PLANT DERIVED CELLULOSE PARTICULAR MATERIAL AND ITS PREPARATION PROCESS

专利摘要:
PLANT-DERIVED CELLULOSE PARTICULATED MATERIAL, ITS PREPARATION PROCESS, ITS USE, COMPOSITION, EMULSION, PAPER AND PARTICLES CONTAINING CELLULOSE. The present invention relates to plant-derived cellulose-containing particles useful as rheology modifiers and a process for preparing cellulose-containing particles from plant material, wherein the process involves treating said plant material with a peroxide reagent . The process can be controlled to produce a cellulose-containing particle having a viscosity of up to about 7.5 or 8 Pa.s (7,500 or 8,000 cps).
公开号:BR112015023908B1
申请号:R112015023908-0
申请日:2014-03-18
公开日:2020-11-24
发明作者:David Hepworth；Eric Whale
申请人:Cellucomp Limited；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to a process for preparing cellulose-containing particles from plant material using a peroxide reagent, in which the particles and compounds comprise the particles. The process can be controlled to provide particles containing cellulose that have a viscosity in water that is included in a wide range. Particles containing cellulose can be useful as rheological modifiers and reinforcing agents in water-based systems. BACKGROUND OF THE INVENTION
[002] Cellulose forms the basic structural component of plant cell walls where it exists in the form of cellulose fibers. The use of cellulose extracted from plant material attracts interest due to the fact that, in general, cellulose has good strength, rigidity, biodegradability and renewable properties. It is known to reinforce materials such as plastics and epoxy resins, with thick vegetable fibers from hemp and linen, for example. It is known to use chemically modified cellulose, such as hydroxyethylcellulose, to increase the viscosity of an aqueous medium such as an emulsion.
[003] However, the production of such chemically modified cellulose is of high energy consumption, which involves several treatment steps. Cellulose fibers can be broken down into microfibril and nanofibril substructures. More recently, the use of these highly purified cellulose substructures as additives to modify the physical properties of a material has attracted interest. In particular, it is known that some microfibrillary and nanofibrillary cellulose compounds can have a high viscosity in water. Such high viscosity compounds can be useful as viscosity modifiers.
[004] The processing of untreated plant material to obtain microfibrillar and nanofibrillar cellulose compounds is also energy intensive and involves several stages that include various chemical treatments and homogenization through, for example, shear mixing or high pressure release or through grinding, filtration and pressing. Generally, the greater the number of process stages required, the greater the energy required to produce the final product. There is a need for alternative and / or improved viscosity modifiers. There is a need to provide a material that contains alternative cellulose that can be produced from plants and that can be used as a viscosity modifier. There is a need to provide a simpler and less energy-consuming process for producing material containing high viscosity cellulose from plants. In addition, some of the commonly used chemical treatment steps, such as acid hydrolysis or alkali from plant material, can take a long time. There is a need to provide a more efficient process for extracting a material containing useful cellulose from plants. More particularly, there is a need to provide a more efficient process for producing a material containing high viscosity cellulose from plants.
[005] The most well-known processes for producing cellulose-containing compounds from plants produce a compound that has a particular characteristic viscosity or a narrow range of viscosities as measured at a particular concentration in water. Thus, in order to produce a wide range of different viscosity classes of material containing cellulose, the manufacturer has to modify between different reaction systems. This may involve cleaning a reactor to modify reaction and product systems. This has implications for waste, both in terms of downtime and loss of reagents. It would be advantageous to have a reaction system for breaking up plant material that could be easily controlled to produce material containing cellulose that has a predetermined viscosity chosen from a wide range of possible viscosities.
[006] Additionally, it is desirable that the broad range of viscosities is a broad range of viscosities that can be achieved by the material in low water concentrations, such as 1% by weight or less (unless otherwise specified, all weight references (p) in this document are references to dry weight). This is not easily achieved as the chemical / biological breakdown of plant material involves complex mechanisms that are not fully understood. It is also desirable to provide a process for preparing cellulose-containing material in which the process has the ability to deliver and be controlled to provide cellulose-containing compounds of different viscosities, that is, it can be controlled to provide both cellulose-containing compounds that have a relatively high viscosity at low concentrations of water and cellulose compounds that have a relatively low viscosity at low concentrations of water.
[007] For many of the end uses of material containing cellulose processed from plants, it is necessary to discolor the material to some extent. Decolorization of cellulose-containing material produced from plants often involves additional chemical / biological treatments that increase total processing time and can reduce yields. It is, therefore, desirable to provide an improved and efficient process for preparing such processed vegetable material in which the process involves discoloring the material. It is also desirable to provide a process for preparing a cellulose-containing material in which the process involves discoloring the material and in which the process can be controlled to provide cellulose-containing compounds of different viscosities. There is also a need for a process for preparing a material containing high viscosity cellulose from plants in which the process also involves discoloring the material.
[008] The present invention seeks to provide a new method of producing a material containing cellulose from plant material that alleviates one or more of the above problems. In addition, the invention seeks to provide new compounds comprising cellulose and uses for it. SUMMARY OF THE INVENTION
[009] The present invention relates to a particulate material that contains plant-derived cellulose. The cellulose-containing particles comprise plant cell wall material, and are useful as rheological modifiers in water-based systems.
[0010] According to a first aspect of the invention, a particulate plant-derived cellulose material is provided which comprises less than 30% by weight of extractable glucose; and extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material.
[0011] According to a second aspect of the invention there is provided a process for preparing particulate material containing cellulose that has a viscosity in a concentration of 1% dry weight in water of at least 2,500 cps, the process comprising the steps to: (i) contact herbaceous plant material with a peroxide and water reagent; (ii) heat the mixture of (i) to a temperature of 30 to 110 ° C and keep said mixture at a temperature of 30 to 110 ° C until the pH of the mixture has dropped to about 1 to 2 pH units ; and (ii) isolating the cellulose-containing particles.
[0012] Advantageously, in the second aspect of the invention, the use of a peroxide reagent to treat plant material has been found to be extremely effective in the production of particles containing cellulose of the first aspect and, in particular, high viscosity particles that contain cellulose. The process of the invention employs the use of only one chemical reagent to break down plant material, the peroxide reagent, and is thus a relatively efficient and simple process. In addition, the process of the invention can be controlled relatively easily to produce cellulose-containing particles that have either a relatively low viscosity in water or a relatively high viscosity in water. In particular, the viscosity of the cellulose-containing particles can be controlled by monitoring the pH of the reaction mixture from step (ii). In addition, the process of the invention can be controlled to provide particles containing discolored cellulose without the use of any additional chemical / biological reagents.
[0013] A third aspect of the invention relates to particles containing cellulose obtained by the process of the invention.
[0014] In the process of the invention, the plant material is broken up into particles comprising a plant cell wall material. These particles comprise a plant cell wall material, retain part of the nature of plant cell walls and, importantly, have the ability to swell with water. The particles have good water retention capabilities and this appropriately contributes to their usefulness as viscosity modifiers in water-based systems that include: coatings, such as epoxy resin based paints; paints based on polyurethane; paints based on acrylic resin; home and personal care products such as shampoos or facial creams; and concrete. They may also have been observed with good shear-thinning properties and good mechanical properties, such as strength and can beneficially reduce the porosity of paper compounds.
[0015] Additional aspects of the invention relate to the use of cellulose-containing particles and compounds and emulsions that comprise cellulose-containing particles. These are formulas beneficial to the environment. BRIEF DESCRIPTION OF THE FIGURES
[0016] Figure 1 is a graph of pH and viscosity versus time for the process of the invention described in Example 1.
[0017] Figure 2 is a graph of viscosity as a function of shear rate for epoxy paint compounds described in Example 5.
[0018] Figure 3 is a graph of viscosity as a function of the shear rate for acrylic paint compounds described in Example 5. DETAILED DESCRIPTION OF THE INVENTION
[0019] Unless stated otherwise, references in this document to particles containing cellulose and particulate cellulose material should be interpreted as any material containing cellulose resulting from the processes described in this document. Such references should not be interpreted as excluding any other materials, on the contrary, the particles contain or comprise cellulose.
[0020] Unless stated otherwise, references in this document to the extractable content of a monosaccharide other than glucose refer to the amount of said monosaccharide that can be extracted by hydrolysis of a fraction of insoluble alcohol from particles that contain cellulose or cellulose particulate material or vegetable material at the beginning when contacted with 2 M trifluoroacetic acid for 4 hours at at least 100 ° C.
[0021] Unless stated otherwise, references in this document to extractable glucose content refer to the amount of glucose that can be extracted by hydrolysis of an insoluble fraction of alcohol from particles containing cellulose or material cellulose particulate or plant material at the beginning when contacted with 72% (w / v) sulfuric acid for 4 hours at 120 ° C.
[0022] Unless stated otherwise, the values in% by weight refer to the extractable amount of the specified compound from a known dry mass of the particulate material following acid hydrolysis.
[0023] Unless stated otherwise, the absolute values in% refer to the extractable amount of the specified compound isolated from the particulate material following acid hydrolysis as a percentage of the extractable amount of the specified compound isolated from the starting plant material following the acid hydrolysis.
[0024] Unless stated otherwise, references in the present document to the starting plant material are to the herbaceous plant material used in the process of the present invention. References to plant material at the beginning are also plant material that has been homogenized to a pulp, but before any chemical treatment.
[0025] Unless stated otherwise, references in this document to the "peroxide process" are to the treatment of plant material with a peroxide reagent with the application of heat. Unless otherwise stated, references in the present document to the "more oxidizing / bleaching peroxide process" or to the "complete process" are to treatment of plant material with a peroxide reagent followed by treatment with an oxidizer / bleach.
[0026] Unless stated otherwise, references in this document to the viscosity of the particles containing cellulose are to the viscosity of the particles at a concentration of 1% dry weight in water as measured at 20 ° C using a Brookfield viscometer with RV rods rotated at 10 rpm.
[0027] Unless stated otherwise, references in this document to particles containing "high viscosity" cellulose are to those particles that have a viscosity of at least about 2.5 Pas (2,500 cps) when measured accordingly. with the method described above.
[0028] Unless otherwise stated, references in this document to particles containing "low viscosity" cellulose are to those particles that have a viscosity of less than about 2.5 Pa s (2,500 cps), for example, less than about 1 Pa s (1,000 cps) when measured according to the method described above.
[0029] Unless stated otherwise, the term "about" is used to provide flexibility to a numerical range endpoint providing that a given value may be slightly above or slightly below the end point to allow variation in test methods or apparatus. The degree of flexibility of that term can be dictated by the particular variable and would be within the knowledge of those skilled in the art to determine based on experience and the associated description in this document. PARTICLES CONTAINING CELLULOSE
[0030] The first aspect of the present invention provides particulate plant-derived cellulose material that comprises less than 30% by weight of extractable glucose; and extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material.
[0031] In the process of the invention, the plant material is broken down into particles containing cellulose which comprise plant cell wall material. The plant cell wall material comprises cellulose, hemicelluloses (such as xyloglucans, xylans, mannins and glucomannans), pectins and proteins such as glycoproteins. The particles can include plant cells, plant cell walls and loose associations of polymeric plant cell wall components, which can be, for example, pieces of a gel formed from cellulose, hemicellulose, pectin and protein. It is believed that, in the process of the invention, the breakdown of plant cell wall occurs through partial degradation of pectins and hemicelluloses and subsequent extraction of pectinic and hemicellulosic monosaccharides. However, it is believed that the process of the present invention does not degrade cellulosic material so that some part of the cell wall structure / nature is retained. The peroxide reagent is also believed to cleave covalent bonds within the cell wall polysaccharide structure, loosening the cell wall structure, with a result that the cellulose containing particles of the invention have the ability to swell with water. This ability to swell with water contributes to the advantageous rheology modifying properties that the particles of the present invention exhibit.
[0032] The particles containing cellulose are insoluble in water. Water-insoluble means that, at a concentration of 1% by weight (solids) or less in water, the particles containing cellulose are distinct particles. A distinct particle is one that can be observed as such with the use of light microscopy at 100X magnification. The cellulose-containing particles preferably have an average head size of 1 to 250 µm. The particles can be an average principal dimension that is greater than 10 pm and up to 200 pm. Preferably, they have an average principal dimension of 10 to 70 pm or 30 to 70 pm. The average principal dimension can be measured by light microscopy. The particles are stained by adding a few drops of methylene blue to a diluted suspension of particles fully hydrated on a slide. The particles are viewed at 100X magnification, using a Dyno-eye (USB) camera in the microscope's eyepiece with Dynocapture 2.0 software on a computer connected to the camera. The largest particle size is measured using image analysis.
[0033] Preferably, the cellulose-containing particles contain less than 5% by weight, preferably less than 3% by weight of microfibrillary material as measured by the amount of material that passes through a 10 pm filter after application. repeated washing followed by drying the washes at 150 ° C.
[0034] The cellulose-containing particles preferably comprise cellulose in an amount of less than 60% by weight, preferably up to 59% by weight, more preferably up to 55% by weight. Preferably, the cellulose-containing particles contain cellulose in an amount of at least 40% by weight or 45% by weight. In one embodiment, the cellulose-containing particles comprise cellulose in an amount of 50 to less than 60% by weight or in an amount less than 53 to 58% by weight.
[0035] In one embodiment, the cellulose-containing particles comprise cellulose in an amount less than about 60% by weight, for example, less than about 59% by weight, less than about 58% by weight, less than about 55% by weight, less than about 53% by weight, less than about 50% by weight, less than about 45% by weight, less than about 40% by weight.
[0036] In one embodiment, the cellulose-containing particles comprise cellulose in an amount greater than about 40% by weight, for example, greater than about 45% by weight, greater than about 50% by weight, greater than about 53% by weight, greater than about 55% by weight, greater than about 58% by weight, greater than about 59% by weight, for example, up to about 60% by weight .
[0037] Preferably, the cellulose-containing particles contain polysaccharides other than cellulose in an amount of 4 to 6% by weight.
[0038] Preferably, the cellulose-containing particles contain hemicellulose in an amount less than 2% by weight and the peccine in an amount less than 10% by weight. The cellulose content and the content of the other polysaccharides can be measured using the following standard method: a sample of the material is converted into alcohol-insoluble residues and a portion of it is then subjected to acid hydrolysis using 2 M trifluoroacetic acid for 1 hour at 120 ° C. This produces a hydrolyzate and a non-hydrolyzable cellulosic / polysaccharide residue. The hydrolyzate is dried and resuspended in distilled water. This solution is then analyzed for monosaccharide content using HPLC.
[0039] The particulate cellulose material contains extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material. Alternatively, the cellulose particulate material contains at least 10% of the amount of extractable xylose in the starting plant material, for example, at least 20%, at least 30%, at least 40% of extractable xylose in the amount of extractable xylose in the material beginning vegetable.
[0040] Alternatively, the particulate cellulose material contains at least 5% of extractable xylose in relation to the amount of extractable xylose in the starting plant material. Alternatively, the cellulose particulate material contains at least 10% of extractable xylose in relation to the amount of extractable xylose in the starting plant material, for example, at least 20%, at least 30%, at least 40% of extractable xylose in relation to to the amount of extractable xylose in the starting plant material.
[0041] Alternatively, the particulate cellulose material contains extractable xylose in an amount of at least 6% of the amount of extractable xylose in the starting plant material. Alternatively, the cellulose particulate material contains at least 7% of the amount of extractable xylose in the starting plant material, for example, at least 8%, at least 9%, at least 10% of extractable xylose in the amount of extractable xylose in the material beginning vegetable.
[0042] Alternatively, the particulate cellulose material contains extractable xylose in an amount less than 10% of the amount of extractable xylose in the starting plant material. Alternatively, the cellulose particulate material contains less than 9% of the amount of extractable xylose in the starting plant material, for example, less than 8%, less than 7%, less than 6% of extractable xylose from the amount of extractable xylose in the starting plant material.
[0043] Alternatively, the cellulose particulate material contains less than 70% extractable xylose in relation to the amount of extractable xylose in the starting plant material. Alternatively, the cellulose particulate material contains less than 60% extractable xylose in relation to the amount of extractable xylose in the starting plant material, for example, less than 55% extractable xylose in relation to the amount of extractable xylose in the plant material from start.
[0044] In an alternative embodiment, the cellulose particulate material is derived from sugar beet, and contains at least about 1.5% by weight, for example, at least about 1.6% by weight, at least about 1.7% by weight, at least about 1.8% by weight, at least about 1.9% by weight, for example, about 2% by weight of extractable xylose.
[0045] In an alternative embodiment, the cellulose particulate material is derived from sugar beet, and contains at least about 1.5% by weight, for example, at least about 1.6% by weight, at least about 1.7% by weight, at least about 1.8% by weight, at least about 1.9% by weight, for example, about 2% by weight of extractable xylose when the amount of extractable xylose in the plant material beginning sugar beet is about 20% by weight.
[0046] In an alternative embodiment, the cellulose particulate material is derived from the carrot, and contains at least about 0.8% by weight, for example, at least about 0.9% by weight, for example, about 1.0% by weight of extractable xylose.
[0047] In an alternative embodiment, the cellulose particulate material is derived from the carrot, and contains at least about 0.8% by weight, for example, at least about 0.9% by weight, for example, about 1.0% by weight of extractable xylose when the amount of extractable xylose in the initial carrot plant material is about 2.0% by weight.
[0048] The particulate cellulose material contains less than 30% by weight of extractable glucose. Alternatively, the cellulose particulate material contains less than 25% by weight extractable glucose, for example, less than 20% by weight, less than 19% by weight, less than 18% by weight, less than 17% by weight, less than 16% by weight, less than 15% by weight of extractable glucose.
[0049] In an alternative embodiment, the cellulose particulate material is derived from sugar beet, and contains less than about 25% by weight, for example, less than about 20% by weight, less than about 15 % by weight, for example, about 13% by weight of extractable glucose when the amount of extractable glucose in the initial sugar beet plant material is about 7% by weight.
[0050] In an alternative embodiment, the cellulose particulate material is derived from the carrot, and contains less than about 25% by weight, for example less than about 20% by weight, for example, about 19% by weight. weight of extractable glucose when the amount of extractable glucose in the starting carrot plant material is about 11% by weight.
[0051] In one embodiment, the cellulose particulate material contains less than about 1% by weight, for example, less than about 0.5% by weight, for example, less than about 0.2% in weight, for example, substantially no mannose. In one embodiment, the cellulose particulate material contains less than about 1% by weight, for example, less than about 0.5% by weight, for example, less than about 0.2% by weight, for example, substantially no rhamnose.
[0052] In one embodiment, the particulate cellulose material may comprise one or more polysaccharides from among homogalacturonan, (1-4) -β-D-galactane, xyloglucan, (1-4) -β-D-xylan and ( 1-4) -β-D- arabinoxylan. In one embodiment, the particulate cellulose material may comprise completely methylesterified homogalacturonane, partially methylesterified homogalacturonane or completely deesterified homogalacturonane. In one embodiment, the particulate cellulose material may comprise one or more glycoproteins. For example, in one embodiment, the particulate cellulose material may comprise extensin. The determination of the presence of such components can be readily performed using the CoMPP glycoarray method as described in Moller I, Marcus SE, Haeger A, Verhertbruggen Y, Verhoef R, Schols H, Ulvskov P, Mikkelen JD, Knox JP , Willats W. (2007) High-throughput screening of monoclonal antibodies against plant cell wall glycans by hierarchical clustering of their carbohydrate microarray binding profiles. Glycoconj J. 25 (1): 37 to 48.
[0053] The cellulose-containing particles preferably comprise a non-saccharide (i.e., non-carbohydrate) component that is present in an amount of 20 to 50, preferably 35 to 48% by weight. That component can comprise proteins, for example, glycoproteins.
[0054] The particles containing cellulose can be hydrated and, preferably, have water holding capacities of 90 to 99.5% by weight of water. The water retention capacity is measured by dispersing the particles in water, allowing them to fully hydrate, then filtering them using a 10 pm paper filter, with no pressure applied during filtration. The material collected in the filter once the liquid has stopped flowing is weighted, then dried using a moisture analyzer set at 150 ° C and then re-weighted to determine the amount of water present.
[0055] Particles containing cellulose can have a viscosity of up to 7.5 or 8 Pas (7,500 or 8000 cps). They can be high viscosity particles and have a viscosity of 2.5 or 3 to 7 Pa s (2,500 or 3,000 to 7,000 cps) or they can be low viscosity particles and have a viscosity of 0.01 to 1 Pa s (10 to 1,000 cps).
[0056] The particles can have a viscosity greater than about 2.5 Pa s (2,500 cps), for example, at least about 3 Pa s (3,000 cps), for example, at least about 3.2 Pa s (3,200 cps), for example, at least about 3.5 Pa s (3,500 cps), at least about 4 Pa s (4,000 cps), at least about 5 Pa s (5,000 cps), at least about of 5.5 Pa s (5,500 cps), at least about 6 Pa s (6,000 cps), at least about 7 Pas (7,000 cps), at least about 7.5 Pa s (7,500 cps), for example , up to 8 Pa s (8,000 cps).
[0057] The particles may have a viscosity of less than about 8 Pa s (8,000 cps), for example, less than about 7.5 Pa s (7,500 cps), less than about 7 Pa s (7,000 cps) cps), less than about 6 Pa s (6,000 cps), less than about 5.5 Pa s (5,500 cps), less than about 5 Pa s (5,000 cps), less than about 4 Pa s (4,000 cps), less than about 3.5 Pa s (3,500 cps), less than about 3.2 Pa s (3,200 cps), less than about 3 Pa s (3,000 cps), for example, about 2.5 Pa s (2,500 cps).
[0058] The particles may have a viscosity of 2.5 or 3 or 4 Pa s (2,500 or 3,000 or 4,000 cps) or more, preferably the particles have a viscosity of 3.5 to 5.5 Pa s (3,500 at 5,500 cps). In this embodiment, the particles can have a water retention capacity in the range of 97 to 99.5% by weight of water. Preferably, they have an average major dimension of 10 to 70 pm or 100 pm and comprise cellulose in an amount of 45 or 50 less than 60% by weight. These high viscosity containing cellulose particles are useful as viscosity enhancers for water-based systems in that only a relatively small amount is required to achieve the required viscosity. In addition, the viscosity of the system is increased by a large amount at low shear rates and by much less at high shear rates. In other words, cellulose-containing particles are quite pseudoplastic in water-based systems and are useful as rheology modifiers in such systems. This can be advantageous when, for example, anti-settling of heavy additives such as pigments is required in a static formulation, for example, paint in a can, but where easy flow is required at high shear rates, for example, during applying paint to a surface by spraying or brushing.
[0059] Particles containing cellulose may have a viscosity of up to 2.5 Pa s (2,500 cps), for example, up to 1 Pa s (1,000 cps) and preferably have a viscosity of at least 0.01 Pa s (10 cps) or at least 0.1 Pa s (100 cps). In this embodiment, the particles can have a water holding capacity in the range of 93 to 96% by weight of water. Preferably, they have an average major dimension of 10 to 70 pm or 100 pm and comprise cellulose in an amount of 45 or 50 less than 60% by weight. These low viscosity containing cellulose particles are useful as viscosity enhancers for water-based systems where a relatively large amount can be added to achieve the required viscosity while adding mechanical strength to the resulting substantially dry and / or cured composite material. Water based. In other words, these particles can act as a reinforcing agent for a water-based system without having a very strong effect on the system's viscosity. In addition, these particles can provide anti-cracking properties during drying and curing of the paint. For example, a load of 3% dry weight in an acrylic paint can allow a cohesive content of the paint to be reduced without causing the paint to crack during drying. This is advantageous because coalescing is a solvent and reducing its content will improve the ink's environmental credentials. A 3% dry weight loading in an acrylic paint also increased the scrub resistance of an acrylic paint. The low viscosity particles are also pseudoplastic, but they start from a lower viscosity, at a low shear, than the high viscosity material.
[0060] Another advantage of the cellulose-containing particles of the invention is that, in water-based formulations, the particles are quite insensitive to pH, that is, the viscosity does not change measurably between a pH of 2 to 14, for example , from 3 to 12. This is in contrast to many other viscosity modifying products, such as hydroxyethylcellulose (HEC), which are sensitive to pHs in this range. PROCESS FOR PREPARING PARTICULATE MATERIAL CONTAINING CELLULOSE Step (i)
[0061] Step (i) of the process of the invention comprises contacting the herbaceous plant material with a peroxide reagent and water to provide a mixture of the plant material, peroxide reagent and water. VEGETABLE MATERIAL
[0062] The plant material used in the present invention is herbaceous plant material. "Herbaceous" is a well-defined botanical term that refers to annual, biennial or perennial vascular plants. They are additionally characterized by their death from the aerial stems after each growing season. Regrowth in subsequent seasons for biannual and perennial species occurs from underground organs, for example, stem or root storage organs, tubers. This is in contrast to species whose stems resume growth each season and thus form growth rings. The particular property of herbaceous plants of relevance to the present invention is the abundance of primary walls in their tissues. These are particularly found in parenchyma tissues. The person skilled in the art will be aware that no organ of a herbal vascular plant is made entirely of parenchyma or entirely of primary walls, as vascular elements with their secondary walls are invariably also a component of all but the simplest organs. However, it will also be appreciated that plant material made from primary polysaccharide-rich cell walls also occurs in two groups of plants that are non-vascular plants: mosses and charophycean green algae. "Herbaceous" must, for the purposes of this invention, also understand the biomass of these groups of plants. The plant material used in the process of the invention therefore includes vegetables, for example, edible roots and fruit. Examples of edible roots include carrots, sugar beets (also referred to herein as "beets") or turnips, parsnips and cabbage. Examples of fruit include apples, pears and grapes. The plant material can be a potato. The plant material can be derived from a type of vegetable, for example, substantially all plant material can comprise material from a specific edible root, for example, one of carrots, sugar beet, turnip, parsnip or turnip cabbage. By substantially all, at least 90% dry weight of plant material is meant. As noted in this document, all weights are dry weight unless otherwise specified. Similarly, substantially all of the plant material can comprise the material of a specific fruit, for example, one among apples, pears or grapes. The plant material can be derived from a mixture of the type of vegetables and fruit, for example, more than one among carrots, beets or turnips, parsnips, turnips, apples, pears and grapes. Preferably, the plant material comprises one of or a mixture of sugar beet and canoura. In one embodiment, the plant material used in the process of the invention is not wood. Preferably, when the fruit or vegetable has a peel that is greater than 3% by weight of the fruit or vegetable, the fruit or vegetable has had the peel removed, for example, by peeling.
[0063] Preferably, the plant material has a parenchymatic cell content greater than 30% by volume, more preferably, greater than 35% by volume or greater than 50% by volume and, preferably maximum, greater than than 70% based on the volume of plant material. The parenchymatic cell content is determined by image analysis, that is, by cutting a section of the plant, observing the section under a microscope and measuring the areas of the parenchymal tissue. Ideally, sections are removed through different parts of the plant or plant organ and these areas can then be converted into a forecast of tissue volumes. Preferably, the plant material contains less than 20% by weight of lignin, more preferably, it contains from 1 to 10% by weight of lignin, preferably maximum, it contains from 1 to 5% by weight of lignin . The lignin content can be measured by a standard method such as the Klason method. This method uses strong acid treatment to break and dissolve all plant materials except lignin. Lignin is defined as the weight of the material that cannot be broken by 72% sulfuric acid.
[0064] In one embodiment, the herbaceous plant material comprises less than about 30% by weight of lignocellulose. In one embodiment, the herbaceous plant material comprises less than about 20% by weight of lignocellulose. In one embodiment, the herbaceous plant material comprises less than about 15% by weight of lignocellulose. In one embodiment, the herbal plant material comprises less than about 10% by weight of lignocellulose, for example, less than about 9% by weight of lignocellulose, less than about 8% by weight of lignocellulose, less than than about 7% by weight of lignocellulose, less than about 6% by weight of lignocellulose, less than about 5% by weight of lignocellulose, less than about 4% by weight of lignocellulose, less than about 3% by weight of lignocellulose, less than about 2% by weight of lignocellulose, less than about 1% by weight of lignocellulose. In one embodiment, the herbaceous plant material comprises substantially no lignocellulose.
[0065] In one embodiment of the present invention the herbaceous starting material is a plant with seeds, that is, that belongs to Magnoliaphyta. In an additional modality, the plant is a single-cotyledonous, more specifically, a member of Poales, typically a cereal. The plant material can be a waste product or lateral flow from agricultural production. In yet another preferred embodiment, the herbaceous plant is a member of the eucotyledons, more specifically, a crop plant or a waste product or lateral flow of agricultural production. The pulps remaining after the production of potato starch or sugar beet are attractive agricultural side flows useful for the present invention. Root crops are generally relevant raw materials. A non-exhaustive list includes carrots, turnip greens, turnips, parsnips and radishes. Jam, jam, juice production is another valuable waste product from which cellulose can be recovered by the methods disclosed in the present invention.
[0066] The vegetable material can be vegetable raw material or vegetable raw material that has been heat treated and / or mechanically treated, it is preferably washed, but it is preferably essentially not treated otherwise. Preferably, it will not have been treated by any chemical reagents that could act to break it. Preferably, it will not have been subjected to treatment by acid or alkaline hydrolysis. Preferably, the plant material has been mechanically treated, for example, cut / crushed so that it is in the form of particles having an average main dimension, for example, less than 10 mm, preferably less than 500 pm, more preferably, less than 250 pm, preferably maximum, less than 200 pm. The plant material can be in the form of a pulp, for example, taken from an industrial waste stream. The pulp can be prepared from the plant raw material by washing the plant raw material, crushing or cutting it, cooking it in water at, for example, 90 to 100 ° C until smooth and optionally homogenizing it to reduce the size of the insoluble particles contained therein. Alternatively, the pulp can be prepared from the plant raw material by washing the plant raw material, grinding or cutting it, cooking it in water in a pressure cooker until soft and optionally homogenizing it to reduce the size of insoluble particles contained therein. It will be recognized that the cooking temperature in this mode can exceed 100 ° C.
[0067] Preferably, the insoluble particles of the pulp have an average main dimension of less than 10 mm, preferably less than 500 pm, preferably less than 250 pm, more preferably less than 200 pm. The pulp can be washed and filtered to remove soluble by-products. In one embodiment, step (i) comprises providing a mixture of plant material, peroxide reagent and water, in which the plant material is made up of particles having an average main dimension of less than 500 pm. Step (i) can comprise preparing the pulp from the vegetable raw material and adding the peroxide reagent and water to it. In another embodiment, step (i) may comprise providing a mixture of plant raw material, peroxide reagent and water and homogenizing the mixture until the plant material is made up of particles having an average main dimension of less than 500 pm.
[0068] The speed at which the process of the invention proceeds depends, in part, on the concentration of the reagents. Preferably, the concentration of plant material in the mixture from step (i) is maintained at a level at which the process can be readily controlled. In one embodiment, the mixture from step (i) comprises plant material in a concentration of 1 to 10% by weight based on the combined amount of water and plant material present. Preferably, this concentration is 1 to 7% by weight, more preferably 2 to 5% by weight. PEROXIDE REAGENT
[0069] The process of the invention uses a peroxide reagent to break up the plant material and discolor it. Preferably, the peroxide reagent is chosen from hydrogen peroxide, an organic peroxide or an inorganic peroxide. Most preferably, the peroxide reagent is hydrogen peroxide or an organic peroxide. Examples of suitable organic peroxides are peroxycarboxylic acids such as peracetic acid and meta-chloroperoxybenzoic acid and organic hydroperoxides, such as benzyl peroxide. Examples of inorganic peroxides include ionic peroxide salts, for example, alkali and alkaline earth metal peroxides and acid peroxide such as peroxysulfuric acid and peroxyphosphoric acid. Most preferably, the peroxide reagent is hydrogen peroxide. The peroxide reagent is preferably present in an amount of between 5 to 40% by weight based on the weight of dry matter of the plant material. In one embodiment, the peroxide reagent is present in an amount between 20 to 35% by weight based on the weight of the plant material. In one embodiment, peroxide is added as a 35% aqueous solution and the ratio of the peroxide reagent solution to the dry solids content of the plant material is at least about 0.25: 1 (by weight), for example at least about 0.5: 1, at least about 0.6: 1, at least about 0.7: 1, at least about 0.8: 1, at least about 0.9: 1 , for example, about 1: 1.
[0070] In the process of the present invention, it is believed that the peroxide reagent acts to loosen the natural cell wall structure by breaking certain bonds within the complex cell wall structure allowing it to hydrate (and swell) more with water and significantly increasing the viscosity of plant material. This effect, its extent and speed were not observed with the use of acid or alkaline hydrolysis of plant material. In addition, it has been shown that particles containing high viscosity cellulose can be obtained effectively by the process of the present invention, with the use of a single chemical treatment step on the plant material. Preferably, the process does not comprise any additional chemical treatments and / or any biological, for example, enzymatic treatments.
[0071] A catalyst, to catalyze the reaction of the peroxide reagent with the plant material, can be added to the mixture of step (i). Examples of catalysts include manganese catalysts. Thus, the mixture of step (i) can also comprise a peroxide reagent catalyst. However, in one embodiment, the process of the present invention is carried out in the absence of a catalyst. Step (ii)
[0072] Step (ii) involves heating the mixture provided in step (i). At this stage, the plant material is broken down by the peroxide reagent and discoloration of the cellulose-containing particles may also occur.
[0073] In step (ii), the mixture is heated to a temperature of 30 to 110 ° C, for example, 30 and 100 ° C and maintained at a temperature of 30 to 110 ° C, for example, 30 and 100 ° C, for a period of time. The period of time that the mixture is kept within this temperature range can be between 1 minute and 6 hours. In one embodiment, the mixture is kept at a temperature of 30 to 110 ° C, for example, 30 to 100 ° C, for less than 6 hours, for example, less than 5 hours, less than 4 hours, less than 3 hours, less than 2 hours, for example, less than 1 hour. Alternatively, the mixture is kept at a temperature of 30 to 110 ° C, for example, 30 to 100 ° C, for at least 1 hour, for example, at least 2 hours, at least 3 hours, at least 4 hours, for at least least 5 hours, at least 6 hours. In one embodiment, the mixture is maintained at a stable temperature within the range of 30 to 110 ° C, for example, 30 to 100 ° C, for the period of time. In another embodiment, the temperature of the mixture can be varied within the range of 30 to 110 ° C, for example, 30 to 100 ° C, for the period of time, that is, increased and / or decreased during that period of time, but remaining within the range of 30 to 110 ° C, for example, 30 and 100 ° C. The choice of temperature (s) and the time period during which the mixture is kept at the temperature (s) depends on the desired viscosity of the particles containing cellulose and, optionally, on the desired degree of discoloration. Preferably, the mixture is heated to a temperature of 70 and 100 ° C and maintained at a temperature of 70 and 100 ° C for a period of time as specified above. VISCOSITY
[0074] The inventors investigated the viscosity behavior of the cellulose-containing particles as a function of the pH of the mixture in step (ii) being maintained at a temperature between 30 to 110 ° C, for example, 30 and 100 ° C, for a period of time. Referring to Figure 1 from which it can be seen that for the process carried out in Example 1, the pH of the reaction mixture varies with time and with the viscosity of the cellulose-containing particles. In one embodiment, the time period during which the mixture is maintained at a temperature between 30 to 110 ° C, for example, 30 and 100 ° C can be determined by monitoring the pH of the reaction liquid of the step reaction mixture (ii). The present inventors have found that the pH of the mixture varies as the viscosity of the cellulose-containing particles varies and, thus, this pH measurement can provide an indicator of the viscosity of the produced cellulose-containing particles. It is believed that, advantageously, this correlation between pH and viscosity is dependent on the temperature at which the mixture of (ii) is heated / maintained. Thus, the correlation can be applied to reaction systems with different heating regimes. However, the correlation between pH and viscosity can vary if the type of plant material changes.
[0075] Thus, in a preferred embodiment of the present invention, the mixture is maintained at a temperature between 30 to 110 ° C, for example, 30 and 100 ° C, until it has a predetermined pH value in order to produce the particles containing cellulose having a desired viscosity. The pH value can be determined by performing a calibration run under the same conditions.
[0076] A process is disclosed in this document which comprises: (i) providing a mixture of plant material, peroxide reagent and water; (ii) heating said mixture to a temperature in the range of 30 to 100 ° C and maintaining said mixture to a temperature in the range of 30 to 100 ° C for a period of time in order to break up the plant material; and (iii) isolating a residue comprising particles containing cellulose, wherein said process comprises monitoring the pH of the mixture during step (ii) and ending the maintenance of the mixture at a temperature in the range of 30 to 110 ° C, for example, 30 to 100 ° C, when the mixture reaches a predetermined pH value.
[0077] In this modality, said pH value can be determined from a calibration giving the viscosity in water of the particles containing cellulose to be expected as a function of the pH of the reaction mixture in step (ii). Thus, an example of the process comprises performing a calibration by which the process is carried out several times under the same conditions except that the period of time during which the mixture of step (ii) is kept at a temperature of 30 to 110 ° C, for example, 30 to 100 ° C, is varied. Each time, the reaction mixture is sampled. The pH is first measured and the sample is then separated into an insoluble residue that contains the particles containing cellulose and a liquid reaction component. The viscosity in water of the cellulose-containing particles is measured and a correlation between the viscosity of the cellulose-containing particles and the pH of the reaction mixture from step (ii) can thus be obtained.
[0078] In particular, the present inventors have revealed that the pH value drops as the viscosity decreases. Therefore, in the process described above, the predetermined pH is Y where Y = X - Δ where X is the pH of the mixture from step (ii) at the beginning of the heating process and 0 <Δ <4. For particles containing cellulose with a higher viscosity, 0 <Δ <2. In another embodiment, 2 <Δ <4, and this generates particles that contain cellulose with a lower viscosity. For carrots as a raw material at a concentration of 5% by weight based on water and plant material in the mixture from step (i): when 0 <Δ <4, particles containing cellulose that have a viscosity in the range of 0 , 01 to 6.8 Pa s (10 to 6,800 cps) can be obtained; when 0 <Δ <1, particles containing cellulose that have a viscosity in the range of 5 to 3.2 Pa s (5,000 to 3,200 cps) can be obtained; when 1 <Δ <2, particles containing cellulose that have a viscosity in the range of 3.2 Pa s (3,200 cps) less than 2.5 Pa s (2,500 cps) can be obtained; and when 2 <Δ <4, particles containing cellulose that have a viscosity in the range of 2.5 Pa s (2500 cps) less than 0.1 Pa s (100 cps) can be obtained.
[0079] Thus, in one embodiment, step (ii) of the process can be maintained until the pH of the mixture has dropped by at least 2 pH units in relation to the initial pH, for example, the pH of the mixture has dropped by at least about of 3 pH units in relation to the initial pH, for example, the pH of the mixture has dropped about 4 pH units in relation to the initial pH. Alternatively, step (ii) of the process can be continued until the pH of the mixture has dropped by less than about 4 pH units from the initial pH, for example, the pH of the mixture has dropped by less than about 3 units of pH in relation to the initial pH, for example, the pH of the mixture has dropped by about 2 pH units in relation to the initial pH.
[0080] Thus, in one embodiment, step (ii) of the process can be maintained until the pH of the mixture has dropped by less than 2 pH units compared to the initial pH, for example, the pH of the mixture has dropped by less than that about 1.9 pH unit in relation to the initial pH, for example, the pH of the mixture has dropped less than about 1.75 pH unit in relation to the initial pH, less than about 1.5 unit pH, less than about 1.4 pH unit, less than about 1.3 pH unit, less than about 1.2 pH unit, less than about 1.1 pH unit , for example about 1 pH unit. Alternatively, step (ii) of the process can be maintained until the pH of the mixture has dropped by less than about 1 pH unit, for example, at least about 1.1 pH unit, at least about 1.2 unit pH, at least about 1.4 pH unit, at least about 1.5 pH unit, at least about 1.75 pH unit in relation to the initial pH, for example, the pH of the mixture has dropped at least about 1.9 pH units in relation to the initial pH, for example, the pH of the mixture has dropped by about 2 pH units in relation to the initial pH. Preferably, no pH modification additives are added to the mixture of step (i) or step (ii) during the process. By pH modification is meant the pH adjustments of the mixture by a magnitude greater than 0.5.
[0081] The present studies involved an investigation into the viscosity behavior of the cellulose-containing particles formed by the process of the invention as a function of the time period in which the mixture of step (ii) is maintained at a temperature between 30 to 110 ° C, for example, 30 and 100 ° C. It has been shown that the viscosity of the cellulose-containing particles does not vary linearly over time. Unless otherwise specified, as noted in this document, the viscosity of the cellulose-containing particles is the viscosity of the particles at a concentration of 1% dry weight in water as measured at 20 ° C using a Brookfield viscometer with RV rods rotated at 10 rpm.
[0082] Referring to Figure 1 from which it can be seen that, for the process carried out in Example 1, the viscosity of the insoluble cellulose particles initially formed increases (from ~ 1.7 to 4.5 Pa s ( ~ 1,700 to 4,500 cps)) and then decreases as the reaction progresses in temperature. The higher the temperature, the faster the viscosity reaches a peak value and begins to drop. Thus, it is possible, with the use of the process of the invention, to produce cellulose-containing compositions that have many different viscosities, simply by controlling the length of time that the mixture in step (ii) is maintained at a temperature between 30 and 100 ° C.
[0083] Thus, the mixture can be maintained at a temperature between 30 to 110 ° C, for example, 30 and 100 ° C for a predetermined period of time in order to produce particulate cellulose that has a desired viscosity. The length of time can be determined by performing a calibration run under the same conditions. The calibration may change if the concentration of the starting materials (plant material and peroxide reagent), the type of plant material or the temperature at which the reaction mixture is maintained changes.
[0084] Therefore, a process is described in this document which comprises: (i) providing a mixture of plant material, peroxide reagent and water; (ii) heating said mixture to a temperature in the range of 30 to 100 ° C and maintaining said mixture to a temperature in the range of 30 to 100 ° C for a period of time in order to break up the plant material; and (iii) isolating a residue comprising particles containing cellulose, wherein said period of time is chosen to produce particles containing cellulose that have a desired viscosity in water. In this process, the said period of time can be determined from a calibration that generates the viscosity in water of the particles containing cellulose to be expected as a function of the period type. Therefore, the process may comprise performing a calibration according to which the process is performed several times under the same conditions, except that the time period in which the mixture of step (ii) is kept at a temperature of 30 to 100 ° C is varied. At each time, the reaction mixture is sampled. The sample is then separated into an insoluble residue that contains the cellulose-containing particles and a liquid reaction component. The viscosity in water of the particles containing cellulose is measured and correlated to said period of time.
[0085] In the process described in this document, materials of higher viscosity are, in general, produced in a short reaction time, while materials of lower viscosity are, in general, produced in a longer reaction time. This is a surprising conclusion and, as a result, the process of the invention can be controlled to provide particles containing cellulose with specific viscosity properties.
[0086] Advantageously, the process described in this document can produce particles that contain significantly discolored cellulose since the peroxide reagent both breaks the plant material and discolours it. However, in the case of production of the higher viscosity cellulose material, the reaction time may be relatively shorter and the discoloration may not have occurred to the maximum or to the extent required. It was concluded that increasing or decreasing the temperature in a series of controlled steps can help to decolorize the cellulose-containing particles while maintaining the high viscosity. Therefore, preferably, in the production of high viscosity material, step (ii) may comprise heating the mixture to a temperature between 90 and 100 ° C and keeping it at that temperature for some time, followed by cooling the mixture to a between 75 and 85 ° C and keep the mixture at that temperature for the rest of the time. Alternatively, step (ii) may comprise heating the mixture up to and maintaining it at a temperature between 75 and 85 ° C for a period of time, then increasing the temperature to between 90 and 100 ° C and retaining that temperature for a period of time until the desired degree of discoloration has been achieved.
[0087] To achieve particles containing cellulose very high viscosity viscosity, that is, particles with a viscosity of 6.8 Pa.s (6,800 cps) or greater, without discoloration of the particles, the mixture may only need to be heated to a relatively low temperature for a relatively short time. Below 30 ° C, it is possible to obtain particles containing high viscosity cellulose of the invention within a reasonable time span, that is, in a time span of hours, rather than days.
[0088] To achieve particles containing high viscosity cellulose, that is, particles with a viscosity greater than 2.5 Pa.s (2,500 cps), for example, 3 Pa.s (3,000 cps) or greater, with discoloration significant amount of the particles and within an acceptable time span of less than 4 hours and preferably less than 2 hours, preferably the mixture should be heated to a temperature between 70 to 100 ° C. Most preferably, the temperature is in the range of 80 to 97 ° C, preferably even higher, in the range of 90 to 96 ° C.
[0089] To achieve particles containing low viscosity cellulose, that is, particles with a viscosity of less than 2.5 Pa.s (2,500 cps), for example, 1 Pa.s (1,000 cps) or less, with significant particle discoloration, preferably the mixture should be heated to a temperature between 90 to 100 ° C and maintained at that temperature for at least 2 hours until the desired viscosity has been reached and maximum discoloration has occurred.
[0090] If the mixture provided in step (i) is already hot, from cooking the vegetable material to provide a pulp, then it is possible that not much more additional heating of the mixture is required. If this is the case, then the heating of step (ii) has already been partially or completely carried out in step (i). The heating step is terminated by cooling the mixture from step (ii). Preferably, the mixture is cooled quickly.
[0091] Step (ii) can also comprise a step according to which the mixture is homogenized. This can occur during warm-up and shorten the duration of step (ii). Alternatively or in addition, homogenization can occur after heating. If hot peroxide is a problem for any of the equipment that is used, then homogenization can be performed after the heating stage is completed and the material has been cooled. In one embodiment, the process of the invention involves homogenizing the mixture from step (ii) either while the mixture is being kept at temperature or after the mixture has been cooled or both.
[0092] In one embodiment of the process described in this document, the 35% aqueous peroxide solution can be added in an amount of 0.5% by weight or less than the weight of the herbaceous plant material (dry content) and treatment with peroxide run until substantially all of the peroxide has been consumed and the reaction is then immediately ended. In this embodiment, a particulate cellulose material with a viscosity of at least 2.5 Pa.s (2,500 cps) (at a solids concentration of 1% by weight) is obtained.
[0093] In one embodiment of the process described in this document, the 35% aqueous peroxide solution can be added in a ratio of 0.5 parts peroxide solution or less to 1 part herbaceous plant material (dry content), for example, 0.25 parts of peroxide solution to 1 part of herbaceous plant material (dry content) and the peroxide treatment carried out until substantially all of the peroxide has been consumed and the reaction immediately ended. In this embodiment, a particulate cellulose material with a viscosity of at least 2.5 Pa.s (2,500 cps) (at a solids concentration of 1% by weight) is obtained.
[0094] In one embodiment of the process described in this document, the conditions for the peroxide treatment step can be continued after substantially all of the peroxide has been consumed. In one embodiment, the reaction can be continued for at least another 30 minutes, for example, at least 40 minutes or at least 60 minutes. In that embodiment, a particulate cellulose material with a viscosity of less than 2.5 Pa.s (2,500 cps), for example, less than 1 Pa.s (1,000 cps) (at a solids concentration of 1% in weight) is obtained. Step (iii)
[0095] In step (iii) of the process of the invention, a residue comprising the particles containing cellulose is isolated. This can be achieved by washing and filtering the product from step (ii). Washing removes any soluble broken products from the reaction and any excess peroxide reagent. Excess peroxide in the product of step (ii) can also be removed by adding a catalyst. Washing can be achieved using several different processes, such as centrifugal filtration (continuous or batch), microfiltration, filter pressing or simple gravity-driven filtration. The peroxide level and pH can be checked. The peroxide content should preferably be less than 30 mg / L (as measured using a peroxide indicator stick) and the pH should preferably be between 6 and 9. Optionally, the material can be then pressed or concentrated to reduce the water content, for example, up to 20 to 50% by weight of solids. This pressed cake can then be resized by cutting / grinding it to a powder. This powder may be capable of rapid redispersion and rehydration when added to water-based systems. Step (iv)
[0096] The process of the invention may optionally comprise an additional step of contacting the particles containing cellulose with an oxidizer. The oxidant may be sodium hypochlorite. The cellulose-containing particles can be washed with water and, optionally, filtered, before being contacted with the oxidizer. The washed and filtered cellulose containing particles can be reconstituted in water before being contacted with the oxidizer. The oxidizer step can be carried out at a temperature of about 60 ° C or less. The oxidant can be added in a ratio of about 1 part of oxidant to 2 parts of solids in aqueous solution. The oxidant may be in the form of a 10% aqueous solution of the active oxidizer. The temperature of the oxidizer step can be maintained for at least 10 minutes, for example, at least 20 minutes, up to about 30 minutes. The resulting particles containing cellulose can be separated from the oxidizer solution and washed with water until they are free of residual oxidant. Washing can be achieved using several different processes, such as centrifugal filtration (continuous or batch), microfiltration, filter pressing or simple gravity-driven filtration. Step (v)
[0097] The process of the invention can optionally comprise the mixture obtained from step (iii) or step (iv). The homogenization step can take place in the filtered and dried material from step (iii) or from step (iv). The homogenization step can occur in the material obtained from step (iii) or from step (iv) that has been reconstituted in water. Homogenization can be carried out until a desired particle is obtained. Stage (vi)
[0098] The process may comprise an additional step of concentrating the particulate cellulose material or particles containing cellulose obtained to a particular concentration. The material can be concentrated to a level of, for example, at least 5% by weight of solids, for example, at least about 10% by weight of solids, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, for example, about 30% by weight of solids. At levels of 15% by weight of solids or more, the material can be grated, which can be advantageous in some applications. Lower loading levels result in a paste-like consistency, which can be advantageous in other applications. USES OF PARTICULATED CELLULOSE MATERIALS
[0099] Cellulose and cellulose-derived materials are known as additives in different industries due, at least in part, to the properties of viscosity modification. The present invention, therefore, also relates to water-based, i.e., aqueous, systems or compositions comprising the cellulose-containing particles of the present invention. Water-based systems, as referred to in this document, include aqueous solutions and emulsions. Examples are water-based epoxy, acrylic, polyurethane paints and water-based cosmetic systems, such as hair shampoos, hair conditioners and facial creams. Additional examples are food compositions. Typically, in water-based systems, the cellulose-containing particles of the invention are present in an amount of less than 10% by weight, less than 5% by weight, for example, less than 3% by weight, of preferably less than 1% by weight, more preferably 0.05 to 0.2 or 0.5% by weight The cellulose containing particles of the invention can be present in any of these compositions in an amount of at least 0 , 05% by weight, at least about 0.2% by weight, at least about 0.5% by weight, at least about 1% by weight, at least about 3% by weight, at least about 5% by weight, at least about 10% by weight. In some embodiments, the cellulose particulate material is incorporated into the aqueous compositions in an amount of less than about 1.5% by weight, less than about 1.2% by weight, less than about 1% by weight. weight, less than about 0.5% by weight, less than about 0.4% by weight, less than about 0.3% by weight, less than about 0.25% by weight, less than about 0.2% by weight, less than about 0.1% by weight, less than about 0.05% by weight, less than about 0.04% by weight, less than than about 0.03% by weight, less than about 0.02% by weight, for example about 0.01% by weight. COMPOSITE MATERIALS
[00100] The invention, therefore, refers to compositions and composite materials, such as concrete and other cementitious materials. The particulate material described in this document is particularly useful as a reinforcing agent in concrete, other cementitious materials and resin composites.
[00101] In one aspect, the invention provides a composite material comprising a resin and up to about 90% by weight of plant-derived cellulose particulate material, wherein the plant-derived cellulose particulate material comprises less than 30% by weight of extractable glucose; and extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material. The plant-derived cellulose particulate material can be present in an amount of up to about 85% by weight, for example, up to about 80% by weight, up to about 75% by weight, up to about 70% by weight, up to about 65% by weight.
[00102] The resin can be a thermostable resin or a thermoplastic resin. The thermostable resin can be based on polyester or based on epoxide, but it should be understood that these are examples only and other thermostable resins, such as polyurethanes, could also be used. There are many thermoplastic resins used in composite manufacturing: polyolefins, polyamides, vinyl polymers, polyacetals, polysulfones, polycarbonates, polyphenylenes and polyimides. In one embodiment, the resin can be an acrylic resin. The resin can be a single resin or the resin can be a mixture of more than one resin, including any of the resins described above. The composite material may further comprise one or more binders, for example, a hydrophilic binder and / or a hydrophobic binder. Such additives for composite resin materials are known in the art and do not need further discussion here.
[00103] In one aspect, the invention provides cementitious compositions comprising particles containing cellulose or particulate cellulose material. The particulate material can be present in an amount of less than 10% by weight, less than 5% by weight, for example, less than about 2% by weight, for example, less than about 1% by weight. Weight. The cementitious composition can comprise any known cement. For example, the cementitious composition may comprise a hydraulic cement, such as Portland cement, which can also be replaced, at least in part, by, for example, soot, slag cement or silica smoke to form a cement mix. Portland. The cementitious composition may comprise other additives and fillers known in the art, such as air introducing agents, settling retardants, settling accelerators and the like.
[00104] In one aspect, the invention provides concrete compositions comprising particles containing cellulose or particulate cellulose material. The particulate material can be present in an amount of less than 10% by weight, less than 5% by weight, for example, less than about 2% by weight, for example, less than about 1% by weight. Weight. The concrete composition generously comprises the particulate cellulose material described in this document, a cement and an inert aggregate material, such as sand or a mixture of sand and larger particles, such as gravel. Cement can be any type of cement, as previously described. Any type of load / aggregate that is commonly used in the construction industry can be used effectively in the context of this invention. Examples of fillers / aggregates, such as silica sand, calcium carbonate, dolomite, as well as light aggregates, such as pearlites, polystyrene microspheres, cork from hollow / expanded glass or ceramic beads, rubber and the like and a mixture of themselves. The proportion of load / aggregate in the cement or mortar is preferably between 50% and about 85%, more preferably between 60% and about 80% and most preferably between 65% and about 75% by weight , based on total dry ingredients. It should be understood that water will subsequently be added in order to produce the final concrete mixture to be cured. COATINGS
[00105] The particulate cellulose material is also known to be used in coating compositions as a viscosity modifier or for reinforcing structure to prevent, for example, cracking.
[00106] Therefore, in one aspect, the invention provides a coating composition comprising particles containing cellulose or particulate cellulose material. The particulate material can be present in an amount of less than 10% by weight, less than 5% by weight, for example, less than about 2% by weight, for example, less than about 1% by weight. Weight. The coating composition can be an ink composition. The coating composition generally comprises a diluent or solvent, typically water, a pigment (for example, calcium carbonate, mica, silica, talc), a filler (whose function can be provided by the pigment or an inert material separate) and one or more additional additives, such as adhesion promoters, texturizers, UV stabilizers, planers or biocides, as non-limiting examples. Such coating additives are typically present in the composition in an amount of about 0 to about 18% by weight or up to 18% by weight and from about 1 to about 15% by weight based on the total weight of the formulation. . FOOD COMPOSITIONS
[00107] The particulate cellulose material is routinely added to food compositions such as a stabilizer, an emulsifier or a thickener to modify the viscosity of the food composition. Therefore, in one aspect, the invention provides a food composition that comprises particles containing cellulose or particulate cellulose material. The particulate material can be present in an amount of less than 10% by weight, less than 5% by weight, for example, less than about 2% by weight, for example, less than about 1% by weight. weight, less than 0.5% by weight. The food composition may be an animal feed composition. The food composition may be a baby food composition.
[00108] These food compositions may include emulsions, beverages, sauces, soups, syrups, toppings, films, milks and dairy and non-dairy products, frozen desserts, elaborated foods, bakery fillings and bread cream. Edible food products can additionally comprise various edible materials and additives, including proteins, fruit and vegetable juices, fruit or vegetable pulps, fruit flavored substances or any combination thereof. Such food products may also include other edible ingredients, such as, for example, mineral salts, protein sources, acidulants, sweeteners, buffering agents, pH modifiers, stabilizing salts or a combination thereof. Those skilled in the art will realize that any number of other edible components can also be added, for example, additional flavorings, colors, preservatives, pH buffers, nutritional supplements, process aids and the like. The additional edible ingredients can be soluble or insoluble and, if insoluble, can be suspended in the food product. Routine adjustment of the composition is completely within the capabilities of an element of ordinary skill in the art and is within the scope and intention of the present invention. These edible food products can be dry mix products (instant sauces, meat sauces, soups, instant cocoa drinks, etc.), low pH dairy systems (sour cream / yogurt, yogurt drinks, stabilized frozen yogurt, etc. .), bakery products and as a bulking agent in non-aqueous food systems and low hydration food systems.
[00109] In some embodiments, food compositions may have enhanced storage capacity without the need for adjunct stabilizers (in addition to the particulate cellulose material used in the compositions). For example, some sauces that lack an adjunct stabilizer, such as xanthan gum, have been shown to maintain relative viscosity for extended periods of time, which in some cases is at least six months. The final compositions can be processed by heat treatment in any number of ways. These methods may, however, include, without limitation, pasteurization, ultra pasteurization, high temperature short term pasteurization ("HTST") and ultra high temperature pasteurization ("UHT"). These compositions can also be processed in retort, or processing and rotary retort or static retort. Some compositions, such as natural or artificially flavored or juice-added soft drinks, can be processed cold. Many of these processes can also incorporate homogenization or other high shear / high compression processes. There may also be Cossack compositions, which can be prepared as a dry mix and then conveniently reconstituted for consumption as needed. The resulting compositions can be refrigerated and stored for a commercially acceptable period of time. Alternatively, the resulting drinks can be stored at room temperature, as long as they are filled under aseptic conditions. PERSONAL CARE AND HOUSEHOLD PRODUCTS
[00110] In accordance with the present invention, the composition can be either a personal care product or a home care product. The personal care product can be a facial cream, a shampoo, a conditioner, a sun protection composition or a moisturizer, for example. When the composition is a personal care product, it can contain at least one active personal care ingredient, including, but not limited to, pain relievers, anesthetics, antibiotic agents, antifungal agents, antiseptic agents, anti-dandruff agents, antibacterial agents, vitamins, hormones , corticosteroids, anti-inflammatory agents, vasodilators, chemotherapy agents, dry eye compositions, wound healing agents, anti-infection agents, as well as solvents, diluents, adjuvants and other ingredients such as water, ethyl alcohol , isopropyl alcohol, propylene glycol, higher alcohols, glycerin, sorbitol, mineral oil, preservatives, surfactants, propellants, fragrances and essential oils.
[00111] Personal care compositions include hair care, peel, sun care, nail care and oral care compositions. Examples of additives in personal care compositions include perfume, peel coolers, emollients, deodorants in addition to perfumes, antiperspirant actives, moisturizing agents, cleaning agents, active sun protection ingredients. Examples of additives in hair compositions include agents that condition and / or clean hair, clean hair, detangle hair, act as styling agents, swelling and shine agents, color retention agent, anti-dandruff agent, hair growth promoters, hair dyes and pigments, hair perfumes, hair relaxers, hair lightening agents, hair moisturizers, hair oil treatment agents and anti-frizz agents.
[00112] The composition may be a household care composition, wherein that household care composition includes cellulose particulate material and at least one active household care ingredient. The active ingredient in home care needs to provide some benefit to the user. The household care composition may comprise a laundry detergent, a fabric softener, a dishwasher detergent, a surface cleaner. The composition may also include retreatment compositions, bleaching agents and water softeners, including, above all, anionic, non-ionic, cationic, amphoteric and zwitterionic surfactants, water-soluble and water-insoluble reinforcers and reinforcers, inorganic and bleaching agents, more specifically peroxide bleaching agents and active chlorine compounds that are advantageously coated, bleaching activators and bleaching catalysts, enzymes and enzyme stabilizers, foam inhibitors, redeposition inhibitors, substances that prevent re-stain fabrics, so-called dirt repellents, and typical inorganic salts, such as organic sulphates and sulphates, such as phosphonates, optical brighteners and dyes and perfumes. Additionally, the use of conventional silver protectors is recommended for dishwasher detergents. These additives can be incorporated in quantities known to the skilled person.
[00113] The particulate cellulose material can be present in an emulsion. The emulsion may comprise an aqueous phase, an oil phase and less than 10% by weight of plant-derived cellulose particulate material, wherein the plant-derived cellulose particulate material comprises less than 30% by weight of extractable glucose; and extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material. The emulsion can form the basis of a personal care product, a home care product or a food composition, as described above. PAPER
[00114] Cellulose materials also form the basis for papers and cardboard. Additives are often added to papers and / or cardboard to enhance physical or chemical properties. In particular, it is desirable to reduce the porosity of a paper or cardboard in order to block the permeation of gases, for example, odors, fragrances or oxidants, or to block the permeation of microbes and viral particles, when packaging food products or products cosmetic or perfumed. Therefore, in one aspect, the invention provides a paper composition that comprises less than about 40% by weight of plant-derived cellulose particulate material, wherein the plant-derived cellulose particulate material comprises less than 30% by weight. extractable glucose weight; and extractable xylose in an amount of at least 5% of the amount of extractable xylose in the starting plant material. The paper composition may comprise less than about 25% by weight, for example less than about 20% by weight, less than about 5% by weight of the plant-derived cellulose particulate material. Alternatively, the paper composition may comprise more than about 5% by weight, for example, more than about 10% by weight, more than about 15% by weight, more than about 20% by weight , more than about 25% by weight, more than about 30% by weight, up to about 40% by weight of the plant-derived cellulose particulate material. The paper composition may comprise a cellulosic pulp known to be useful in paper production, in combination with the particulate cellulose material described herein. The paper composition may further comprise one or more additives, such as inorganic fillers, optical bleaching agents and pigments.
[00115] The invention is further described, however, without limitation, by the following examples. EXAMPLES EXAMPLE 1: Method for measuring viscosity and pH with reaction time for root vegetable pulp treated with hydrogen peroxide
[00116] Fresh carrots were peeled, cut and cooked at 90 ° C for 2 hours. The carrots were then homogenized in the cooking liquid, using a Silverson FX homogenizer, to form a pulp with particles less than 500 microns in diameter. The pulp concentration was measured, using a hydration analyzer, as being 5% solids in water. The batch was then divided into several 1-liter samples, each contained in a polypropylene bottle with a tight fitting cap. These bottles were then placed in a 90 ° C hot water bath. The internal temperatures of the bottles were checked periodically. When the temperature reached 90 ° C, 35% hydrogen peroxide was added to each bottle in a ratio of 1 part 35% peroxide to 1 part carrot solids. The bottles were then left in the water at 90 ° C for varying lengths of time. The bottles were removed from the water bath at intervals and cooled quickly by placing them in a cold water bath. The pH of the contents was immediately measured using a pH meter. The contents were then poured into a thick filter made of frozen horticultural wool (pore size of approximately 250 microns) and the liquid allowed to drain. The remaining solids were washed 3 times with clean water. Then, the remaining solids were scraped from the filter in a clean beaker. This pulp was homogenized with the use of a Silverson L5M bench with a fine notched collar attached to the head. Homogenization was performed for 15 minutes at 8,000 rpm. The content of solids in the homogenized pulp was then measured using a hydration analyzer and adjusted to 1% with fresh water. The temperature at that point was measured as 20 ° C. The pulp viscosity was then measured at a concentration of 1% in dry weight using a Brookfield DVII + Pro EXTRA viscometer, with RV axis heads, running at 10 rpm. Viscosity was recorded in pascal-seconds (Pa.s) (centipoise (cps)). The data from these experiments were then used to plot viscosity as a function of time and pH as a function of time and this graph is shown in Figure 1. EXAMPLE 2: Preparation of high-viscosity cellulose particulate material from sugar beet
[00117] 900 g of sugar beet pellets were washed and drained by adding them to warm water, with dirty water being drained through a sieve. This sugar beet hydrate is placed in a large bucket of excess water and stirred before being removed with a colander and washed with water, to ensure that no stones / gravel enter the next stage of processing.
[00118] The washed sugar beet is then cooked for 3 hours at 100 ° C, before being homogenized using a Silverson FX homogenizer adjusted with initially thick stator screens and moving down until the emulsifier sieve with a small hole (15 min process time for each sieve). The solids are measured using an Oxford solid meter and the mixture adjusted to 2% solids by adding clean water.
[00119] The mixture is then placed in a 25 liter glass reaction vessel and the dry solids content in the vessel is calculated. Peroxide, based on the ratio of aqueous peroxide solution (35%) to dry solids of 0.25: 1, is added when the mixture is heating. The temperature is maintained for 2 hours at 90 ° C (once it has reached 90 ° C), during which time the pH has been reduced from about 5 to 3.5.
[00120] The reaction liquid is then removed from the vessel and washed before bleaching.
[00121] The bleaching is then carried out by resuspending the washed material in clean water and placing it back in the vessel. Bleaching is carried out at 60 ° C, with a 2: 1 bleach (2 parts of bleaching solution with 10% active chlorine to 1 part of solids, for 30 minutes).
[00122] The material is then washed and homogenized for 30 minutes in the fine notched stator sieve of the Silverson FX homogenizer.
[00123] The material is then drained through a filter and pressed between absorbent cloths to a desired final solids content. Resuspending the solids in water at 1% by weight of solids resulted in a viscosity (measured as previously described) of 4.6 Pa.s (4,600 cps). EXAMPLE 3: Comparative Study: Carrots (A) Process that results in high viscosity material
[00124] Fresh carrots were cooked and homogenized to produce a pulp in water with 5% carrot pulp solids. Hydrogen peroxide was then added in the ratio of 1 part of carrot solids to 0.35 part of peroxide solids. The mixture formed the reaction liquid. The liquid was then heated to 90 ° C and the reaction allowed to progress for 1 h, at which point the pH dropped from 5.2 to 4.75. The resulting liquid was quickly cooled and washed and filtered, at which point the viscosity of a mixture of 1% solids in water was 3.8 Pa.s (3,800 cps) at 10 rpm (measured by the Brookfield Viscometer with RV shaft heads at 20 ° C). (B) Process that results in low viscosity material
[00125] Fresh carrots were cooked and homogenized to produce a pulp in water with 5% carrot pulp solids. Hydrogen peroxide was then added in the ratio of 1 part of carrot solids to 0.35 part of peroxide solids. The mixture formed the reaction liquid. The liquid was then heated to 90 ° C and the reaction allowed to progress for 6 h, at which point the pH dropped from 5 to 2.
[00126] The resulting liquid was quickly cooled and washed and filtered, at which point the viscosity of a mixture of 1% solids in water was 0.6 Pa.s (600 cps) at 10 rpm (measured by the Brookfield Viscometer with heads axis, at 20 ° C). EXAMPLE 4: Product Analysis
[00127] The dry material of three stages of the process (beginning; after treatment with peroxide; after treatment with sodium hypochlorite) was analyzed by extractable monosaccharide / polysaccharide content. The starting vegetable materials tested were sugar beet and carrots. Comparative examples in the form of (i) cellulosic particulate material obtained from treatment with sodium hydroxide and carrots, as described in WO 2014/017911 ("Cellucomp 8"); and (ii) the material from (i) also subjected to a subsequent bleaching treatment ("Cellucomp 9") and subjected to some analysis.
[00128] The test procedure was performed according to the standard two-step protocol below, which is based on the separation of monosaccharides and oligosaccharides from polysaccharides by boiling the sample in an 80% alcohol solution. Monosaccharides and oligosaccharides are soluble in alcoholic solutions, while polysaccharides and fibers are insoluble.
[00129] Soluble components can be separated from insoluble components by filtration or centrifugation. The two fractions (soluble and insoluble) can then be dried and weighed to determine their concentrations.
[00130] The dry materials can then be used for analysis by HPLC, after acid hydrolysis. (I) Separation of soluble and insoluble components Materials
[00131] • Dry samples
[00132] • 80% Ethanol
[00133] • Compressed Nitrogen Method
[00134] For each material sample, 50 mg was extracted three times with 5 ml_ of 80% ethanol, by boiling the samples in glass tubes covered in a 95 ° C water bath for 10 min each. After each extraction, the tubes were centrifuged at 5,000 x g for 5 min, and the supernatants from the three extractions combined for sugar analysis.
[00135] The residue and the supernatant are dried in the oven before acid hydrolysis. Acid hydrolysis with the use of trifluoroacetic acid degrades pectins, hemicelluloses and highly amorphous regions of cellulose, while acid hydrolysis with the use of 72% (w / v) sulfuric acid degrades all polysaccharides except for highly crystalline regions of cellulose. (ii) (a) Analysis of matrix polysaccharides - Hydrolysis with trifluoroacetic acid Materials
[00136] • Dry samples
[00137] • Tubes with screw cap
[00138] • 2 M trifluoroacetic acid = 11.4 g in 50 ml (or 3 ml of 99.5% TFA and 17 ml of dH2O)
[00139] • Compressed Nitrogen
[00140] • Monosaccharide standards
[00141] o Mixture of standard sugars from three monosaccharides (glucose, fructose, xylose). Each sugar is in a 10 mM (100X) stock solution. The preparation of the standards is done by pipetting 250, 500 and 750 pl into flasks with a screw cap and evaporating to dryness. Proceed for hydrolysis in the same way with the samples. METHOD DAY 1
[00142] • Weigh 5 mg of the alcohol-insoluble fraction from step (i) in tubes with screw cap
[00143] • Dry all monosaccharide samples and standards (250 pl, 500 pl, 750 pl) DAY 2
[00144] • In the hood, hydrolyze by adding 0.5 mL of 2 M TFA. Flush the flasks with dry nitrogen, put the cap on and mix well. Rub the nitrogen nozzle with ethanol fabric between samples to prevent contamination.
[00145] • Heat the flasks at 100 ° C for 4 h and mix several times during hydrolysis.
[00146] • Evaporate completely in a centrifugal evaporator or under a jet of nitrogen with steam extraction overnight. DAY 3
[00147] • Add 500 pl of propan-2-ol, mix and evaporate.
[00148] • Repeat
[00149] • Resuspend samples and standards in 200 pl dhW. Mix well.
[00150] • Centrifuge and transfer the supernatant to a new tube.
[00151] • Filter the supernatant through 0.45 pm PTFE filters before HPLC analysis. (ii) (b) Analysis of matrix polysaccharides - hydrolysis with sulfuric acid Materials
[00152] Sulfuric acid 72% (w / v) (AR)
[00153] Barium hydroxide (150 mM)
[00154] Bromophenol blue (1% solution in water)
[00155] 0.45 pm filters
[00156] Reverse phase of SPE (styrene divinylbenzene); for example, Strata-X 30 mg, 1 mL in volume. Method
[00157] • Weigh precisely 4 mg of the alcohol-insoluble fraction from step (i) in a 2.0 ml screw-top microcentrifuge tube. Alternatively, the dry residue pig from the digestion of matrix sugar.
[00158] • Additional 70 pl of 72% (w / v) sulfuric acid to the screw top bottle. Mix until the solids are dispersed / dissolved.
[00159] • Incubate in a water bath at 30 ° C for 2 hours. Mix samples every 15 minutes.
[00160] • Add water to reduce the sulfuric acid concentration to 4.6% (w / w) - add 1,530 pi of water.
[00161] • Mix well and heat in a block heater at 121 ° C or 4 hours. Vortex every 30 minutes.
[00162] • Cool to room temperature. (Samples can be stored in a refrigerator for up to 2 weeks at this point).
[00163] • Take 300 pl in a new tube and add 1 pl of 1% bromophenol blue. Partially neutralize by adding 0.8 mL of 150 mM barium hydroxide. Finish by adopting powdered barium carbonate. The indicator turns blue.
[00164] • Centrifuge to remove precipitated barium sulfate (10 min at 10,000 x g). Transfer the supernatant to a new tube. Freeze / thaw to finish the precipitation and repeat the centrifugation (total volume 1.050 pl).
[00165] • Before HPLC, the samples (700 pl aliquot) are passed through a reverse phase column (for example, strata X 30 mg) and filtered through a 0.45 pm filter.
[00166] The results of these analyzes, in relation to the xylose content and the glucose content, are shown in Table 1 below. Quantitative data can be obtained by injecting an amount of a reference monosaccharide, for example, glucose or xylose, as is routine in the art. TABLE 1

EXAMPLE 5: Ink Study
[00167] Two sets of ink formulations were made (see Tables 2 and 3 below). One was produced with an epoxy resin system and the other with an acrylic resin system. For each set, several batches were produced containing different amounts of the primary cellulose containing particles of Example 3a. The weight of all additives in both epoxy and acrylic formulations was kept constant from one batch to the next, except for water and viscosity modifier. The viscosity modifier weight was varied from batch to batch, to test the effects of different levels of addition on the formulation's viscosity. In order to keep the formulation weight constant, the weight of water added to a batch was also adjusted depending on the level of addition of the viscosity modifier, so that the weight of water plus the viscosity modifier were constant from one batch to another. .
[00168] The particles containing cellulose were pressed to reduce the water content up to 25% solids, then grated with the use of a parmesan cheese grater in a coarse powder. The ingredients of each formulation were mixed together at room temperature with the use of a Dispermat paint mixer, with a 4 cm diameter sawtooth blade at 3,000 rpm. The mixing was carried out for 1 h to ensure that all ingredients were completely dispersed. The mixed formulations were allowed to rest for 1 day. Then, the viscosity of each sample was scanned by a range of shear rates using a rheometer.
[00169] For the epoxy formulation, a reference mark, which was a well-known bentonite clay rheology modifier, was used to allow comparison with the cell wall material. It was mixed in the formulation at a concentration of 0.25% by weight of total formulation.
[00170] Similarly for the acrylic formulation, a suitable reference mark was used for comparison, which was an associative thickener Acrysol. It was mixed in the formulation at 0.6% by weight of total formulation. TABLE 2

[00171] A graph showing viscosity as a function of shear rate for an epoxy paint formulation with varying amounts of cellulose containing particles added as a viscosity modifier (identified here as A) and compared to a viscosity modifier of Bentonite clay (identified as Bentone EW) is shown in Figure 2. It can be seen that the use of 0.15% of particles containing cellulose generates higher viscosities in the epoxy formulation than in Bentonite clay, particularly at low shear rates. TABLE 3

[00172] A graph showing viscosity as a function of shear rate for an acrylic paint formulation with varying amounts of cellulose-containing particles added as a viscosity modifier (identified here as A) and compared to an associative thickener that acts as a viscosity modifier (Acrysol) is shown in Figure 3. These data show that cellulose-containing particles are more pseudoplastic than Acrysol and are particularly effective in generating high viscosity at low shear rates. EXAMPLE 6: CEMENTAL MATERIALS / CONCRETE
[00173] The particulate cellulose material described in this document has been tested for its suitability in composite materials, particularly cementitious materials, such as concrete and mortar.
[00174] The particulate cellulose material was incorporated into a mixture of mortar in quantities of 1% by weight, 5% by weight and 10% by weight as prepared below. The mortar used was a decorative mortar called Enduit Béton Coloré, available from Mercardier. Composition:
[00175] 4.3 kg of powdered cement
[00176] 1 kg of acrylic resin binder
[00177] 1% by weight or 5% by weight of particulate cellulose material (CPM)
[00178] The penetration resistance of the composite material was tested using a 2 mm thick material sample. The test used a 62.5 MPa punch with a 1 cm diameter punch template. The results are shown in Table 4 below: TABLE 4

[00179] These data show that the inclusion of up to 5% by weight of the cellulose particulate material described in this document led to an improvement in the strength of the material, demonstrating that the cellulose particulate material can strengthen or reinforce inorganic composite materials, such as concrete. EXAMPLE 7: PAPER COMPOSITIONS
[00180] A paper composition comprising different amounts of the particulate cellulose material (CPM) described in this document has been tested for opacity and porosity.
[00181] The inclusion of particulate cellulose material, described in this document, decreased the porosity relative to a base paper formed from a standard cellulose. Decreasing the porosity of a paper composition provides advantages for fragrance, cosmetic and food packaging in cases where the permeation of gases, microbes and other substances is undesirable.
[00182] From the examples above, it can be seen that the particulate cellulose materials described in this document and the processes for producing such particulate cellulose materials find use in many different applications.

权利要求:
Claims (19)
[0001]
1. Plant-derived cellulose particulate material, characterized by the fact that it comprises less than 30% by weight of extractable glucose; and extractable xylose in an amount of at least 0.8% by weight, and the particulate cellulose material increases the viscosity of an aqueous composition to more than 2500 cps when added to a concentration of 1% by weight.
[0002]
2. Plant-derived cellulose particulate material according to claim 1, characterized by the fact that it comprises less than 60% by weight of cellulose.
[0003]
3. Cellulose particulate material derived from plant, according to claim 1, characterized by the fact that it is derived from sugar beet.
[0004]
4. Plant-derived cellulose particulate material, according to claim 1, characterized by the fact that it has a non-carbohydrate content of 20 to 50% in dry weight.
[0005]
5. Plant derived cellulose particulate material according to claim 1, characterized by the fact that it comprises particles with an average main dimension of 1 to 250 pm.
[0006]
6. Plant derived cellulose particulate material according to claim 1, characterized by the fact that it comprises a plurality of particles with a water holding capacity in the range of 90 to 99.5% by weight.
[0007]
7. Plant-derived cellulose particulate material according to claim 1, characterized by the fact that it comprises particles with a cellulose content of 40 to 60% by weight, an average principal dimension of 10 to 70 pm, and the material being cellulose particulate increases the viscosity of an aqueous composition up to 5000 cps when added to a concentration of 1% by weight.
[0008]
8. Process for the preparation of particulate material containing cellulose from an herbaceous plant material, characterized by the fact that it comprises the steps of: (i) coming into contact with the herbaceous plant material with a peroxide and water reagent to form a mixture ; (ii) heating the mixture to a temperature of 30 to 110 ° C and maintaining said mixture at a temperature of 30 to 110 ° C until the pH of the mixture drops from about 1 to 2 pH units; and (iii) isolating the cellulose-containing particles, the cellulose-containing particulate material containing less than 30% by weight of extractable glucose, extractable xylose in an amount of at least 0.8% by weight, and the particulate material increases the viscosity of an aqueous composition to more than 2500 cps when added to a concentration of 1% by weight%
[0009]
9. Process according to claim 8, characterized by the fact that the herbaceous plant material comprises more than 30% by volume of parenchymal cell material.
[0010]
10. Process according to claim 8, characterized by the fact that the herbaceous plant material comprises less than 10% by weight of lignocellulose.
[0011]
11. Process according to claim 8, characterized by the fact that the herbaceous plant material is a root vegetable.
[0012]
12. Process according to claim 8, characterized by the fact that the contact step includes the mechanical treatment of the herbal plant material so that it comprises particles with a main dimension of less than 10 mm.
[0013]
13. Process according to claim 8, characterized by the fact that the heating step involves mechanically homogenizing the mixture while the mixture is being kept at that temperature.
[0014]
14. Process according to claim 8, characterized in that the heating of the mixture comprises heating to a temperature of 70 and 100 ° C and maintenance to a temperature of 70 and 100 ° C.
[0015]
15. Process according to claim 8, characterized by the fact that it is carried out in the absence of an alkaline or acidic reagent, and being carried out in the absence of a pH modifying additive.
[0016]
16. Process, according to claim 8, characterized by the fact that it also comprises the contact of particulates containing cellulose with an oxidizer.
[0017]
17. Plant-derived cellulose particulate material according to claim 1, characterized by the fact that it comprises extractable xylose in an amount of at least 1.5% by weight.
[0018]
18. Cellulose particulate material derived from plants, according to claim 1, characterized by the fact that it comprises less than 2% by weight of hemicellulose.
[0019]
19. Process according to claim 8, characterized by the fact that the particulate material containing cellulose comprises extractable xylose in an amount of at least 1.5% by weight and less than 2% by weight of hemicellulose.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C08H 8/00 (2010.01), C08J 3/12 (2006.01), C08L 1/0 |

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2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-24| 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 18/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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2022-01-11| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 8A ANUIDADE. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1304939.0|2013-03-18|

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GB201304939A|GB201304939D0|2013-03-18|2013-03-18|Process for Preparing Cellulose-Containing Particles from Plant Material|

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PCT/GB2014/050858|WO2014147392A1|2013-03-18|2014-03-18|Cellulose particulate material|

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