Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
  • C08J2301/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2397/00—Characterised by the use of lignin-containing materials
  • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

• the present invention is directed to a method for producing a cellulose-containing mass according to claim 1 , a cellulose-containing mass according to claim 17 , a method for producing a composite material according to claim 18 , a composite material according to claim 23 and a product according to claim 24 .
• the method may be employed for a diversity of practical uses. For instance, production of new building materials, different hardware, trimmings, interior stuff, various finishing coats of high resistibility and fastness etc. from farm waste of cereals (for example maize, rye, wheat, oats, barley, sorghum, rape, rice etc. and combinations thereof), staple fibers (cotton, flax, hemp, etc.), what makes such production economically compatible due to low price of inputs.
• farm waste of cereals for example maize, rye, wheat, oats, barley, sorghum, rape, rice etc. and combinations thereof
• staple fibers cotton, flax, hemp, etc.
• U.S.2006043629A proposes to produce a reinforced bio-composite by processing of natural fibers (such as grass, rice straw, wheat straw, industrial hemp, pineapple leaf fibers) with a matrix of soy based bioplastic, by employing a coupling agent, i.e. a functional monomer modified polymer.
• a coupling agent i.e. a functional monomer modified polymer.
• modified soy flour with functional monomers is explained in the context of industrial applications such as reactive extrusion and injection molding.
• U.S. 2008/181969 A addresses discoloration and structural, that is chemical or mechanical, degradation of composite materials comprising cellulosic components such as wood fibers, straw, grasses and other organic material that is cross linked by means of coupling agents to polymer components.
• the coupling agents such as grafted-maleic anhydride polymers or copolymers, incorporate functionality capable of forming covalent bonds within or between the polymer and cellulosic components.
• the invention relates to production of high-strength composite materials and various items made of cheap organic raw-materials, preferably of stalk parts of higher plants, cell envelopes or membrane that contain sufficient quantity of cellulose, i.e. a high-molecular polysaccharide or glucan composed of ⁇ -1,4-linked D-glucose, or chitin, a glycan composed of beta-1,4-linked N-acetyl-D-glucosamine.
• cellulose-containing mass, input and/or composite shall comprise also chitin containing masses, inputs and/or composites or mixtures of cellulose and chitin containing masses, inputs and/or composites.
• Cellulose the most common organic compound on Earth—is a high-molecular polysaccharide (glycan) with formula [C 6 H 7 O 2 (OH) 3 ] n structured into polymer chains of ⁇ -glucose units, where n ranges from hundreds to some thousands.
• the invention allows to produce composite materials without requiring the use of exogenous polymeric components for bonding the organic materials, for example the plant particles to each other.
• exogenous denotes that the polymeric component origins not from the organic raw material being processed. It is an essential feature of the novel method of producing a cellulose-containing mass that the organic material is exposed to an active zone of an artificial electromagnetic field.
• the new method for producing a cellulose-containing mass that may be used for producing a composite material being suitable for a high-strength product comprises at least the steps of
• said input is further to step b) or alternatively to step b) exposed to an active zone of an artificial electromagnetic field.
• natural forms of inputs are destructed, as well as their organic linkages of intracellular and intercellular structures, until a liquid and/or paste mass is produced.
• This mass is used further as molding sand: it is reshaped with new geometrical form, and structural linkages are recovered while this paste is curing. Cured paste becomes the end-use item.
• the term input is used to refer to the starting substance or mixture of substances that is exposed to the electromagnetic field whereas the term cellulose-containing mass denotes the product produced by the aforementioned method according to the invention.
• Said product is considered to be an intermediate product (also called output) as it is used further for the production of a wide variety of products.
• the idea of the method lies in the fact that during manufacturing natural forms of inputs are destructed, as well as their organic linkages of intracellular and intercellular structures do, until homogenous liquid and/or paste mass is produced.
• a cellulose-containing mass is used further as molding sand: it is reshaped with new geometrical form, and structural linkages are recovered while this paste is curing. Cured paste becomes the end-use item.
• additional cellulose preferably methyl cellulose and/or carboxy methyl cellulose, preferably in the form of a sodium salt, and/or microcrystalline cellulose is added to the cellulose-containing mass.
• the additional cellulose is at least partially added as concentrated cellulose containing fraction generated in the wet-milling procedure.
• the cellulose containing liquid fraction separated during or after wet-milling can be concentrated by filtration or dehydration until the fraction reaches a desired level of cellulose content in relation to the water content.
• the term organic material is understood to comprise any cellulose containing material.
• the input organic material comprises fibers mixed of cellulose molecules.
• the organic material origins from higher plants preferably from the group of true grasses of the family Gramineae (Poaceae) such as cereal crop or from cotton, hemp or flax or a mixture thereof. Good results have been produced in tests using at least one of cereal straw or rice straw or mixtures thereof as the organic material.
• the organic material is reduced to small particles or even pulp in a pre-processing step before the exposure to the electromagnetic field.
• the organic material of the input is preferably pre-processed/pre-treated depending on the type and conditions of the material. Such conditions are moisture, cleanness, presence of irrelevant natural or artificial elements, the microbial population, the percentage of ⁇ -cellulose in the pure input material responsible for generating bundles of micelles in the form of superfine fibrils. Preliminary determination of organic base content between fibrils and cellulose agglutinating these fibrils into the solidest fibers proved to be advantageous.
• organic materials containing agglutinating or gelling substances like pectin are suitable, but organic materials containing substances like suberins or cutin that are by nature more hydrophobic are suitable as well.
• organic materials containing lignin may also be used. Basic features and properties of products or produced items may be predefined by changing correlation of these and other secondary substances in the cellulose-containing mass.
• Pre-treatments of the organic material encompass maceration, supplemented by electromechanical, hydrodynamic and ultrasonic exposure, as well as boiling, steaming and other known methods of processing raw plant material.
• Cellulose fibers have a noted distinction of high resistance against laceration, barely coming short of steel, and resistance against variance of mechanical and physical exposures.
• a liquid having a pH-value of about 8 or above, more preferably about 8.4 or above may be used for maceration purposes followed and/or accompanied by electromechanical exposure, hydrodynamic exposure, ultrasonic exposure, boiling, steaming or a combination thereof.
• Pretreatment refers to a process that converts lignocellulosic biomass from its native form, in which it is recalcitrant to cellulase enzyme systems, into a form for which cellulose hydrolysis is effective.
• effectively pretreated lignocellulosic materials are characterized by an increased surface area (porosity) accessible to cellulase enzymes, and solubilization or redistribution of lignin.
• Increased porosity results mainly from a combination of disruption of cellulose crystallinity, hemicellulose disruption/solubilization, and lignin redistribution and/or solubilization. The relative effectiveness in accomplishing some (or all) of these factors differs greatly among different existing pretreatment processes.
• the endogenous liquid content i.e. the liquid content provided by the raw organic material itself or originating from the raw organic material
• the liquid content is formed by water.
• other liquids like organic solvents or gases or other fluids may be suitable as liquid contents depending on the demands on the manufacturability and on the characteristics of the article to be formed of the composite material later on.
• it is important that a proper function of the liquid content with the organic material is achievable.
• an excess of the liquid content is extractable in a suitable manner after the cellulose-containing mass is produced, where necessary.
• the liquid content comprises preferably a solvent, e.g. for mellowing the organic material.
• method comprises the steps of providing a reactor having a reaction volume, filling said reaction volume of said reactor with a plurality of substances, which take part in a physical and/or chemical reaction, adding a predetermined portion of ferromagnetic particles into said reaction volume, placing said reactor with its reaction volume between at least two inductors, such that the magnetic fields of said inductors interfere with each other in said reaction volume of said reactor, and supplying each of said inductors with an alternating current of predetermined amplitude and frequency.
• the ferromagnetic particles have an average length in a range of about 0.3 to about 25 mm, preferably in a range of about 3 to 5 mm and diameters of about 0.1 to about 5 mm, preferably of about 0.1 to about 2.5 mm.
• a ratio of 1:3 to 1:5 between diameter and length of the particles has been shown to be especially advantageous.
• the particles are cylindrical according to preferred embodiments. Based on the teachings of the present inventions the person skilled in the art will know that the size of the ferromagnetic particles depends upon and can be optimized according to the input material whereby the sizes may be out of the above mentioned ranges.
• the size and shape of the ferromagnetic particles may be chosen depending on the properties of the cellulose-containing mass, its workability and/or its producibility. Hence other sizes of the ferromagnetic particles may be suitable for working the present invention, too.
• the ratio of the ferromagnetic particles to the input was about 1 to about 20 weight percent.
• a liquid content of the input between 0 to about 40 percent.
• other ratios may be chosen according to particular demands on the workability and/or the producibility of the cellulose-containing mass. They depend upon the type of process (periodic or constant) and within which volume of a container the process is worked. In a preferred embodiment with straw as input material, the working volume of a 2-zone container was 180 millilitres and the amount of the ferromagnetic particles was 14 grams per zone. The particles had the diameter of 250 micrometers on average and a length of 1500 micrometers on average.
• the ratio of liquid to input was as 1 to 3.
• the container was of continuous type. The time of exposure was up to 20 seconds.
• the ferromagnetic particles support the disintegration of the organic material supra- and subcellular level, as well as the breaking of organic linkages of intracellular and/or intercellular structures.
• the stirred fluidized bed of ferromagnetic particles is energetically charged, and has increased capacities to destruct the whole range of organic materials in comparison to means known in the art. By mechanical crushing, breaking and/or grinding the until a more homogenous cellulose-containing mass is produced. Disintegration of the organic material is a key point of the invention.
• a further advantage of the inventive method resides in the mechanical stirring effect of the ferromagnetic particles.
• Said ferromagnetic particles contribute to a mixing and milling effect of the liquid content, the solvent, if any, and the organic material such that the quality of the cellulose-containing mass is further improved.
• the cellulose-containing mass forms the base material for a vast range of composite products with a wide range of shapes, forms and designs.
• Said composites may be produced by direct shaping methods like casting, moulding, pressing or extruding or by subsequently machining the afore mentioned.
• the active zone of the electromagentic field is located between at least two linear electromagnetic inductors which are separated from each other by a gap measuring about 1 mm to about 5 m, preferably about 50 mm to about 1 m.
• the amount of ferromagnetic particles of non-retentive, i.e. low-coercive materials are added to the the input material before and/or during exposure of the input to the electromagnetic field.
• a non-ferromagnetic mixing container may serve as the receptacle during the exposure of the input to the electromagnetic field, Depending on the requirements said mixing container may stretch over the whole distance between the inductors such that a stirred fluidized bed in the whole space of the zone is generated.
• Other receptacles or a passage for a continuous production mode are also suitable for working the present invention.
• ferromagnetic particles of non-retentive, i.e. low-coercive materials in input to be processed in the active zone is particularly advantageous in large scale operations, where the distance between the inductors is about up to 1 or even several meters. In case of such large distances between the inductors it is preferred to increase the amount of ferromagnetic particles accordingly.
• the linear electromagnetic inductors generate alternating electromagnetic fields that run towards each other from opposite directions. At every point in the active zone the inductors excite common alternating electromagnetic field with circular or elliptic podograph of intensity of magnetic component, spinning around a common axis that is situated between inductors. The magnitude of magnetic component at every point of the axis equals to zero, but in every other direction and/or points it grows up to an amplitude value predetermined in the inductor.
• Tests proved that good results are achievable with amplitude values of about 0.2 Tesla (SI-Unit: T) to 0.25 T in the center of a 50 mm gap between the inductors with 14 g ferromagnetic particles present in a 180 ml container and an active zone between inductors of 50 ⁇ 165 ⁇ 80 mm and a magnetic force of about 0.03 T.
• the duration of exposure of the input to the magnetic field was about 20 seconds.
• the electromagnetic field produced by the at least two electromagnetic inductors has a force of about 0.01 to about 20 T, preferably about 0.01 to about 10 T, most preferred about 0.03 to about 1.2 T.
• the exposure time of the input to the electromagnetic field is depending on the magnetic force applied and the material treated. Good results, that means cellulose-containing masses with superior properties have been achieved with a duration of said exposure measuring about 1 second to about 3 hours, preferably about 5 seconds to 5 minutes, most preferred about 20 seconds.
• the degree of the homogeneity of the cellulose-containing mass is adjustable by the electric parameters of the inductors.
• the wet-milling procedure is performed with high-speed cutting mills with high frequency cutting strokes for the fine grinding of the cellulose-containing input, for example straw.
• a fine cutting mill of the CONDUX CS 500 or CS 1000Z type, available from Netzsch-Condux Mahltechnik GmbH, Rodenbacher Chausee 1, D-63457 Hanau/Wolfgang, Germany which is intended for dry milling was adapted and used for wet-milling of the input at elevated temperatures.
• the intermediate product can—according to further preferred embodiments—be mixed with additional cellulose, for example in a high-performance Ringlayer Mixer CoriMix® CM available from Gebr. Lödige Maschinenbau GmbH, Elsener Stra ⁇ e 7-9, 33102 Paderborn, Germany.
• Such mixers are actually not only mixing but also further homogenizing and comminuting. Their preferred performance is based on the high peripheral speed of the mixing mechanism of up to 40 m/s.
• the resultant centrifugal force forms a concentric annular layer of the input comprising the least one organic material and the hot liquid content.
• the profile of the annular layer features a high mixing intensity, which is caused by the high differential speed between the rotating specially shaped mixing tools and the mixer wall.
• the product is moved through the mixing chamber in a plug-like flow, with the residence time being influenced by the degree of filling, the number of revolutions, the geometry and adjustment of the mixing tools as well as the mixing vessel length and the volume flow rate,
• the mixing chamber may be divided into zones of different shear intensity, and preferably the mixer is combined with a turbulent mixer also known from and available from Lödige Maschinenbau GmbH.
• MCC microcrystalline cellulose
• microcrystalline cellulose especially when added to inputs containing primarily cereal straw, resulted in cellulose-containing mass which were preferably used for producing composite materials of high strength, Said composite materials produced form microcrystalline cellulose containing masses have increased hardness and tensile strength when compared to similar composites produced without the addition of microcrystalline cellulose.
• the cellulose-containing mass After termination of the mixing the cellulose-containing mass is ready to be used for producing a composite material and for producing a desired product of said cellulose-containing mass.
• step number 2 is optional.
• products encompasses end-products, such as for example panels, as well as semi-products, e.g. a core material of a laminated construction such as a sandwich construction, for example.
• semi-products e.g. a core material of a laminated construction such as a sandwich construction
• certain properties of the product may be improved for example in that at least one liner is adhesively bonded to said semi-product.
• An advantage of such sandwich constructions is that different properties such as structural strength, light-weight construction, fire resistance or a combination thereof are conferrable to a product.
• one or several layers or liners may be made of metal, glass or carbon fibers or meshing.
• Such non-organic fibers may be even added to the input or added later on to the cellulose-containing masses according to the invention.
• the cured composite material may be subject to suitable surface treatment that is discussed later on in this description.
• the process of drying and/or curing denotes an extracting of excessive liquid from the cellulose-containing mass.
• Processes of structural linkage recovery appear while the cellulose-containing mass is shaped, for example by curing in casts or molds. Such processes are actually an integration of remains of ⁇ -glucose n-molecules into molecular compound with common to polymers formula [C 6 H 7 O 2 (OH) 3 ] n .
• the presence of glucose molecules with three hydroxyl groups [(OH) groups] in each rest allow that linkage between said rests is facilitated through lateral hydroxyl groups by abstraction of water molecules from them. Therefore, structural linkage recovery of the organic material in the cellulose-containing mass takes place as soon as excessive liquid of the cellulose-containing mass is extracted, for example by desiccation or drying in case of water, resulting in a curing process.
• the dehydration process is carried out under a predetermined temperature by any of a range of known suitable techniques.
• suitable techniques are comprising and/or combining compression, extrusion and filtration as well as absorption, vacuum drying, blowdrying, heating, radiation, patting, vaporization under blower and other methods of desiccation, including natural air drying for example. Selection of a specific method of dehydration depends upon the specific requirements on the process and/or the article to be molded.
• the post-processing of the cellulose-containing mass is performed by at least one of molding, compression molding, injection molding.
• other shaping techniques for producing the product may be suitable.
• the molding and curing operation are carried out together or in sequence.
• Further post-processing may be performed, e.g. for improving the resistance of the article made of the composite material against moisture or water, or to enhance its durability against chemically aggressive environments, the microbiological resistance, to confer the composite material and/or the product with required characteristics in view of a special type of resistance, a specific color, a particular smell or a combination thereof.
• specific modifiers and/or additives may be added into the input and/or the cellulose-containing mass prior to the extraction of any excessive liquid content.
• said specific modifiers and/or additives may be employed for achieving a particular homogeneity of the cellulose-containing mass and/or the composite material.
• the stalk part of cereal crop is chosen.
• the spike of the crop is missing.
• the straw is taken after harvest. In this example straw of wheat is used.
• the straw has been pre-treated by chopping up the stalks of straw until the straw pieces had an average size of about 5 to 7 millimeters, mixing them with water and macerating them until the organic particles in the input had an average size of about 0.8 to 1 mm.
• the pH-value of the aqueous mixture was brought to a value of more than 8.4 and macerated for 1.5 to 2 hours.
• the time of maceration was reduced to 1.5 to 2 minutes.
• One part of water was added to three parts of straw (weight/weight).
• the input comprising the straw mass was poured into a stainless steel container serving as a mixing container to be put in the active zone between two inductors,.
• An alternating electromagnetic field was generated such that it penetrated the active zone of 80 cm 3 between the inductors (50 mm gap width) in the mixing container.
• the magnetic force measured about 0.3 T was applied.
• the input was exposed for 20 seconds to said alternating magnetic field.
• the electric source had 50 Hz.
• the ferromagnetic particles churned the input in the container lively.
• every ferromagnetic particle performed a role of micro-mixer and micro-grinder due to its interaction with different hodographs of intensity vector H i at different i points within the container.
• the particles with an average particle size of the organic material remained in the cellulose-containing mass measured not less than 1 ⁇ m.
• the magnetic treatment ensured a sufficient disintegration of the input material, so that sufficient numbers of cells and intra- and intercellular structures are destroyed.
• the cellulose-containing material was carried over from the mixing container to a mold, in the form of a Büchner Funnel. Suction filtration was used to increase the speed of filtration and subsequently the cellulose-containing mass was left to dry so that the dry and solid piece of composite material is left remaining.
• the evaporation process encompassed a combined method of filtration and natural drying until the weight mass of the composite material became permanent at a temperature of 30° C. Drying was controlled by a gravimetrical method until the sample product underwent structural and strength tests.
• Wheat straw was pre-treated by chopping up the stalks of straw until the straw pieces had an average size of about 5 to 7 millimeters. 100 g of chopped straw were mixed with 1000 ml of a master solution in order to produce a trial batch. All trial batches were allowed to settle for 6 hours before further treatment steps.
• CMC Carboxy Methyl Cellulose
• the Carboxy Methyl Cellulose (CMC) used in the present experiments was obtained from Fischer Chemicals Chemicals AG, Riesbachstrasse 57, CH-8034 Zurich, Switzerland with the CAS Number 9004-32-4. 7 g of CMC were added to and mixed with each trial batch in each experiment. In further experiments microcrystalline cellulose (MCC) was used which had according to preferred embodiments a mean size range of about 15 to 40 microns.
• Non-standardized mechanical tests preformed on the resulting test blocks of experiments 2 to 13 revealed that the materials produced according to examples 2 and 5 are hardest and strongest. All the samples according to experiments 2 to 8 and 11 to 13 resulted in cellulose-containing masses suitable for the production of shaped composites. However the inherent strength and stability of the test blocks produced with the cellulose-containing masses according to examples 9 and 10 were considerable lower.
• Wheat straw was pre-treated by chopping up the stalks of straw until the straw pieces had an average size of about 5 to 7 millimeters.
• 100 kg of chopped straw were mixed with 1000 l of hot water in order to produce a trial batch. All trial batches were wet-milled immediately after production of the batches in CONDUX Fine cutting mills CS 500, available from Netzsch-Condux.
• the preferred temperature range of the water straw mixture during wet milling was kept at about 92 to 94° C.
• the milling product was of excellent fineness and homogeneity and already suitable for the production of a composite material and for producing a desired product of said cellulose-containing mass.
• Wheat straw was pre-treated by chopping up the stalks of straw until the straw pieces had an average size of about 5 to 7 millimeters, 100 kg of chopped straw were mixed with 1000 l of hot water in order to produce a trial batch. All trial batches were again wet-milled immediately after production of the batches in CONDUX Fine cutting mills CS 500, available from Netzsch-Condux, The preferred temperature range of the water straw mixture during wet milling was kept ate about 92 to 94° C. During wet-milling, an aqueous, liquid cellulose-containing fraction was separated and drained from the mill. Said hot liquid fraction can be recycled to the mill. According to preferred embodiments however, it was further concentrated by filtering or by dehydration and added during mixing. The mixing was again performed in a a high-performance Ringlayer Mixer CoriMix® CM available from Gebr, Lödige Maschinenbau GmbH.
• microcrystalline cellulose and/or powdered cellulose is added to achieve further desired properties.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Paper (AREA)

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