, kraft fiber, in particular, is already flexible and compressible which further reduces the slack in the board. If the plate gap is too small, it is difficult to evacuate the steam, it is difficult to load the refinery and the operation is unsustainable.
    [00043] Finally, at a given energy, Miles (US 6,336,602) prescribes that when low intensity refining is achieved by reducing the speed of rotation of the disc, the residence time of the pulp in the refining zone increases, resulting in a better mass of the fiber to carry the applied load. As a consequence, a higher motor load and thus more energy can be applied without damaging the fiber. This is well illustrated by comparing the results obtained in the present pilot plants in low intensity refining and conventional refining of kraft pulp. With the increase in specific energy, the long fiber fraction decreases very fast with conventional refining than with low intensity refining (Figure 1). This makes low intensity refining the preferred method for the production of CNF with a high aspect ratio. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1: Comparison of the fraction of long fiber (Bauer McNett R28) after conventional and low intensity refining of a kraft pulp submitted to bleaching. Figure 2: SEM photomicrography of the cellulose nanofilaments produced in the high consistency refining using coniferous kraft pulp submitted to bleaching. Figure 3: Microscopic photomicrograph of cellulose nanofilaments produced in the high consistency refining using coniferous kraft pulp subjected to bleaching as in figure 2. Figure 4: (a) SEM SEM micrograph of the CNF film, (b) SEM micrograph of superior amplification of CNF film and (c) force-elongation curve of CNF sheet. Figure 5: Tensile strength (a) and PPS porosity (b) of sheets made of BHKP combined with both refined BSKP and CNF. Figure 6: Comparison of CNF with commercial MFC in terms of reinforcement of wet continuous sheet. Figure 7: Photomicrographs of cellulose nanofilaments produced in high-consistency refining using mechanical pulp. Figure 8: Comparison of Scott binding of leaves made with and without CNF of chemical and mechanical pulps, respectively. Figure 9: Comparison of length in the breaking of leaves made with and without CNF of chemical and mechanical pulps, respectively. Figure 10: Comparison of tension energy absorption (TEA) of sheets made with and without CNF made from chemical and mechanical pulps, respectively. EXAMPLES
    [00044] The following examples help to understand the present invention and to carry out the method of producing said cellulose nanofilaments and the application of the product as a reinforcement additive for paper. These examples should be taken as illustrative and should not limit the scope of the invention. Example 1:
    [00045] CNF was produced from a coniferous kraft pulp submitted to bleaching using a 36 ”double disc refining with a Bauer 36104 disc pattern and running at 900 RPM and 30% consistency. Figure 2 shows electron scanning microscopy (SEM) image of CNF done this way after 8 passes. Figure 3 is the corresponding micrograph using microscopy. The high aspect ratio of the material is clearly visible. Example 2:
    [00046] CNF produced from coniferous kraft pulp subjected to bleaching of example 1 was dispersed in water at 2% consistency in a British standard laboratory disintegrator (TAPPI T205 sp-02). The dispersed suspension was used to prepare 100 µm thick melted films. The air-dried leaf was semi-transparent and rigid with a specific density of 0.98 g / cm3 and an air permeability of zero (as measured by a standard PPS porosity meter). Figure 4a and Figure 4b show SEM micrographs of the CNF film at two levels of amplification. The CNF formed a film-like microstructure, well connected with tangled filaments.
    [00047] Figure 4c shows the load-voltage curve measured on an Instron test equipment at a crosshead speed of 10 cm / min using a strip measuring 10 cm long x 15 mm wide x 0.1 mm thickness. The tensile strength and stretching at the break point were 168 N and 14%, respectively. Example 3:
    [00048] Figure 5a and Figure 5b compare the properties of 60 g / m2 handmade sheets made from kraft pulp subjected to resuspended dry fold resistant (BHKP) bleaching combined with various levels of a coniferous kraft pulp subjected to refined bleaching in a crusher (BSKP) or CNF produced according to this invention using the same procedure described in example 1. BSKP refined with a 400 mL Canadian standard CSF was received from a crusher that produces copy and degrees of fine offset paper. All leaves were made with the addition of 0.02% cationic polyacrylamide as a retention aid. The results clearly show that by increasing the CNF dosage, the tensile strength (a) is drastically increased and the PPS porosity (b) is drastically reduced. A low PPS porosity value corresponds to very low air permeability. Comparing CNF with crushed refined BSKP, the CNF reinforced sheet was 3 times stronger than BSKP reinforced sheet. Example 4:
    [00049] A CNF was produced according to this invention from a coniferous kraft pulp submitted to bleaching after 10 passages in HCR operated at 30% consistency. This product was first dispersed in water using a British standard laboratory disintegrator (TAPPI T205 sp-02) and then added to a thin paper piece containing 25% bleached coniferous wood and 75% hardwood kraft pulps submitted to bleaching to produce 60 g / m2 hand sheets containing 10% CNF of this invention and 29% precipitated calcium carbonate (PCC). Manual control sheets were also made with PCC only. For all leaves, a 0.02% amount of cationic polyacrylamide was used to aid retention. Figure 6 shows the tensile strength of wet web as a function of web solids. Clearly, in the addition of PCC alone to the pulp furniture a drastic reduction in the resistance of the wet continuous sheet was measured compared to the control sheet without PCC. The introduction of 10% commercial MFC slightly improved the strength of the wet continuous sheet of the filled sheet, while an addition of 10% CNF substantially improved the strength of the wet continuous sheet of the PCC-filled sheet and the strength was even greater than the unfilled control sheet. This illustrates that the CNF produced in accordance with the present invention is a super reinforcing agent for never dry moisture sheet.
    [00050] The tensile strength of dry leaves containing CNF has also been significantly improved. For example, the sheet containing 29% PCC had a strain energy absorption index (TEA) of 222 mJ / g in the absence of CNF. When CNF was added to the paper load before preparing the sheet at a dosage of 10%, the TEA was improved at 573 mJ / g, an increase of 150%. Example 5:
    [00051] Experiments were also carried out with splinters of black fir wood as raw material. In these experiments, the first refining stage was done with a 22 ”pressurized refining running at 1800 RPM using the Andritz D17C002 plate pattern. The consecutive refining stages were carried out with the Bauer 36 ”atmospheric refining under the same conditions described in example 1. Figure 7 shows SEM and optical images of CNF produced with mechanical pulps after a pressurized refining stage of the black fir flakes followed by 12 consecutive atmospheric refining stages. Example 6:
    [00052] The CNF produced from black fir wood chips following the same procedure as example 5. The CNF was disintegrated according to the PAPTAC standard (C-8P) then still disintegrated for 5 min in a standard British disintegrator laboratory (TAPPI T205 sp-02). The well dispersed CNF was added at 5% (based on weight) to the base kraft mixture which contained 20% coniferous kraft pulp submitted to northern bleaching, refined to 500 mL of freedom and 80% kraft pulp eucalyptus tree subjected to unrefined bleaching. Standard laboratory hand sheets were made from the final blend of the base kraft and the CNF. For comparison, a similar mixture was also made with 5% CNF produced from a chemical pulp, instead of mechanical pulp. Dry resistance properties were measured on all leaves. Figures 8, 9 and 10 clearly show that adding 5% CNF significantly increased the resistance to the internal bond (Scott bond), length in the break and absorption of voltage energy. The CNF made with wood chips and mechanical pulp had a lower reinforcement performance than those made from chemical pulp. However, they still significantly increased the resistance properties of the leaf when compared to the sample made without any addition of CNF (control). Example 7:
    [00053] More than 100 kg of cellulose nanofilaments were produced from a coniferous kraft pulp subjected to bleaching in accordance with the present invention. This CNF was used in a pilot paper machine experiment to validate the present laboratory findings in improving the wetted sheet resistance by CNF. The machine was run at 800 m / min using a typical thin paper piece made up of 80% BHKP / 20% BSKP. 75 g / m2 paper weight containing up to 27% PCC was produced in the absence and presence of 1 and 3% CNF dosages. During the experiment, drag tests were carried out to determine the resistance of the wet web to breaking due to the higher tension of the web. In this test, the web tension was gradually increased, increasing the speed difference between the pinch of the third press and the 4th press where the web was not supported by press printing (open drag). A high drag at the web break point reflects a strong wet web that can lead to the good running capacity of the paper machine. The results of the drag test indicated that CNF increased the drag substantially from 2% to more than 5%. This improvement suggests that CNF is a powerful reinforcing agent for continuous sheets of moisture never dried and thus can be used to reduce breaks in the continuous sheet, especially in the paper machine equipped with long opening scraps. It should be noted that at the moment there is no commercial additive that can improve the resistance of the never dry wet sheet, including dry resistance agents and even wet resistance agents to improve the resistance of the rewetted leaves.
    [00054] In addition to the strength of the superior wet continuous sheet CNF it also improved the tensile strength of dry paper. For example, the addition of 3% CNF allowed the production of paper with 27% PCC having tension energy absorption (TEA) comparable to paper made with only 8% PCC made without CNF.
    [00055] The previous examples clearly show that CNF produced by this unprecedented invention can substantially improve the strength of the leaves of both wet continuous sheets and dry paper. Its unique powerful reinforcement performance is believed to be due to its long length and very thin width, thus a very high aspect ratio, which results in high flexibility and high surface area. CNF can provide entanglements in the paper structure and significantly increase the bonding area per unit mass of cellulose material. CNF is believed to be very suitable for reinforcing many products including all grades of paper and cardboard, fabric and towel products, coating formulations, as well as plastic composites.
    权利要求:
    Claims (20)
    [0001]
    1. Method for producing high-aspect ratio (CNF) cellulose nanofilaments, characterized by the fact that it comprises: refining a pulp consisting of cellulose fibers in a disc refiner at a high specific total refining energy of at least 2,000 kWh / t in a condition of high pulp fiber consistency of at least 20% by weight and recovering a population of filaments consisting essentially of refined cellulose nanofilaments in a disc refiner (CNF), free and bonded, having an aspect ratio of at least 200 to 5,000 and a width of 30 nm to 500 nm from the disc refiner.
    [0002]
    2. Method according to claim 1, characterized by the fact that said high total specific refining energy is 5,000 to 20,000 kWh / t, preferably 5,000 to 12,000 kWh / t.
    [0003]
    3. Method according to claim 1, characterized by the fact that said refining is carried out in a plurality of refining passages.
    [0004]
    4. Method according to claim 3, characterized by the fact that said plurality is greater than 2 and less than 15 for atmospheric refining and less than 50 for pressurized refining.
    [0005]
    5. Method according to claim 2, characterized by the fact that said refining is in low intensity comprising refining in a double disc refiner at a rotational speed less than 1200RPM.
    [0006]
    6. Method according to claim 5, characterized by the fact that said rotational speed is 900RPM or less.
    [0007]
    7. Method according to claim 2, characterized by the fact that said refining is in low intensity refining in a single disc refining at a rotational speed less than 1800RPM.
    [0008]
    8. Method according to claim 7, characterized by the fact that said rotational speed is 1500RPM or less.
    [0009]
    9. Method according to claim 1, characterized by the fact that said refining is open discharge refining.
    [0010]
    10. Method according to claim 1, characterized by the fact that said refining is closed discharge refining.
    [0011]
    11. Method according to claim 1, characterized by the fact that it additionally comprises a step of: feeding a disc refiner with a stock of wood pulp and water, and in which the pulp is refined with high total specific refining energy of at least 2,000 to 20,000 kWh / t in a condition of high consistency of the pulp fibers from 20% to 65% by weight.
    [0012]
    12. Method according to claim 11, characterized by the fact that the said high total specific refining energy is from 5,000 to 12,000 kWh / t, said cellulose nanofilaments (CNF) have an aspect ratio of 400 to 1,000 and a length greater than 10 μM.
    [0013]
    13. Method according to claim 11, characterized by the fact that said refinement is conducted in said disc refiner, in a plurality of refining passages.
    [0014]
    14. Method according to claim 13, characterized by the fact that said plurality is greater than 2 and less than 15 for atmospheric refining and less than 50 for pressurized refining.
    [0015]
    15. Method according to claim 12, characterized by the fact that the refining is under low intensity comprising refining in a double disc refiner at a rotational speed less than 1200RPM.
    [0016]
    16. Method according to claim 15, characterized by the fact that said rotational speed is 900 RPM or less.
    [0017]
    17. Method according to claim 12, characterized by the fact that the refining is under low intensity comprising refining in a single disc refiner at a rotational speed less than 1800RPM.
    [0018]
    18. Method according to claim 17, characterized by the fact that said rotational speed is 900 RPM or less.
    [0019]
    19. Method according to claim 11, characterized by the fact that said refining is open discharge refining.
    [0020]
    20. Method according to claim 11, characterized by the fact that the refining is closed discharge refining.
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    同族专利:
    公开号 | 公开日
    EP2665859A1|2013-11-27|
    WO2012097446A1|2012-07-26|
    RU2013138732A|2015-02-27|
    EP2665859A4|2016-12-21|
    CA2824191A1|2012-07-26|
    EP2665859B1|2019-06-26|
    CN103502529B|2016-08-24|
    CN103502529A|2014-01-08|
    AU2012208922A1|2013-08-01|
    AU2012208922B2|2016-10-13|
    RU2596521C2|2016-09-10|
    US20130017394A1|2013-01-17|
    KR101879611B1|2018-07-18|
    CA2824191C|2015-12-08|
    BR112013018408A2|2016-10-11|
    US9051684B2|2015-06-09|
    KR20140008348A|2014-01-21|
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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]|
    2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-06-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161435019P| true| 2011-01-21|2011-01-21|
    US61/435,019|2011-01-21|
    PCT/CA2012/000060|WO2012097446A1|2011-01-21|2012-01-19|High aspect ratio cellulose nanofilaments and method for their production|
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