CA2774506A1 - Cellulose-containing mass - Google Patents
Cellulose-containing mass Download PDFInfo
- Publication number
- CA2774506A1 CA2774506A1 CA2774506A CA2774506A CA2774506A1 CA 2774506 A1 CA2774506 A1 CA 2774506A1 CA 2774506 A CA2774506 A CA 2774506A CA 2774506 A CA2774506 A CA 2774506A CA 2774506 A1 CA2774506 A1 CA 2774506A1
- Authority
- CA
- Canada
- Prior art keywords
- cellulose
- input
- containing mass
- organic material
- inductors
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000001913 cellulose Substances 0.000 title claims abstract description 89
- 229920002678 cellulose Polymers 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 70
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 239000011368 organic material Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 230000005672 electromagnetic field Effects 0.000 claims abstract description 20
- 235000010980 cellulose Nutrition 0.000 claims description 84
- 239000002245 particle Substances 0.000 claims description 35
- 239000010902 straw Substances 0.000 claims description 34
- 230000005294 ferromagnetic effect Effects 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 22
- 230000005291 magnetic effect Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 11
- 239000008108 microcrystalline cellulose Chemical class 0.000 claims description 11
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 235000013339 cereals Nutrition 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 241000196324 Embryophyta Species 0.000 claims description 7
- 241000209504 Poaceae Species 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 244000025254 Cannabis sativa Species 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 5
- 238000002803 maceration Methods 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 4
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 235000009120 camo Nutrition 0.000 claims description 4
- 229940106135 cellulose Drugs 0.000 claims description 4
- 235000005607 chanvre indien Nutrition 0.000 claims description 4
- 239000011487 hemp Substances 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 240000006240 Linum usitatissimum Species 0.000 claims description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 241000219146 Gossypium Species 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229920000136 polysorbate Polymers 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 9
- 238000001238 wet grinding Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 241000209140 Triticum Species 0.000 description 7
- 235000021307 Triticum Nutrition 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 150000004676 glycans Polymers 0.000 description 5
- 230000003834 intracellular effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000002906 microbiologic effect Effects 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 244000299507 Gossypium hirsutum Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000209056 Secale Species 0.000 description 2
- 235000007238 Secale cereale Nutrition 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 230000004523 agglutinating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002029 lignocellulosic biomass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003110 molding sand Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920000832 Cutin Polymers 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 208000034693 Laceration Diseases 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229930183415 Suberin Natural products 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002169 hydrotherapy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- -1 inorganic minerals Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000002879 macerating effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 229920003124 powdered cellulose Polymers 0.000 description 1
- 235000019814 powdered cellulose Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Landscapes
- 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)
Abstract
The invention concerns a method for producing a cellulose-containing mass comprising an organic material, the method comprising the steps a) preparation of an input comprising organic material and a liquid content, and b) exposing said input to a wet-mixmg procedure at a temperature in the range of 40 to 90 °C preferably 50 to 80 °C and most preferred around 60 °C or exposing said input to an active zone of an electromagnetic field Accord¬ ing to a further embodiment of the present invention cellulose of different types is added to the input Moreover a method for producing a composite material that is based on said cel- lulose-containmg mass is disclosed as well as a product produced of said composite material
Description
Cellulose-containing mass FIELD OF THE INVENTION
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 pro-ducing 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 io 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.
BACKGROUND OF THE INVENTION
Currently there are several composite materials of organic origin known which are for exam-ple suitable for packaging and construction applications. While wood fibers are quite com-mon other natural fibers from crop or grain are used occasionally as fibrous fillers.
U52006043629A 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. Moreover the use of modified soy flour with functional monomers is ex-plained in the context of industrial applications such as reactive extrusion and injection molding US 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 s copolymers, incorporate functionality capable of forming covalent bonds within or between the polymer and cellulosic components, PROBLEM TO BE SOLVED
It is an object of the present invention to provide an improved method of production of cel-lulose-containing masses, to provide said cellulose-containing masses and to provide meth-ods for producing high-strength composite materials comprising original structures of or-ganic materials, preferably originating from higher plants, which evolve their natural forms (e.g. stalks) through intracellular and intercellular structural linkage between different poly-mers and/or their moieties of different substances, functional groups, side chains and/or is rests, SUMMARY OF THE INVENTION
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 enve-lopes or membrane that contain sufficient quantity of cellulose, i,e, a high-molecular poly-saccharide or glucan composed of [3-1,4-linked D-glucose, or chitin, a glycan composed of beta-1,4-linked N-acetyl-D-glucosamine. In the present application the term cellulose-containing mass, input and/or composite shall comprise also chitin containing masses, in-puts 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 [C6H7O2(OH)3]n structured into polymer chains of 3-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.
In the context of the present application, the term exogenous denotes that the polymeric component origins not from the organic raw material being processed. It is an essential fea-ture 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 To of a) preparation of an input comprising organic material and a liquid content;
and b) exposing said input to a wet-milling procedure at a temperature in the range of 70 to 120 C, preferably 80 to 100 C, and most preferred at about 92 to 94 C.
According to preferred embodiments said input is further to step b) or alternatively to step b) 1s exposed to an active zone of an artificial electromagnetic field.
According to preferred embodiments during manufacturing natural forms of inputs are de-structed, 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 re-shaped with new geometrical form, and structural linkages are recovered while this paste is 20 curing. Cured paste becomes the end-use item.
Hereinafter, the term input is used to refer to the starting substance or mixture of sub-stances that is exposed to the electromagnetic field whereas the term cellulose-containing mass denotes the product produced by the aforementioned method according to the inven-tion. 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. Such a cellulose-containing mass is used further as molding sand; it is reshaped with new geometrical form, and struc-tural linkages are recovered while this paste is curing. Cured paste becomes the end-use item.
io According to preferred embodiments, additional cellulose preferably methyl cellulose and/or carboxy methyl cellulose, preferably in the form of a sodium salt, and/or microcrys-talline cellulose is added to the cellulose-containing mass. According to a further preferred embodiment of the present invention, the additional cellulose is at least partially added as concentrated cellulose containing fraction generated in the wet-milling procedure. The cellu-is lose 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 rela-tion to the water content.
In the present patent application, the term organic material is understood to comprise any cellulose containing material. Preferably, the input organic material comprises fibers mixed 20 of cellulose molecules, Advantageously, the organic material origins from higher plants pref-erably 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.
Preferably, 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, 5 the microbial population, the percentage of 0-cellulose in the pure input material responsi-ble for generating bundles of micelles in the form of superfine fibrils.
Preliminary determina-tion of organic base content between fibrils and cellulose agglutinating these fibrils into the solidest fibers proved to be advantageous. As a rule, organic materials containing aggluti-nating or gelling substances like pectin are suitable, but organic materials containing sub io stances like suberins or cutin that are by nature more hydrophobic are suitable as well. Al-ternatively organic materials containing lignin may also be used. Basic features and proper-ties 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 electrome-45 chanical, 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 vari-ance of mechanical and physical exposures. In case that the organic material is straw, e.g.
rice or wheat or rye straw, a liquid having a pH-value of about 8 or above, more preferably 20 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.
It is known from the prior art, for example from WO 08/112191 that in lignocellulosic bio-mass, crystalline cellulose fibrils are embedded in a less well-organized hemicellulose matrix 25 which, in turn, is surrounded by an outer lignin seal, Contacting naturally occurring cellu-losic materials with hydrolyzing enzymes generally results in cellulose hydrolysis yields that are less than 20% of theoretically predicted results, Hence, some "pretreatment" of the biomass is invariably carried out prior to attempting the enzymatic hydrolysis of the polysac-charides (cellulose and hemicellulose) in the biomass. Pretreatment refers to a process that converts lignocellulosic biomass from its native form, in which it is recalcitrant to cellulase s enzyme systems, into a form for which cellulose hydrolysis is effective.
Compared to un-treated biomass, effectively pretreated lignocellulosic materials are characterized by an in-creased surface area (porosity) accessible to cellulase enzymes, and solubilization or redistri-bution of lignin. Increased porosity results mainly from a combination of disruption of cellu-lose crystallinity, hemicellulose disruption/solubilization, and lignin redistribution and/or to solubilization. The relative effectiveness in accomplishing some (or all) of these factors dif-fers greatly among different existing pretreatment processes. These include dilute acid, steam explosion, hydrothermal processes, "organosolv" processes involving organic solvents in an aqueous medium, ammonia fiber explosion (AFEX), strong alkali processes using a base such as, ammonia, NaOH or lime, and highly-concentrated phosphoric acid treatment.
is Those methods known from the art as mentioned above and further known methods for treatment of cellulose containing biomaterials may advantageously be combined with the method steps according to the present invention.
Depending on the desired properties of the cellulose-containing mass (i.e. the output) and/or the pre-processing preparation, the endogenous liquid content, i.e. the liquid content 20 provided by the raw organic material itself or originating from the raw organic material, is sufficient so that no exogenous or additional liquid has to be added. In its simplest em-bodiment, the liquid content is formed by water. However, other liquids, like organic sol-vents 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 com-25 posite material later on. However, it is important that a proper function of the liquid content with the organic material is achievable, In case of liquids other than water it is essential to preferred embodiments of the invention that an excess of the liquid content is extractable in a suitable manner after the cellulose-containing mass is produced, where necessary.
Depending on the intended use and the intended processing method, the liquid content comprises preferably a solvent, e.g. for mellowing the organic material.
Processes of structural linkages recovery appear while homogenous mass is curing in new moulds; such processes are actually an integration of remains of j3-glucose n-molecules into molecular compound with common to polymers formula [C6H7O2(OH)3]n. Known presence of glucose molecules of three hydroxyl groups [(OH)3 groups] in each remain makes it obvious that linkage of every remain couple of glucose molecule between each other is happened i0 through lateral hydroxyl groups by abstraction of water molecules from them, Therefore, structural linkages recovery in homogeneous mass is taken place inadvertently when this mass is dehydrated, and results in its curing.
Tests have shown that the properties of the cellulose-containing mass hereinafter also called output are enhanced when the input which is exposed in the active zone of an electromag-netic field comprises an amount of ferromagnetic particles.
According to preferred embodiments of the present invention method according to the in-vention 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 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 pro-ducing 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 io 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.
BACKGROUND OF THE INVENTION
Currently there are several composite materials of organic origin known which are for exam-ple suitable for packaging and construction applications. While wood fibers are quite com-mon other natural fibers from crop or grain are used occasionally as fibrous fillers.
U52006043629A 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. Moreover the use of modified soy flour with functional monomers is ex-plained in the context of industrial applications such as reactive extrusion and injection molding US 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 s copolymers, incorporate functionality capable of forming covalent bonds within or between the polymer and cellulosic components, PROBLEM TO BE SOLVED
It is an object of the present invention to provide an improved method of production of cel-lulose-containing masses, to provide said cellulose-containing masses and to provide meth-ods for producing high-strength composite materials comprising original structures of or-ganic materials, preferably originating from higher plants, which evolve their natural forms (e.g. stalks) through intracellular and intercellular structural linkage between different poly-mers and/or their moieties of different substances, functional groups, side chains and/or is rests, SUMMARY OF THE INVENTION
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 enve-lopes or membrane that contain sufficient quantity of cellulose, i,e, a high-molecular poly-saccharide or glucan composed of [3-1,4-linked D-glucose, or chitin, a glycan composed of beta-1,4-linked N-acetyl-D-glucosamine. In the present application the term cellulose-containing mass, input and/or composite shall comprise also chitin containing masses, in-puts 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 [C6H7O2(OH)3]n structured into polymer chains of 3-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.
In the context of the present application, the term exogenous denotes that the polymeric component origins not from the organic raw material being processed. It is an essential fea-ture 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 To of a) preparation of an input comprising organic material and a liquid content;
and b) exposing said input to a wet-milling procedure at a temperature in the range of 70 to 120 C, preferably 80 to 100 C, and most preferred at about 92 to 94 C.
According to preferred embodiments said input is further to step b) or alternatively to step b) 1s exposed to an active zone of an artificial electromagnetic field.
According to preferred embodiments during manufacturing natural forms of inputs are de-structed, 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 re-shaped with new geometrical form, and structural linkages are recovered while this paste is 20 curing. Cured paste becomes the end-use item.
Hereinafter, the term input is used to refer to the starting substance or mixture of sub-stances that is exposed to the electromagnetic field whereas the term cellulose-containing mass denotes the product produced by the aforementioned method according to the inven-tion. 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. Such a cellulose-containing mass is used further as molding sand; it is reshaped with new geometrical form, and struc-tural linkages are recovered while this paste is curing. Cured paste becomes the end-use item.
io According to preferred embodiments, additional cellulose preferably methyl cellulose and/or carboxy methyl cellulose, preferably in the form of a sodium salt, and/or microcrys-talline cellulose is added to the cellulose-containing mass. According to a further preferred embodiment of the present invention, the additional cellulose is at least partially added as concentrated cellulose containing fraction generated in the wet-milling procedure. The cellu-is lose 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 rela-tion to the water content.
In the present patent application, the term organic material is understood to comprise any cellulose containing material. Preferably, the input organic material comprises fibers mixed 20 of cellulose molecules, Advantageously, the organic material origins from higher plants pref-erably 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.
Preferably, 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, 5 the microbial population, the percentage of 0-cellulose in the pure input material responsi-ble for generating bundles of micelles in the form of superfine fibrils.
Preliminary determina-tion of organic base content between fibrils and cellulose agglutinating these fibrils into the solidest fibers proved to be advantageous. As a rule, organic materials containing aggluti-nating or gelling substances like pectin are suitable, but organic materials containing sub io stances like suberins or cutin that are by nature more hydrophobic are suitable as well. Al-ternatively organic materials containing lignin may also be used. Basic features and proper-ties 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 electrome-45 chanical, 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 vari-ance of mechanical and physical exposures. In case that the organic material is straw, e.g.
rice or wheat or rye straw, a liquid having a pH-value of about 8 or above, more preferably 20 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.
It is known from the prior art, for example from WO 08/112191 that in lignocellulosic bio-mass, crystalline cellulose fibrils are embedded in a less well-organized hemicellulose matrix 25 which, in turn, is surrounded by an outer lignin seal, Contacting naturally occurring cellu-losic materials with hydrolyzing enzymes generally results in cellulose hydrolysis yields that are less than 20% of theoretically predicted results, Hence, some "pretreatment" of the biomass is invariably carried out prior to attempting the enzymatic hydrolysis of the polysac-charides (cellulose and hemicellulose) in the biomass. Pretreatment refers to a process that converts lignocellulosic biomass from its native form, in which it is recalcitrant to cellulase s enzyme systems, into a form for which cellulose hydrolysis is effective.
Compared to un-treated biomass, effectively pretreated lignocellulosic materials are characterized by an in-creased surface area (porosity) accessible to cellulase enzymes, and solubilization or redistri-bution of lignin. Increased porosity results mainly from a combination of disruption of cellu-lose crystallinity, hemicellulose disruption/solubilization, and lignin redistribution and/or to solubilization. The relative effectiveness in accomplishing some (or all) of these factors dif-fers greatly among different existing pretreatment processes. These include dilute acid, steam explosion, hydrothermal processes, "organosolv" processes involving organic solvents in an aqueous medium, ammonia fiber explosion (AFEX), strong alkali processes using a base such as, ammonia, NaOH or lime, and highly-concentrated phosphoric acid treatment.
is Those methods known from the art as mentioned above and further known methods for treatment of cellulose containing biomaterials may advantageously be combined with the method steps according to the present invention.
Depending on the desired properties of the cellulose-containing mass (i.e. the output) and/or the pre-processing preparation, the endogenous liquid content, i.e. the liquid content 20 provided by the raw organic material itself or originating from the raw organic material, is sufficient so that no exogenous or additional liquid has to be added. In its simplest em-bodiment, the liquid content is formed by water. However, other liquids, like organic sol-vents 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 com-25 posite material later on. However, it is important that a proper function of the liquid content with the organic material is achievable, In case of liquids other than water it is essential to preferred embodiments of the invention that an excess of the liquid content is extractable in a suitable manner after the cellulose-containing mass is produced, where necessary.
Depending on the intended use and the intended processing method, the liquid content comprises preferably a solvent, e.g. for mellowing the organic material.
Processes of structural linkages recovery appear while homogenous mass is curing in new moulds; such processes are actually an integration of remains of j3-glucose n-molecules into molecular compound with common to polymers formula [C6H7O2(OH)3]n. Known presence of glucose molecules of three hydroxyl groups [(OH)3 groups] in each remain makes it obvious that linkage of every remain couple of glucose molecule between each other is happened i0 through lateral hydroxyl groups by abstraction of water molecules from them, Therefore, structural linkages recovery in homogeneous mass is taken place inadvertently when this mass is dehydrated, and results in its curing.
Tests have shown that the properties of the cellulose-containing mass hereinafter also called output are enhanced when the input which is exposed in the active zone of an electromag-netic field comprises an amount of ferromagnetic particles.
According to preferred embodiments of the present invention method according to the in-vention 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.
According to preferred embodiments of the present invention 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 rang-es.
io The size and shape of the ferromagnetic particles maybe chosen depending on the proper-ties 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.
Test have shown, that high quality cellulose-containing masses were obtained when if the ratio of the ferromagnetic particles to the input was about 1 to about 20 weight percent, A
is liquid content of the input between 0 to about 40 percent. However, in further embodi-ments of the method, other ratios may be chosen according to paticular 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 2-20 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 con-tainer was of continuous type. The time of exposure was up to 20 seconds, The ferromagnetic particles support the desintegration of the organic material supra- and 25 subcellular level, as well as the breaking of organic linkages of intracellular and/or intercel-lular 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 mecanical crushing, breaking and/or grinding the until a more homogenous cellulose-containing mass is produced. Desintegration 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 ef-fect 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 prod-ucts 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 electro-magnetic 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.
Depending on the requirements that have to be fulfiled by the cellulose-containing mass and/or the composite article 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.
According to preferred embodiments in which the production is set to a batchwise mode, 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.
The presence of 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, s 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 fer-romagnetic 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 io excite common alternating electromagnetic field with circular or elliptic holograph of inten-sity of magnetic component, spinning around a common axis that is situated between in-ductors. 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 50x165x80 mm and a magnetic force of about 0.03 T. The duration of expo-sure of the input to the magnetic field was about 20 seconds.
The destructive influence of the ferromagnetic particles on the particles of the organic mate-rial in the active zone is explained in more detail below, The impact of those ferromagnetic particles on intracellular and intercellular structures by means of its magnetic components A
(A is vector potential of magnetic field), and B (B is magnetic field induction; A and B are related by formula B=rotA) is amplified through reduction of reluctance R
within the active zone resulting in an increase of the magnetic flux in this active zone. The term rotA denotes the rotation of the vector potential.
The ferromagnetic particles increase the magnitude B; under H;=constant at every point i such that the active value of gradA is increased, GradA denotes a gradient A.
Depending on the input and the desired characteristics of the cellulose-containing mass, 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 io about I 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 ad-justable by the electric parameters of the inductors.
According to preferred embodiments 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
10002 type, available from Netzsch-Conflux 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.
After the wet-milling step, the intermediate product can - according to further preferred 2a embodiments - be mixed with additional cellulose, for example in a high-performance Rin-glayer Mixer CoriMix CM available from Gebr. Lodige Maschinenbau GmbH, Elsener StraBe 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 40m/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 s flow, with the residence time being influenced by the degree of filling, the number of revolu-tions, 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 Lodige Maschinenbau GmbH.
io It has been shown in a series of experiments that it is advantageous to add cellulose in the form of microcrystalline cellulose (MCC), a highly crystalline particulate cellulose consisting primarily of crystallite aggregates obtained by removing amorphous (fibrous cellulose) re-gions of a purified cellulose source material by hydrolytic degradation, to the cellulose con-taining mass, 5 to 10 weight percent, preferably 7 weight percent of MCC were added to 15 each batch in each experiment.
The addition of microcrystalline cellulose, especially when added to inputs containing pri-marily 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 20 when compared to similar composites produced without the addition of microcrystalline cellulose.
After termination of the mixing the cellulose-containing mass is ready to be used for produc-ing a composite material and for producing a desired product of said cellulose-containing mass.
The technology and technique of producing products in accordance with preferred embodi-ments of the invention include at least the following basic steps:
1. Preliminary preparation of inputs (comprising additives/improvers where necessary) including the previously described additional techniques of manufacturing;
2. electromagnetic exposure;
1 post-processing by at least one of curing and molding of the cellulose-containing mass until a product (end-use item) is produced.
According to the present invention, step number 2. is optional The term products encompasses end-products, such as for example panels, as well as semi-1o products, e.g, a core material of a laminated construction such as a sandwich construction, for example. In case of the latter, certain properties of the product may be improved for ex-ample 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.
Depending on the embodiment of the 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.
Alternatively and/or in addition thereto, the cured composite material maybe 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 cellu-lose-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 ac-tually an integration of remains of J3-glucose n-molecules into molecular compound with common to polymers formula [C6H702(OH)3]n. The presence of glucose molecules with three hydroxyl groups [(OH) groups] in each rest allow that linkage between said rests is faciliated 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 dessication or drying in case of water, resulting in a curing process.
In case of water being used as the liquid content the dehydration process is carried out un-der a predetermined temperature by any of a range of known suitable techniques. Such techniques are comprising and/or combining compression, extrusion and filtration as well to 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, Depending on the characteristics of the cellulose-containing mass and/or the requirements is on the composite material or the product to be produced thereof, the post processing of the cellulose-containing mass is performed by at least one of molding, compression molding, injection molding. However, other shaping techniques for producing the product may be suitable.
In case of a post-processing by compression molding it is conceivable that the mixing con-20 tainer or a part thereof form a half of the mold at the same time. As general molding tech-niques are known to the person skilled in the art there a detailed description thereof is omit-ted.
Depending on the demands and the manufacturability, 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 5 type of resistance, a specific color, a particular smell or a combination thereof. For this pur-pose, 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.
Depending on the requirements, said specific modifiers and/or additives may be employed for achieving a particular homogeneity of the cellulose-containing mass and/or the compos-10 ite material.
Special attention shall be paid to the fact, that several types of plant cells are encrusted by or containing compounds like inorganic minerals, for example silicates, or organic minerals like oxalates. The directed selection of organic materials containing certain amounts of said compounds like for example minerals can be used to provide cellulose-containing masses 15 and composite materials according to the invention providing certain properties demanded by end-users. For instance, by selecting raw materials with employing the ability that the mentioned materials can acquire or significantly improve such characteristics and properties as conductance, transcalency (Le. the thermal conductivity), soundproofness, resistance against moisture deformation, chemical and microbiological exposure and so on.
In addition exogenous modifiers may be added if the cellulose-containing mass does not satisfy the requirements on the composite material.
Production of materials with predetermined properties (resistance, hydropathy, durability against chemically aggressive milieu, microbiological resistance, additional and/or special type of resistance, color, smell etc.) including those required by consumer's priorities is achieved by adding specific modifiers into homogeneous mass before dehydration and/or using special supplemental techniques while preparing homogeneous mass for curing.
Now, a few possibilities for surface treatment shall be addressed in brief.
Depending on the requirements on the product made of the composite material, certain characteristics are s achievable e.g. by applying one or several coatings with an impregnation, e.g. by way of immersion. Moreover, a coating layer with a specific color is applicable likewise.
All declarations in the description above apply likewise for the cellulose-containing mass, the method for producing the composite material, the composite material itself as well as for the produced thereof.
io EXAMPLE 1 As a raw organic material the stalk part of cereal crop is chosen. Preferably the spike of the crop is missing. Preferably 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 15 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. In this example, 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. In further examples 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).
20 After maceration the input comprising the straw mass was poured into a stainless steel con-tainer serving as a mixing container to be put in the active zone between two inductors.
An amount 14 g of ferromagnetic particles with cylindrical forms having an average diame-ter of 250 pm, an average length of 1500 pm were added to the straw-and-water mixture in the container prior to exposing the cellulose-containing mass to the electromagnetic field in order to increase the magnitude B; under H;=constant at every point i such that the active s value of An alternating electromagnetic field was generated such that it penetrated the active zone of 80 cm3 between the inductors (50 mm gap width) in the mixing container. The magnetic field provided that a vector of magnetic component created a circle or/and elliptic hodo-graph at any i point within that space excluding points of central axis defined between the io inductors such that B, = p*H; where diva; =0, and, therefore, rotA, = B;.
The intensity of the magnetic component was equal to zero at any j point on the central axis and the condition Hi=O, Bj=0 and rotAj=O was satisfied, So, activity of vector potential A of magnetic field with amplitude value from Ai toy A; was generated within the alternating electromagnetic field, such that gradA took effect in the space between the inductors.
is The magnetic force measured about 0.3 T was applied. The input was exposed for 20 sec-onds to said alternating magnetic field. The electric source had 50 Hz.
Upon applying of the magnetic field, the ferromagnetic particles churned the input in the container lively. In this process every ferromagnetic particle performed a role of micro-mixer and micro-grinder due to its interaction with different hodographs of intensity vector H; at 20 different i points within the container.
After termination of the exposure of the input to the electromagnetic field, the particles with an average particle size of the organic material remained in the cellulose-containing mass measured not less than 1 pm. However the magnetic treatment ensured a sufficient desin-tegration of the input material, so that sufficient numbers of cells and intra-and intercellular structures are destroyed.
Then, the cellulose-containing material was carried over from the mixing container to a mold, in the form of a Buchner Funnel. Suction filtration was used to increase the speed of filtra-tion and subsequently the cellulose-containing mass was left to dry so that the dry and solid piece of composite material is left remaining. In this example, the evaporation process en-compassed 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.
1o EXAMPLES 2 to 13 In the present example No. 2 and the following examples No. 3 to 13 the following basic settings were employed.
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.
In each of the experiments 2 to 13 Carboxy Methyl Cellulose (CMC) was used, The Carboxy Methyl Cellulose(CMC) used in the present experiments was obtained from Fischer Chemi-cals 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.
In four of the experiments the input was exposed to an active zone of an electromagnetic field generated between linear electromagnetic inductors as described above.
The time of exposure to the electromagnetic filed is listed in column "Inductor" in Table 1 below.
In experiments 3, 6, 9 and 12 the straw material in the master solution is cooked for 3 s hours as indicated in Column Cooking below. The NaOH based mixture of example 12 is neutralized after cooking.
All experimental samples were transferred onto a paper filter afterwards.
Excess water was pressed off and the remaining filter cake was allowed to settle for 2 hours.
The samples of experiments 2, 5, 8 and 11 were exposed to the active zone between the io inductors for 1 Minute before transferring them to the filter.
All samples were dried afterwards at temperatures between 80 to 85 C for 16 or 24 hours as indicated in column Drying.
Table 1; Experiments 2 to 13 Experiment Master Solution Cooking Inductor Pressing off / CMC Drying Filter 2 0.1 NHCI - 1 min 2 h 7 g 24 h 3 0.1 N HCI 3 h 2 h 7g 24 h LITHCI 2h 7g 16h 5 0.1 NH2SO4 - 1 min 2 h 7 g 24 h 6 0.1 NH2SO4 3 h - 2 h 7g 24 h 7 O.1 NH2SO4 - 2h 7g 16h H2O 1 min 2 h 7 g _16 hh 9 H2O 3 h - 2 h 7 g 24 h 10 H2O - - 2h 7g 16h 11 (1N)NaOH - 1 min 2h 7g 16h 12 (1N)NaOH 3h 2h 7g 24h 13 (IN) NaOH - - 2 h 7 g 24 h 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 cellu-5 lose-containing masses suitable for the production of shaped composites.
However the in-herent 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 I 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-Conflux. 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 pro-ducing a desired product of said cellulose-containing mass, 1o EXAMPLE 15 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 I of hot water in order to produce a trial batch. All trial batches were again wet-milled im-mediately 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 concen-trated by filtering or by dehydration and added during mixing. The mixing was again per-formed in a a high-performance Ringlayer Mixer CoriMix CM available from Gebr, Lodige Maschinenbau GmbH.
The above listed experiments show that according to the present invention the addition of cellulose based adhesives and binders, preferably in a water-soluble form as methyl cellulose and carboxy methyl cellulose enhances the properties of the produced masses and materials.
in further preferred embodiments microcrystalline cellulose and/or powdered cellulose is added to achieve further desired properties;
io The size and shape of the ferromagnetic particles maybe chosen depending on the proper-ties 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.
Test have shown, that high quality cellulose-containing masses were obtained when if the ratio of the ferromagnetic particles to the input was about 1 to about 20 weight percent, A
is liquid content of the input between 0 to about 40 percent. However, in further embodi-ments of the method, other ratios may be chosen according to paticular 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 2-20 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 con-tainer was of continuous type. The time of exposure was up to 20 seconds, The ferromagnetic particles support the desintegration of the organic material supra- and 25 subcellular level, as well as the breaking of organic linkages of intracellular and/or intercel-lular 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 mecanical crushing, breaking and/or grinding the until a more homogenous cellulose-containing mass is produced. Desintegration 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 ef-fect 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 prod-ucts 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 electro-magnetic 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.
Depending on the requirements that have to be fulfiled by the cellulose-containing mass and/or the composite article 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.
According to preferred embodiments in which the production is set to a batchwise mode, 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.
The presence of 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, s 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 fer-romagnetic 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 io excite common alternating electromagnetic field with circular or elliptic holograph of inten-sity of magnetic component, spinning around a common axis that is situated between in-ductors. 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 50x165x80 mm and a magnetic force of about 0.03 T. The duration of expo-sure of the input to the magnetic field was about 20 seconds.
The destructive influence of the ferromagnetic particles on the particles of the organic mate-rial in the active zone is explained in more detail below, The impact of those ferromagnetic particles on intracellular and intercellular structures by means of its magnetic components A
(A is vector potential of magnetic field), and B (B is magnetic field induction; A and B are related by formula B=rotA) is amplified through reduction of reluctance R
within the active zone resulting in an increase of the magnetic flux in this active zone. The term rotA denotes the rotation of the vector potential.
The ferromagnetic particles increase the magnitude B; under H;=constant at every point i such that the active value of gradA is increased, GradA denotes a gradient A.
Depending on the input and the desired characteristics of the cellulose-containing mass, 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 io about I 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 ad-justable by the electric parameters of the inductors.
According to preferred embodiments 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
10002 type, available from Netzsch-Conflux 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.
After the wet-milling step, the intermediate product can - according to further preferred 2a embodiments - be mixed with additional cellulose, for example in a high-performance Rin-glayer Mixer CoriMix CM available from Gebr. Lodige Maschinenbau GmbH, Elsener StraBe 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 40m/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 s flow, with the residence time being influenced by the degree of filling, the number of revolu-tions, 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 Lodige Maschinenbau GmbH.
io It has been shown in a series of experiments that it is advantageous to add cellulose in the form of microcrystalline cellulose (MCC), a highly crystalline particulate cellulose consisting primarily of crystallite aggregates obtained by removing amorphous (fibrous cellulose) re-gions of a purified cellulose source material by hydrolytic degradation, to the cellulose con-taining mass, 5 to 10 weight percent, preferably 7 weight percent of MCC were added to 15 each batch in each experiment.
The addition of microcrystalline cellulose, especially when added to inputs containing pri-marily 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 20 when compared to similar composites produced without the addition of microcrystalline cellulose.
After termination of the mixing the cellulose-containing mass is ready to be used for produc-ing a composite material and for producing a desired product of said cellulose-containing mass.
The technology and technique of producing products in accordance with preferred embodi-ments of the invention include at least the following basic steps:
1. Preliminary preparation of inputs (comprising additives/improvers where necessary) including the previously described additional techniques of manufacturing;
2. electromagnetic exposure;
1 post-processing by at least one of curing and molding of the cellulose-containing mass until a product (end-use item) is produced.
According to the present invention, step number 2. is optional The term products encompasses end-products, such as for example panels, as well as semi-1o products, e.g, a core material of a laminated construction such as a sandwich construction, for example. In case of the latter, certain properties of the product may be improved for ex-ample 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.
Depending on the embodiment of the 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.
Alternatively and/or in addition thereto, the cured composite material maybe 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 cellu-lose-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 ac-tually an integration of remains of J3-glucose n-molecules into molecular compound with common to polymers formula [C6H702(OH)3]n. The presence of glucose molecules with three hydroxyl groups [(OH) groups] in each rest allow that linkage between said rests is faciliated 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 dessication or drying in case of water, resulting in a curing process.
In case of water being used as the liquid content the dehydration process is carried out un-der a predetermined temperature by any of a range of known suitable techniques. Such techniques are comprising and/or combining compression, extrusion and filtration as well to 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, Depending on the characteristics of the cellulose-containing mass and/or the requirements is on the composite material or the product to be produced thereof, the post processing of the cellulose-containing mass is performed by at least one of molding, compression molding, injection molding. However, other shaping techniques for producing the product may be suitable.
In case of a post-processing by compression molding it is conceivable that the mixing con-20 tainer or a part thereof form a half of the mold at the same time. As general molding tech-niques are known to the person skilled in the art there a detailed description thereof is omit-ted.
Depending on the demands and the manufacturability, 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 5 type of resistance, a specific color, a particular smell or a combination thereof. For this pur-pose, 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.
Depending on the requirements, said specific modifiers and/or additives may be employed for achieving a particular homogeneity of the cellulose-containing mass and/or the compos-10 ite material.
Special attention shall be paid to the fact, that several types of plant cells are encrusted by or containing compounds like inorganic minerals, for example silicates, or organic minerals like oxalates. The directed selection of organic materials containing certain amounts of said compounds like for example minerals can be used to provide cellulose-containing masses 15 and composite materials according to the invention providing certain properties demanded by end-users. For instance, by selecting raw materials with employing the ability that the mentioned materials can acquire or significantly improve such characteristics and properties as conductance, transcalency (Le. the thermal conductivity), soundproofness, resistance against moisture deformation, chemical and microbiological exposure and so on.
In addition exogenous modifiers may be added if the cellulose-containing mass does not satisfy the requirements on the composite material.
Production of materials with predetermined properties (resistance, hydropathy, durability against chemically aggressive milieu, microbiological resistance, additional and/or special type of resistance, color, smell etc.) including those required by consumer's priorities is achieved by adding specific modifiers into homogeneous mass before dehydration and/or using special supplemental techniques while preparing homogeneous mass for curing.
Now, a few possibilities for surface treatment shall be addressed in brief.
Depending on the requirements on the product made of the composite material, certain characteristics are s achievable e.g. by applying one or several coatings with an impregnation, e.g. by way of immersion. Moreover, a coating layer with a specific color is applicable likewise.
All declarations in the description above apply likewise for the cellulose-containing mass, the method for producing the composite material, the composite material itself as well as for the produced thereof.
io EXAMPLE 1 As a raw organic material the stalk part of cereal crop is chosen. Preferably the spike of the crop is missing. Preferably 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 15 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. In this example, 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. In further examples 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).
20 After maceration the input comprising the straw mass was poured into a stainless steel con-tainer serving as a mixing container to be put in the active zone between two inductors.
An amount 14 g of ferromagnetic particles with cylindrical forms having an average diame-ter of 250 pm, an average length of 1500 pm were added to the straw-and-water mixture in the container prior to exposing the cellulose-containing mass to the electromagnetic field in order to increase the magnitude B; under H;=constant at every point i such that the active s value of An alternating electromagnetic field was generated such that it penetrated the active zone of 80 cm3 between the inductors (50 mm gap width) in the mixing container. The magnetic field provided that a vector of magnetic component created a circle or/and elliptic hodo-graph at any i point within that space excluding points of central axis defined between the io inductors such that B, = p*H; where diva; =0, and, therefore, rotA, = B;.
The intensity of the magnetic component was equal to zero at any j point on the central axis and the condition Hi=O, Bj=0 and rotAj=O was satisfied, So, activity of vector potential A of magnetic field with amplitude value from Ai toy A; was generated within the alternating electromagnetic field, such that gradA took effect in the space between the inductors.
is The magnetic force measured about 0.3 T was applied. The input was exposed for 20 sec-onds to said alternating magnetic field. The electric source had 50 Hz.
Upon applying of the magnetic field, the ferromagnetic particles churned the input in the container lively. In this process every ferromagnetic particle performed a role of micro-mixer and micro-grinder due to its interaction with different hodographs of intensity vector H; at 20 different i points within the container.
After termination of the exposure of the input to the electromagnetic field, the particles with an average particle size of the organic material remained in the cellulose-containing mass measured not less than 1 pm. However the magnetic treatment ensured a sufficient desin-tegration of the input material, so that sufficient numbers of cells and intra-and intercellular structures are destroyed.
Then, the cellulose-containing material was carried over from the mixing container to a mold, in the form of a Buchner Funnel. Suction filtration was used to increase the speed of filtra-tion and subsequently the cellulose-containing mass was left to dry so that the dry and solid piece of composite material is left remaining. In this example, the evaporation process en-compassed 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.
1o EXAMPLES 2 to 13 In the present example No. 2 and the following examples No. 3 to 13 the following basic settings were employed.
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.
In each of the experiments 2 to 13 Carboxy Methyl Cellulose (CMC) was used, The Carboxy Methyl Cellulose(CMC) used in the present experiments was obtained from Fischer Chemi-cals 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.
In four of the experiments the input was exposed to an active zone of an electromagnetic field generated between linear electromagnetic inductors as described above.
The time of exposure to the electromagnetic filed is listed in column "Inductor" in Table 1 below.
In experiments 3, 6, 9 and 12 the straw material in the master solution is cooked for 3 s hours as indicated in Column Cooking below. The NaOH based mixture of example 12 is neutralized after cooking.
All experimental samples were transferred onto a paper filter afterwards.
Excess water was pressed off and the remaining filter cake was allowed to settle for 2 hours.
The samples of experiments 2, 5, 8 and 11 were exposed to the active zone between the io inductors for 1 Minute before transferring them to the filter.
All samples were dried afterwards at temperatures between 80 to 85 C for 16 or 24 hours as indicated in column Drying.
Table 1; Experiments 2 to 13 Experiment Master Solution Cooking Inductor Pressing off / CMC Drying Filter 2 0.1 NHCI - 1 min 2 h 7 g 24 h 3 0.1 N HCI 3 h 2 h 7g 24 h LITHCI 2h 7g 16h 5 0.1 NH2SO4 - 1 min 2 h 7 g 24 h 6 0.1 NH2SO4 3 h - 2 h 7g 24 h 7 O.1 NH2SO4 - 2h 7g 16h H2O 1 min 2 h 7 g _16 hh 9 H2O 3 h - 2 h 7 g 24 h 10 H2O - - 2h 7g 16h 11 (1N)NaOH - 1 min 2h 7g 16h 12 (1N)NaOH 3h 2h 7g 24h 13 (IN) NaOH - - 2 h 7 g 24 h 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 cellu-5 lose-containing masses suitable for the production of shaped composites.
However the in-herent 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 I 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-Conflux. 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 pro-ducing a desired product of said cellulose-containing mass, 1o EXAMPLE 15 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 I of hot water in order to produce a trial batch. All trial batches were again wet-milled im-mediately 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 concen-trated by filtering or by dehydration and added during mixing. The mixing was again per-formed in a a high-performance Ringlayer Mixer CoriMix CM available from Gebr, Lodige Maschinenbau GmbH.
The above listed experiments show that according to the present invention the addition of cellulose based adhesives and binders, preferably in a water-soluble form as methyl cellulose and carboxy methyl cellulose enhances the properties of the produced masses and materials.
in further preferred embodiments microcrystalline cellulose and/or powdered cellulose is added to achieve further desired properties;
Claims (26)
1. A method for producing a cellulose-containing mass, the method comprising the steps:
preparing an input comprising at least one organic material and a liquid con-tent; and exposing said input to a wet-mixing procedure at a temperature in the range of 70 to 120 °C, preferably 80 to 100 °C, and most preferred at about 92 to 94 °C.
preparing an input comprising at least one organic material and a liquid con-tent; and exposing said input to a wet-mixing procedure at a temperature in the range of 70 to 120 °C, preferably 80 to 100 °C, and most preferred at about 92 to 94 °C.
2. The method according to claim 1, comprising the step of separating an aqueous, liq-uid cellulose-containing fraction during or after the wet-mixing,
3. The method according to claim 1 or 2, comprising the step of adding additional cellu-lose to the cellulose-containing mass, preferably methyl cellulose and/or carboxy methyl cellulose, preferably in the form of a sodium salt, and/or microcrystalline cellu-lose, or adding cellulose by returning a cellulose containing fraction generated in the wet-mixing procedure after concentration or dehydration,
4. The method according to one of the previous claims, wherein the input is exposed to an active zone of an electromagnetic field and the input preferably comprises a plural-ity of ferromagnetic particles.
5. The method according to claim 4, wherein an average length of the ferromagnetic particles is in a range of about 0.3 to about 25 mm, preferably in a range of about 3 to about 5 mm and wherein an average diameter of the ferromagnetic particles is in a range of about 0.1 to about 5 mm, preferably in a range of about 0.1 to about 2.5 mm.
6. The method according to claim 4 or 5, wherein the ferromagnetic particles have a ratio of diameter to length of about 1:3 to 1:5 and preferably an essentially cylindri-cal form.
7. The method according to any one of claims 4 to 6, wherein a ratio of the ferromag-netic particles to the input is about 1 to about 25 weight percent, preferably about to 15 weight percent.
8. The method according to any one of claims 2 to 7, wherein said active zone is gener-ated between linear electromagnetic inductors generating electromagnetic fields that run towards each other from opposite directions, wherein the inductors preferably ex-cite a common alternating electromagnetic field with circular or elliptic hodograph of intensity of magnetic component, spinning around a common axis that is situated be-tween said inductors.
9. The method according to claim 8, wherein the electromagnetic inductors are sepa-rated from each other by a distance measuring 1 mm to about 5 m, preferably about 50 mm to about 1 m.
10. The method according to claims 8 or 9, wherein a magnetic force of electromagnetic inductors measures about 0.01 to about 20 Tesla, preferably about 0.01 to about 10 Tesla.
11. The method according to any one of claims 2 to 10, wherein the duration of said ex-posure measures about 1 second to about 3 hours, preferably about 5 seconds to about 5 minutes, most preferred about 20 or 60 seconds.
12. The method according to claim 11, wherein the organic material comprises fibers.
13. The method according to claims 11 or 12, wherein the organic material origins from higher plants, preferably selected form the group of true grasses of the family Gramineae (Poaceae) cereal crops being especially preferred, cotton, hemp, flax or mixtures thereof.
14. The method according to claim 13, wherein the organic material origins from at least one of cereal straw and rice straw.
15. The method according to any one of claims 2 to 14, wherein the liquid content com-prises at least one of water and a solvent.
16. The method according to any one of claims 2 to 15, wherein the organic material, is pre-treated by at least one of maceration in a liquid having a pH-value of about 8, more preferably more than 8, most preferably more than 8.4, electromechanical expo-sure, hydrodynamic exposure, ultrasonic exposure, boiling, steaming.
17. A cellulose-containing mass being produced by a method according to any one of claims 1 to 16.
18. A method for producing a composite material comprising a cellulose-containing mass according to claim 17.
19. The method according to claim 18, wherein at least an additive or a modifier are added to at least one of the input or the cellulose-containing mass,
20. The method according to claim 18 or 19, wherein the cellulose-containing mass is homogenized.
21. The method according to any one of claims 18 to 20, wherein the cellulose-containing mass is post-processed by at least one of molding, compression molding, injection molding.
22. The method according to claim 21, wherein an excessive portion of the liquid content is extracted by at least one of drying and curing.
23. A composite material produced by a method according to any one of claims 17 to 22.
24. A product produced from a composite material according to claim 23.
25. The product according to claim 24, being coated with an impregnation, for example by way of immersion.
26. The product according to claim 24 or 25, comprising at least one liner being adhe-sively bonded to the post-processed cellulose-containing mass.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH01532/09A CH701959B1 (en) | 2009-10-01 | 2009-10-01 | Cellulosic mass. |
CH01532/09 | 2009-10-01 | ||
PCT/EP2010/064189 WO2011039121A1 (en) | 2009-10-01 | 2010-09-24 | Cellulose-containing mass |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2774506A1 true CA2774506A1 (en) | 2011-04-07 |
Family
ID=43304827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2774506A Abandoned CA2774506A1 (en) | 2009-10-01 | 2010-09-24 | Cellulose-containing mass |
Country Status (10)
Country | Link |
---|---|
US (1) | US20120193048A1 (en) |
EP (1) | EP2483345A1 (en) |
JP (1) | JP2013506723A (en) |
CN (1) | CN102159637A (en) |
BR (1) | BR112012007295A2 (en) |
CA (1) | CA2774506A1 (en) |
CH (1) | CH701959B1 (en) |
EA (1) | EA201270501A1 (en) |
MX (1) | MX2012003895A (en) |
WO (1) | WO2011039121A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102120870A (en) * | 2011-02-28 | 2011-07-13 | 殷正福 | Degradable plastic and production method thereof |
CH704766A1 (en) * | 2011-04-01 | 2012-10-15 | Vadim Gogichev | A process for preparing a cellulose-containing material for producing a composite material. |
CN109705600A (en) * | 2018-12-28 | 2019-05-03 | 广州鸿绵合成材料有限公司 | A kind of high-performance ligno cellulose fiber and preparation method |
CN113182023B (en) * | 2021-04-21 | 2022-06-03 | 南京工程学院 | On-line detection method for mill load of non-measurable disturbance self-adaptive monitoring and compensation |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB592633A (en) * | 1945-04-25 | 1947-09-24 | English Metal Powder Company L | Metal-containing cellulose-acetate films |
US3691130A (en) * | 1970-08-06 | 1972-09-12 | Dmitry Danilovich Logvinenko | Method of producing metal-polymer compositions |
US4093189A (en) * | 1976-10-18 | 1978-06-06 | Iosif Borisovich Sokol | Apparatus for continuous preparation of a suspension |
FR2378084A1 (en) * | 1977-01-21 | 1978-08-18 | Rostovsky O Neftemaslozavod | PROCESS FOR PREPARING PLASTIC AND LIQUID LUBRICANTS |
US4601431A (en) * | 1982-09-13 | 1986-07-22 | Fuji Electric Company, Ltd. | Traveling magnetic field type crusher |
US5139861A (en) * | 1990-06-21 | 1992-08-18 | E. I. Du Pont De Nemours And Company | Process for bonding blends of cellulosic pulp and fusible synthetic pulp or fiber by high-speed dielectric heating and products produced thereby |
EP1220031A3 (en) * | 2000-12-29 | 2002-08-14 | Eastman Kodak Company | Film support with improved adhesion upon annealing |
GB0101630D0 (en) * | 2001-01-23 | 2001-03-07 | Amylum Europ Nv | Method for preparing composite materials containing natural binders |
AU2003245564A1 (en) * | 2002-06-20 | 2004-01-06 | Arizona Board Of Regents | Method and arrangement of rotating magnetically inducible particles |
US7576147B2 (en) | 2004-08-27 | 2009-08-18 | Board Of Trustees Of Michigan State University | Cellulosic biomass soy flour based biocomposites and process for manufacturing thereof |
EP1815198A4 (en) * | 2004-11-12 | 2014-01-15 | Michigan Biotech Inst | Process for treatment of biomass feedstocks |
CN101062572A (en) * | 2006-04-29 | 2007-10-31 | 山东贺友集团有限公司 | New technique for producing wood-plastic clad plate |
SG174746A1 (en) * | 2006-10-26 | 2011-10-28 | Xyleco Inc | Processing biomass |
US7579396B2 (en) | 2007-01-31 | 2009-08-25 | Eastman Kodak Company | Polymer composite |
CH700073A2 (en) * | 2008-12-03 | 2010-06-15 | Corp Vadim Gogichev C O Kremlin Group | Current generator, e.g. galvanic cell for supplying medicinal implants, comprises separating layer containing zwitterionic and/or radical compound between two electrodes |
BRPI0823319A2 (en) * | 2008-12-03 | 2015-06-23 | Vadim Gogichev | Cellulose-containing pasta |
FR2940297B1 (en) * | 2008-12-18 | 2013-12-20 | Ab7 Ind | COMPOSITE PLASTIC MATERIAL IN THE FORM OF GRANULATES FROM PLANT PROTEIN MATERIALS AND METHOD OF MANUFACTURING THE SAME |
-
2009
- 2009-10-01 CH CH01532/09A patent/CH701959B1/en not_active IP Right Cessation
-
2010
- 2010-09-24 EA EA201270501A patent/EA201270501A1/en unknown
- 2010-09-24 CN CN2010800034722A patent/CN102159637A/en active Pending
- 2010-09-24 BR BR112012007295A patent/BR112012007295A2/en not_active Application Discontinuation
- 2010-09-24 CA CA2774506A patent/CA2774506A1/en not_active Abandoned
- 2010-09-24 MX MX2012003895A patent/MX2012003895A/en not_active Application Discontinuation
- 2010-09-24 EP EP10757768A patent/EP2483345A1/en not_active Withdrawn
- 2010-09-24 JP JP2012531336A patent/JP2013506723A/en not_active Withdrawn
- 2010-09-24 WO PCT/EP2010/064189 patent/WO2011039121A1/en active Application Filing
- 2010-09-24 US US13/498,870 patent/US20120193048A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO2011039121A1 (en) | 2011-04-07 |
CH701959A1 (en) | 2011-04-15 |
EP2483345A1 (en) | 2012-08-08 |
US20120193048A1 (en) | 2012-08-02 |
JP2013506723A (en) | 2013-02-28 |
CH701959B1 (en) | 2012-04-30 |
MX2012003895A (en) | 2012-07-25 |
EA201270501A1 (en) | 2012-09-28 |
BR112012007295A2 (en) | 2016-04-19 |
CN102159637A (en) | 2011-08-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Blanco et al. | Nanocellulose for industrial use: cellulose nanofibers (CNF), cellulose nanocrystals (CNC), and bacterial cellulose (BC) | |
Lalit et al. | Natural fibers and biopolymers characterization: A future potential composite material | |
Trache et al. | Microcrystalline cellulose: Isolation, characterization and bio-composites application—A review | |
Laadila et al. | Green synthesis of novel biocomposites from treated cellulosic fibers and recycled bio-plastic polylactic acid | |
CA2801989C (en) | A novel method to produce microcellulose | |
US11524921B2 (en) | Composite materials containing hemp and nanocellulose | |
CN108264743A (en) | A kind of preparation method of plant polyphenol/nano-cellulose polymer composite based on multiple hydrogen bonding effect | |
CA2774506A1 (en) | Cellulose-containing mass | |
CN111690178A (en) | Starch-based fully-degradable nano antibacterial material and preparation method thereof | |
US20140053756A1 (en) | Method for producing cellulose-containing mass for producing composite material | |
Jančíková et al. | The role of deep eutectic solvents in the production of cellulose nanomaterials from biomass | |
CN111138719A (en) | Preparation method of powder containing nano-cellulose | |
Fauziyah et al. | Bagasse nanocellulose (Saccharum officinarum L.): process optimization and characterization | |
US8877919B2 (en) | Cellulose-containing mass | |
Kusmono et al. | Influence of Hydrolysis Conditions on Characteristics of Nanocrystalline Cellulose Extracted from Ramie Fibers by Hydrochloric Acid Hydrolysis | |
Liu | Isolation and characterization of nanocelluloses from wheat straw and their application in agricultural water-saving materials | |
WO2015011066A1 (en) | Method for producing molded products | |
CN116462920B (en) | Preparation method of nut shell/polyvinyl chloride composite material | |
CN107936305A (en) | A kind of preparation method of no glue middle-high density vegetable fibre board | |
Liu et al. | Production of microfibrillated cellulose fibers and their application in polymeric composites | |
Köhnlein | Preparation of films and nonwoven composites from fungal microfibers grown in bread waste | |
CN115961495A (en) | Production process of environment-friendly paper pulp molding garbage can | |
Renugaa et al. | NANOCELLULOSE-AN EMERGING RESOURCE FOR FUTURE TECHNOLOGY: A REVIEW | |
CN106012628A (en) | Preparation method for environment-friendly ramie paper pulp | |
Ramesh et al. | Extraction of cellulose nano fibers and development of nano cellulose fiber composites-a review |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |
Effective date: 20140924 |