WO1998031764A1 - Adhesifs a base de lignine pour la fabrication de panneaux de particules - Google Patents
Adhesifs a base de lignine pour la fabrication de panneaux de particulesInfo
- Publication number
- WO1998031764A1 WO1998031764A1 PCT/FI1998/000026 FI9800026W WO9831764A1 WO 1998031764 A1 WO1998031764 A1 WO 1998031764A1 FI 9800026 W FI9800026 W FI 9800026W WO 9831764 A1 WO9831764 A1 WO 9831764A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- fibers
- wood
- pulping
- composition according
- Prior art date
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 78
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000000835 fiber Substances 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002023 wood Substances 0.000 claims abstract description 38
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 23
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000004537 pulping Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 7
- 239000012978 lignocellulosic material Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 28
- 102000004316 Oxidoreductases Human genes 0.000 claims description 20
- 108090000854 Oxidoreductases Proteins 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 102000004190 Enzymes Human genes 0.000 claims description 14
- 108090000790 Enzymes Proteins 0.000 claims description 14
- 239000011094 fiberboard Substances 0.000 claims description 14
- 229920005611 kraft lignin Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 102000003992 Peroxidases Human genes 0.000 claims description 8
- 229920002522 Wood fibre Polymers 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000002025 wood fiber Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 230000000930 thermomechanical effect Effects 0.000 claims description 3
- 241001251054 Formica truncorum Species 0.000 claims description 2
- 239000007970 homogeneous dispersion Substances 0.000 abstract 1
- 108010029541 Laccase Proteins 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920001807 Urea-formaldehyde Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZMWAXVAETNTVAT-UHFFFAOYSA-N 7-n,8-n,5-triphenylphenazin-5-ium-2,3,7,8-tetramine;chloride Chemical compound [Cl-].C=1C=CC=CC=1NC=1C=C2[N+](C=3C=CC=CC=3)=C3C=C(N)C(N)=CC3=NC2=CC=1NC1=CC=CC=C1 ZMWAXVAETNTVAT-UHFFFAOYSA-N 0.000 description 5
- 108700020962 Peroxidase Proteins 0.000 description 5
- 102000003425 Tyrosinase Human genes 0.000 description 5
- 108060008724 Tyrosinase Proteins 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004026 adhesive bonding Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 poly(acryl amide) Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 description 2
- 102000030523 Catechol oxidase Human genes 0.000 description 2
- 108010031396 Catechol oxidase Proteins 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- PDBXHPORMXSXKO-UHFFFAOYSA-N 8-benzyl-7-[2-[ethyl(2-hydroxyethyl)amino]ethyl]-1,3-dimethylpurine-2,6-dione;hydron;chloride Chemical compound Cl.N=1C=2N(C)C(=O)N(C)C(=O)C=2N(CCN(CCO)CC)C=1CC1=CC=CC=C1 PDBXHPORMXSXKO-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 108010015428 Bilirubin oxidase Proteins 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 241001465180 Botrytis Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 1
- 108090000604 Hydrolases Proteins 0.000 description 1
- 102000004157 Hydrolases Human genes 0.000 description 1
- 241000222418 Lentinus Species 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 241000221960 Neurospora Species 0.000 description 1
- 241000222395 Phlebia Species 0.000 description 1
- 241000221945 Podospora Species 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 108010059820 Polygalacturonase Proteins 0.000 description 1
- 241000222640 Polyporus Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241001361634 Rhizoctonia Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 241000222354 Trametes Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006872 enzymatic polymerization reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000123 paper Substances 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J1/00—Fibreboard
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/005—Lignin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J197/00—Adhesives based on lignin-containing materials
- C09J197/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/08—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers using foamed adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
Definitions
- the present invention relates to the manufacture of particle boards and similar wood-based products comprising lignocellulosic particles, fibers or flakes mixed with and bonded together with an adhesive binder.
- the present invention concerns novel lignin and/or carbohydrate -based adhesives and a preparation process thereof as well as particle boards manufactured using the adhesives.
- SSL As an adhesive for fiber board manufacture is its hygroscopicity. For this reason it cannot really compete with otner natural or synthetic adhesives.
- SSL When SSL is applied as an adhesive, it can be converted to an insoluble substance by curing. Chemically the curing of lignin is a cross-linking process, which leads to new carbon-carbon and ether bonds between different lignin molecules or within one macromolecule. Inter- as well as intramolecular cross-linking reactions decrease the solubility and swelling of lignin. Cross-links in lignin can be acnieved either by condensation or by radical coupling reactions.
- laccase enzymes and other peroxidases can be used as polymerization or curing catalysts of lignin (DE Patent No. 3 037 992, WO 96/03546).
- the enzymes for creating radical reaction have shown limited success so far.
- Fibers and wood chips used in the production of fiber boards contain 5 - 20 % water and the laccases used need some water to effectively catalyze the polymerization reaction needed for extensive bonding of the fiberboard.
- Kraft lignin like native lignin to its major part is, however, insoluble in water and thus two solid phases are formed on the production line. An uneven distribution of the solids cause spotting and major failure in the strength properties of the board formed in the pressing stage.
- a further problem relating to the use of isolated lignin is the high price of kraft lignin, which is near the limit for economical production of particle boards.
- the present invention aims at eliminating the problems relating to the prior art.
- lignin or lignin polymerized with oxidative enzymes or a soluble fraction of carbohydrates obtained from mechanical refining of lignocellulosic materials is added to and mixed with the fibers or chips or flakes used as lignocellulosic raw material of the wood-based product in the form of a foam to provide an even dispersion of the solids.
- Foamed UF and PF adhesives are known in the art. Said foams are used for improving process performance and product quality especially in adhesives with high solid contents.
- CA Patent Application No. 2,114,258 describes particle board production by using foamed mixtures of UF resins and animal blood.
- DE 3,644,067 describes the use of foamed materials in binding of fibers and flakes to produce a homogeneous adhesive application of fine particles (fibres or powders) on the furnish.
- T. Sellers describes in Forest Prod. J. 38
- the lignin-based adhesive composition according to the present invention comprises an aqueous suspension of lignin and/or carbohydrates obtained from a process of pulping lignocellulosic materials.
- the suspension has been foamed to 1.05 to 10, preferably 1.1 to 8, in particular to 1.2 to 5 times the volume of the liquid mixture.
- polymerized kraft lignin as the lignin component.
- natural lignin in wood fibers is used to replace a substantial part of the lignin in the adhesive binder intended for particle board production.
- the present adhesive binders comprise an aqueous mixture of fibers together with lignin and/or carbohydrates obtained from a process of pulping lignocellulosic raw materials.
- the fibers in the adhesive binder as well as the added lignin and/or other lignocellulosic material radical polymerize due to the effect of the enzyme in an even oxygen- containing foam matrix.
- the use of native lignin -containing fibers of MDF or TMP types leads to savings in adhesive use, and, however, to a corresponding strength.
- the foam will homogenize the solid phase and the liquid phase, increase the viscosity of the mixture and prevent the sedimentation of the solids.
- the oxygen-containing foamed structure will also provide more oxygen for the oxygen-dependent oxidase catalyzed lignin carbohydrate polymerization. Because of its large volume, the foam will cover more homogeneously the wood fibers and wood particles in the preparation of the boards. This will lead to better strength values and better control of the use of the adhesive in the production.
- resin designate a chemical composition which, in the wet stages of the manufacture of, e.g. particle and fiber boards, provides adhesion between the particles or fibers. After heat compression during board manufacture, the composition containing polymerized resin works as a binder which keeps the particles or fibers or flakes bonded together.
- wood-based product denotes any lignocellulose-based product, such as particle boards, fiber boards (including high and medium density fiber boards, i.e. hard boards and MDF boards), flake boards, plywood and similar products constituted by particles, fibers or flakes of vegetable origin, in particular derived from wood or annular or perennial plants mixed with and bonded together with adhesive binders.
- the present invention is used for preparing particle boards and similar wood-based products in which wood particles can be crosslinked and joined together with the fibers of the adhesive composition, which will be attached to the particles by the lignin-based adhesive.
- fibers encompasses organic and inorganic fibers of any suitable material having a length-to-thickness ratio of more than 6, preferably more than 10, in particular more than 20. It is preferred to use lignin-containing fibers, because the lignin of the fibers will be oxidized in the presence of oxidases and work as an adhesive in mixtures of wood particles and the adhesive foam. Particularly preferred lignocellulosic fibers are derived from wood or annular or perennial plants. Such fibers can be obtained from mechanical refining of wood or plants by refiner mechanical pulping, pressurized refiner mechanical pulping, thermomechanical pulping, groundwood or pressurized groundwood pulping, or chemi- thermomechanical pulping. Furthermore, fibers from the preparation of fiber boards (e.g. medium density or high density fiber boards) can be used in the preparation of particle boards.
- fiber boards e.g. medium density or high density fiber boards
- cellulosic fibers In addition to the cellulosic fibers mentioned above, other natural fibers, such as cotton fibers, Abaca hemp fibers, sisal fibers, ramie fibers, flax fibers or jute fibers, can be used. Inorganic fibers such as glass fibers, carbon fibers, gypsum fibers, etc. can also be employed.
- oxidative enzymes capable of catalyzing oxidation of phenolic groups can be used. These enzymes are oxidoreductases, such as peroxidases and oxidases. "Peroxidases” are enzymes which catalyze oxidative reaction using hydrogen peroxide as their substrate, whereas “oxidases” are enzymes which catalyze oxidative reactions using molecular oxygen as their substrate.
- Phenoloxidases (EC 1.10.3.2 benzenediol: oxygen oxidoreductase) catalyze the oxidation of o- and p-substituted phenolic hydroxyl and amino/amine groups in monomeric and polymeric aromatic compounds.
- the oxidative reaction leads to the formation of phenoxy radicals and finally to the polymerization of lignin and possibly the carbohydrate matter.
- the enzyme used may be any of the enzymes catalyzing the biological radical formation and secondary chemical polymerization of low molecular weight lignins, such as laccase, tyrosinase, peroxidase or oxidase.
- oxidases As specific examples of oxidases the following can be mentioned: laccases (EC 1.10.3.2), catechol oxidases (EC 1.10.3.1), tyrosinases (EC 1.14.18.1) and bilirubin oxidases (EC
- Laccases are particularly preferred oxidases. They can be obtained from bacteria and fungi belonging to, e.g., the following strains: Aspergillus. Neurospora, Podospora, Botrytis, Lentinus, Polyporus, Rhizoctonia, Coprimis, Co iol s, Phlebia, Ple rotus, Fusarium and Trametes.
- Suitable peroxidases can be obtained from plants or fungi or bacteria.
- Preferred peroxidases are those which originate from plants, in particular horseradish peroxidase and soy bean peroxidase.
- surfactant or "surface active agent” are synonymously used to designate compounds which have affinity to water and to hydrophobic (e.g. fatty) materials, thus aiding the hydrophobic materials to suspend in water.
- lignin of different origins can be used as the adhesive component of the present foamed adhesive binders.
- isolated lignin of, e.g., the sulphate, sulphite, ORGANOSOLV and MILOX processes can be used.
- soluble wood fractions can also be employed.
- This fraction contains primarily the same chemical components as the fibers (carbohydrates, extractives and lignin).
- the soluble fraction of softwood chips contains some 40 to 70 % carbohydrates, 10 to 25 % lignin and 1 to 10 % extractives, whereas hardwood pulping process water contains some 20 to 60 % carbohydrates, 10 to 25 % lignin and 10 to 40 % extractives.
- this soluble lignin/carbohydrate fraction obtainable from mechanical or chemimechanical pulping is particularly useful as an additive or adjuvant for gluing of particles boards, fiber boards and other similar wood-based composite products. Particularly good gluing is achieved if this fraction (as is the case with lignin) is polymerized with laccase (or similar) oxidase enzyme(s). The results are on the same level as those obtainable with conventional phenol or urea formaldehyde resins. It should be noticed that a similar soluble fraction can be obtained by treating lignocellulosic raw material, such as wood fibers or saw dust, with hydrolases, e.g. cellulases, hemicellulases and pectinases.
- hydrolases e.g. cellulases, hemicellulases and pectinases.
- the present invention relates to foam-based technology for providing good dispersion of the different solids.
- efficient contact during economical production of particle board is achieved using adhesive binders based on oxidase-activated lignin and/or carbohydrates together with wood fibers or other lignocellulosic fibers.
- 0.1 to 50 %, preferably 0.5 to 30 % and in particular about 1 to 10 % by weight of the kraft lignin or similar lignin is replaced by fibers in the foam-based, oxidase-activated adhesive formulation.
- lignin and the fibers are activated by oxidases are mixed with the chips in the form of a foam that provides a good viscose suspending medium to form an even dispersion of the solids and hence improves substantially the quality of the particle board formed.
- the use of the foamed adhesives as described in this invention leads also to better control of the application and to substantial savings in adhesive use.
- the foam is produced by the use of a surface active agent.
- the foamed, activated fiber and lignin/carbohydrate dispersion can be produced separately from the chips, which are mixed into the foam by known mixing technology, e.g. by extruding or spraying the foam onto the fibers or chips.
- the foam can also be produced simultaneously by mixing the fibers and chips with the foam chemicals, the lignin/carbohydrates and the laccase.
- the foam is produced by dispersing the mixture of lignin and fibers into water to form a suspension and bubbling a gas through the suspension to form bubbles having a medium diameter of 0.001 to 1 mm, in particular about 0.01 to 0.1 mm.
- the foam is produced by the use of a surface active agent that can be anionic, cationic or non-ionic.
- the surfactant can be selected from the group consisting of alkylsulfonate or alkyl benzene sulfonate, Tween® and other commercial compounds, fatty acid soaps, lignosulfonates, sarcosinates, fatty acid amines or amines or poly(oxyetylene alcohol)s and wood and plant extractives.
- Foam stabilizers and solid surfactants such as CMC, gelatin, pectin, wood extractive and similar compounds, can be used to produce and enhance the foam stability.
- a small amount of the surface active compounds is needed, i.e. about 0.01 to 10 %, in particular about 0.05 to 5 %.
- the foam can be produced by foaming in a static foamer or in a turbulent foam cell by using known mixing technology.
- any gas can be used for foaming, it is preferred to use oxygen-containing gases, such as air, oxygen enriched air, oxygen or pressurized systems of these. The importance of using oxygen-containing gases is discussed in further detail below.
- the foam produced is essentially stable during handling, storage, transport and manufacture of wood-based products and it has a density in the range of 0.1 to 0.9 kg/1, in particular about 0.2 to 0.7 kg/1, and a medium foam bubble diameter in the range of 0.005 to 0.1 mm, in particular about 0.01 to 0.1 mm, preferably about 0.02 mm.
- the method according to the present invention can be used for all oxidase-catalyzed, previously unsuccessfully suggested enzyme-catalyzed glueing processes using oxidases
- the enzyme used can be any of the enzymes catalyzing the oxidation and polymerization of aromatic compounds or lignins, such as laccase, tyrosinase, or other oxidases, as mentioned above.
- the amount of enzyme used varies depending on the activity of the enzyme and on the amount of dry matter content of the composition.
- the oxidases are used in amounts of 0.001 to 10 mg protein/g of dry matter, preferably about 0, 1 to 5 mg protein/g of dry matter.
- the activity of the oxidase is about 1 to 100,000 nkat/g, preferably over 100 nkat/g.
- oxygen plays a decisive role in the enzymatic polymerization of lignin of any origin. This is important in particular for the production of adhesives for the manufacture of fiber boards, particle boards and flake boards and other similar wood-based products. Thus, in addition to the aromatic reactant, also oxygen is needed. The oxidative reaction leads to the formation of phenoxy radicals and finally to the polymerization of lignin.
- Oxygen can be supplied by various means, such as efficient mixing, air enriched with oxygen or introducing oxygen supplied by enzymatic or chemical means to the solution.
- Oxygen can be supplied by various means, such as efficient mixing, air enriched with oxygen or introducing oxygen supplied by enzymatic or chemical means to the solution.
- by foaming the suspension with an oxygen- containing gas it is possible to provide the oxygen needed for full polymerization of the lignin.
- the foamed structure gives enough strength to the adhesive so as to prevent sedimentation of water-insoluble lignin or the polymerized lignin from the adhesive thus producing failure in the production and in the board product.
- the foamed structure can be utilized in the preparation of particle boards of lignin and/or carbohydrates or polymerized lignin by utilizing the adhesive properties of the lignin or polymerized lignin, whereas the fibers work as crosslinkers between the particles.
- the foam will homogenize the inhomogenous solid phase and the liquid phase, increase the viscosity of the mixture and prevent the sedimentation of the solids and the fibers.
- the oxygen-containing foamed structure will also provide more oxygen for oxygen-enhanced oxidase catalyzed lignin/carbohydrate polymerization. Because of its large volume the foam will cover more homogeneously the wood fibres and wood particles in the preparation of the boards.
- the adhesive binder is evenly distributed throughout the wood-based product, about 0.02 ⁇ 0.002...0.2 ⁇ 0.02 g/cm 3 , preferably 0.04 to 0.08 g/cm 3 in any randomly selected volume unit of the product This leads to better strength values and better control of the use of the adhesive in the production.
- MDF fibers were prepared from hardwood (Swedish birch) by refining birch chips in a conventional TMP process at a refiner pressure of 4 bar.
- This Example describes the preparation of a foamed adhesive consisting of kraft lignin, laccase, wood fibre and the manufacture of particle boards from the adhesive.
- the test has been carried out on laboratory scale.
- Kraft lignin Indulin AT and 1 - 10 % of its weight substituted with the MDF fibers of Example 1 were used as a binder mixture in particle board test panel manufacture.
- particle board panels of the size of 50 mm x 50 mm x 2 mm were prepared by pressing 2 min in 30 kp/cm 2 of pressure and 190 °C of temperature. After pressing, the panels were then cut into four pieces (50 mm x 12 mm x 2 mm). These pieces were tested for parallel tensile strength with Zwick tensile strength testing equipment.
- the strength properties of particle boards prepared according to the present invention are quite comparable to those of conventional UF resin glued boards.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98900858A EP0953030A1 (fr) | 1997-01-14 | 1998-01-14 | Adhesifs a base de lignine pour la fabrication de panneaux de particules |
SK941-99A SK94199A3 (en) | 1997-01-14 | 1998-01-14 | Lignin-based adhesives for particle board manufacture |
CA002277286A CA2277286A1 (fr) | 1997-01-14 | 1998-01-14 | Adhesifs a base de lignine pour la fabrication de panneaux de particules |
BR9806909-8A BR9806909A (pt) | 1997-01-14 | 1998-01-14 | Adesivos à base de lignina a fabricação de prancha de partiìcula |
AU56645/98A AU5664598A (en) | 1997-01-14 | 1998-01-14 | Lignin-based adhesives for particle board manufacture |
NZ336668A NZ336668A (en) | 1997-01-14 | 1998-01-14 | Lignin and/or carbohydrate-based adhesives for particle board manufacture and method for preparation |
HU0200620A HUP0200620A2 (hu) | 1997-01-14 | 1998-01-14 | Ligninalapú ragasztók forgácslemezgyártáshoz, forgácslemezek és eljárás e ragasztók, valamint forgácslemez előállítására |
PL98334548A PL334548A1 (en) | 1997-01-14 | 1998-01-14 | Lignin-based glues for use in manufacture of chipboards |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI970160A FI104835B (fi) | 1997-01-14 | 1997-01-14 | Ligniinipohjaiset sideaineet lastulevyvalmistusta varten |
FI970160 | 1997-01-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998031764A1 true WO1998031764A1 (fr) | 1998-07-23 |
Family
ID=8547605
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1998/000026 WO1998031764A1 (fr) | 1997-01-14 | 1998-01-14 | Adhesifs a base de lignine pour la fabrication de panneaux de particules |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0953030A1 (fr) |
KR (1) | KR20000070164A (fr) |
CN (1) | CN1250463A (fr) |
AU (1) | AU5664598A (fr) |
BR (1) | BR9806909A (fr) |
CA (1) | CA2277286A1 (fr) |
FI (1) | FI104835B (fr) |
HU (1) | HUP0200620A2 (fr) |
ID (1) | ID22657A (fr) |
NZ (1) | NZ336668A (fr) |
PL (1) | PL334548A1 (fr) |
SK (1) | SK94199A3 (fr) |
WO (1) | WO1998031764A1 (fr) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6217942B1 (en) | 1998-12-08 | 2001-04-17 | Genencor International, Inc. | Lignin based coating |
WO2004085521A1 (fr) * | 2003-03-28 | 2004-10-07 | Bakelite Oy | Composition de colle |
WO2006076814A1 (fr) * | 2005-01-21 | 2006-07-27 | 9119-3656 Quebec Inc. | Composition hybride de fibres de bois et de vegetaux autres que le bois et utilisations de celle-ci |
US8143335B2 (en) | 2003-03-28 | 2012-03-27 | Momentive Specialty Chemicals Inc. | Adhesive composition |
WO2012126709A1 (fr) | 2011-03-24 | 2012-09-27 | Annikki Gmbh | Procédé de production de dérivés de lignine |
WO2016057390A1 (fr) * | 2014-10-07 | 2016-04-14 | Georgia-Pacific Chemicals Llc | Adhésifs contenant une résine, une lignine kraft, et un tensioactif, et leurs procédés de fabrication et d'utilisation |
CN111100581A (zh) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | 一种全生物基胶黏剂及其制备方法和应用 |
US10793646B2 (en) | 2014-09-26 | 2020-10-06 | Renmatix, Inc. | Adhesive compositions comprising type-II cellulose |
FR3125822A1 (fr) * | 2021-07-27 | 2023-02-03 | Rene Massard | Mousse aqueuse |
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Publication number | Priority date | Publication date | Assignee | Title |
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FI123936B2 (en) | 2012-03-29 | 2019-03-29 | Upm Kymmene Corp | A method for increasing the reactivity of lignin |
FI126736B (en) | 2013-11-26 | 2017-04-28 | Upm Kymmene Corp | Process for treating lignin and preparing a binder composition |
CN104097247B (zh) * | 2014-07-23 | 2016-08-17 | 浙江农林大学 | 一种自清洁环保竹碎料板及其制备方法 |
US11690332B2 (en) | 2020-04-03 | 2023-07-04 | Rockwool A/S | Method of growing plants |
GB2608951A (en) * | 2020-04-03 | 2023-01-18 | Rockwool As | Method of draining water |
EP4497861A3 (fr) * | 2020-04-03 | 2025-04-23 | Rockwool A/S | Procédé de drainage d'eau |
CN114410707B (zh) * | 2022-01-25 | 2023-08-15 | 齐鲁工业大学 | 一种纯化阔叶木制浆预水解液中糖分的方法 |
CN114368053A (zh) * | 2022-01-25 | 2022-04-19 | 浙江省林业科学研究院 | 一种高粘度流动态纤维悬浮液及其制备方法和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2848038A1 (de) * | 1977-11-10 | 1979-05-17 | Furniere & Platten Vvb | Verfahren und vorrichtung zum aufschaeumen eines fluessigen bindemittels |
DE3644067A1 (de) * | 1986-12-22 | 1988-06-30 | Kiss G H | Verfahren zum beleimen von fasern, faeden, spaenen, schliff oder dergleichen schuettfaehigen rohstoffen und vorrichtung zur durchfuehrung des verfahrens |
EP0492016A1 (fr) * | 1990-12-28 | 1992-07-01 | K.C. Shen Technology International Ltd. | Résine thermodurcissable et produit composite à partir de matière lignocellulosique |
WO1992020857A1 (fr) * | 1991-05-17 | 1992-11-26 | Call Hans Peter | Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases |
WO1993025622A1 (fr) * | 1992-06-12 | 1993-12-23 | Novo Nordisk A/S | Procede pour augmenter la solubilite de la lignine |
-
1997
- 1997-01-14 FI FI970160A patent/FI104835B/fi active
-
1998
- 1998-01-14 AU AU56645/98A patent/AU5664598A/en not_active Abandoned
- 1998-01-14 HU HU0200620A patent/HUP0200620A2/hu unknown
- 1998-01-14 EP EP98900858A patent/EP0953030A1/fr not_active Withdrawn
- 1998-01-14 NZ NZ336668A patent/NZ336668A/en unknown
- 1998-01-14 BR BR9806909-8A patent/BR9806909A/pt not_active Application Discontinuation
- 1998-01-14 KR KR1019997006390A patent/KR20000070164A/ko not_active Withdrawn
- 1998-01-14 CN CN98803315A patent/CN1250463A/zh active Pending
- 1998-01-14 CA CA002277286A patent/CA2277286A1/fr not_active Abandoned
- 1998-01-14 ID IDW990681A patent/ID22657A/id unknown
- 1998-01-14 SK SK941-99A patent/SK94199A3/sk unknown
- 1998-01-14 WO PCT/FI1998/000026 patent/WO1998031764A1/fr not_active Application Discontinuation
- 1998-01-14 PL PL98334548A patent/PL334548A1/xx unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2848038A1 (de) * | 1977-11-10 | 1979-05-17 | Furniere & Platten Vvb | Verfahren und vorrichtung zum aufschaeumen eines fluessigen bindemittels |
DE3644067A1 (de) * | 1986-12-22 | 1988-06-30 | Kiss G H | Verfahren zum beleimen von fasern, faeden, spaenen, schliff oder dergleichen schuettfaehigen rohstoffen und vorrichtung zur durchfuehrung des verfahrens |
EP0492016A1 (fr) * | 1990-12-28 | 1992-07-01 | K.C. Shen Technology International Ltd. | Résine thermodurcissable et produit composite à partir de matière lignocellulosique |
WO1992020857A1 (fr) * | 1991-05-17 | 1992-11-26 | Call Hans Peter | Procede a rendement ameliore pour la delignification de produits lignocellulosiques, ainsi que pour le blanchiment et le traitement d'eaux residuaires au moyen de laccases |
WO1993025622A1 (fr) * | 1992-06-12 | 1993-12-23 | Novo Nordisk A/S | Procede pour augmenter la solubilite de la lignine |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6217942B1 (en) | 1998-12-08 | 2001-04-17 | Genencor International, Inc. | Lignin based coating |
CN1761701B (zh) * | 2003-03-28 | 2013-01-16 | 禾逊专业化学有限公司 | 粘合剂组合物 |
US8143335B2 (en) | 2003-03-28 | 2012-03-27 | Momentive Specialty Chemicals Inc. | Adhesive composition |
WO2004085521A1 (fr) * | 2003-03-28 | 2004-10-07 | Bakelite Oy | Composition de colle |
WO2006076814A1 (fr) * | 2005-01-21 | 2006-07-27 | 9119-3656 Quebec Inc. | Composition hybride de fibres de bois et de vegetaux autres que le bois et utilisations de celle-ci |
WO2012126709A1 (fr) | 2011-03-24 | 2012-09-27 | Annikki Gmbh | Procédé de production de dérivés de lignine |
EP2522690A1 (fr) | 2011-03-24 | 2012-11-14 | Annikki GmbH | Procédé de fabrication de dérivés de lignine |
US9206292B2 (en) | 2011-03-24 | 2015-12-08 | Annikki Gmbh | Method for producing lignin derivatives |
US10793646B2 (en) | 2014-09-26 | 2020-10-06 | Renmatix, Inc. | Adhesive compositions comprising type-II cellulose |
WO2016057390A1 (fr) * | 2014-10-07 | 2016-04-14 | Georgia-Pacific Chemicals Llc | Adhésifs contenant une résine, une lignine kraft, et un tensioactif, et leurs procédés de fabrication et d'utilisation |
CN111100581A (zh) * | 2019-12-02 | 2020-05-05 | 福建农林大学 | 一种全生物基胶黏剂及其制备方法和应用 |
CN111100581B (zh) * | 2019-12-02 | 2020-11-06 | 福建农林大学 | 一种全生物基胶黏剂及其制备方法和应用 |
FR3125822A1 (fr) * | 2021-07-27 | 2023-02-03 | Rene Massard | Mousse aqueuse |
Also Published As
Publication number | Publication date |
---|---|
FI970160A0 (fi) | 1997-01-14 |
FI970160L (fi) | 1998-07-15 |
CN1250463A (zh) | 2000-04-12 |
NZ336668A (en) | 2000-02-28 |
PL334548A1 (en) | 2000-03-13 |
EP0953030A1 (fr) | 1999-11-03 |
ID22657A (id) | 1999-12-02 |
AU5664598A (en) | 1998-08-07 |
SK94199A3 (en) | 2000-05-16 |
FI104835B (fi) | 2000-04-14 |
KR20000070164A (ko) | 2000-11-25 |
HUP0200620A2 (hu) | 2003-07-28 |
CA2277286A1 (fr) | 1998-07-23 |
BR9806909A (pt) | 2000-05-16 |
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