WO2022132077A1 - Using whey protein-based natural adhesive in the production of mdf and composite board - Google Patents
Using whey protein-based natural adhesive in the production of mdf and composite board Download PDFInfo
- Publication number
- WO2022132077A1 WO2022132077A1 PCT/TR2021/050862 TR2021050862W WO2022132077A1 WO 2022132077 A1 WO2022132077 A1 WO 2022132077A1 TR 2021050862 W TR2021050862 W TR 2021050862W WO 2022132077 A1 WO2022132077 A1 WO 2022132077A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- urea
- formaldehyde
- resin
- wood
- reactor
- Prior art date
Links
- 108010046377 Whey Proteins Proteins 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 102000007544 Whey Proteins Human genes 0.000 title claims abstract description 34
- 235000021119 whey protein Nutrition 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 239000000227 bioadhesive Substances 0.000 title description 2
- 239000003292 glue Substances 0.000 claims abstract description 29
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 18
- 239000002023 wood Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 14
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005862 Whey Substances 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 235000013351 cheese Nutrition 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 6
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- 239000004202 carbamide Substances 0.000 claims description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 102100035024 Carboxypeptidase B Human genes 0.000 claims description 27
- 101000946524 Homo sapiens Carboxypeptidase B Proteins 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000008098 formaldehyde solution Substances 0.000 claims description 9
- 239000011094 fiberboard Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 238000010411 cooking Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- 235000018102 proteins Nutrition 0.000 description 10
- 102000004169 proteins and genes Human genes 0.000 description 10
- 108090000623 proteins and genes Proteins 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 241001070947 Fagus Species 0.000 description 4
- 235000010099 Fagus sylvatica Nutrition 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008101 lactose Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- -1 amino, carboxyl Chemical group 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Classifications
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
Definitions
- the present invention relates to the use of protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production.
- Whey proteins are often referred to as waste proteins. In general, it consists of multiple components with a dense spherical structure and low molecular weight. While the biological value of PASP is quite high, this high biological value is shown as a criterion showing that the amount of amino acids is high and almost all of the digested protein will be used by the muscles and the body.
- Concentrated whey protein is the fast, isolated whey protein (IPASP) is the faster, and hydrolyzed whey protein is the fastest digested protein.
- IPASP isolated whey protein
- Isolated whey protein (IPASP) is the purest. Isolated whey protein is obtained by ion exchange of concentrated whey protein or cross-stream microfiltering and subsequent complete purification. In this type of whey protein, the carbohydrates and fat ratio is very low and it contains almost no lactose. Isolated whey protein contains around 90-95% protein and almost all of the lactose is destroyed during the application of ionized filtration (ion exchange).
- Wood or lignocellulosic fiber materials and chemicals are used as raw materials in MDF production. Wood is the most important raw material in MDF.
- the composition of MDF produced by the dry method is as follows;
- Urea formaldehyde resins are glues which are cheap, have short hardening time during pressing and are easy to use. Also, this glue is white or colorless. However, this glue is not used in the production of resistant fiberboards for external aims.
- fiberboard is defined as a composite material that is obtained as a result of utilizing the self-adhesion and felting properties of plant fiber bundles or additionally bringing the roughcast of the board formed by the use of adhesive to certain humidity and pressing.
- Synthetic resins such as urea formaldehyde, phenol formaldehyde, and melamine formaldehyde are used in the forest products industry.
- Synthetic resins such as urea formaldehyde, phenol formaldehyde, and melamine formaldehyde are used in the forest products industry.
- the present invention is related to use whey as an adhesive additive in MDF production which fulfill the abovementioned requirements, eliminate all disadvantages and bring some additional advantages.
- Whey protein (PASP) which is a biomass type, is obtained as a by-product during cheese making.
- MDF boards are obtained using UF-containing whey protein (PASP) glue.
- PASP UF-containing whey protein
- the aim of the present invention is to use protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production.
- the aim of said invention is to make MDFs produced with PASP-based glue, preferably by using 10% PASP and/or IPASP, suitable for construction materials and wood panels used in open environments
- Another aim of said invention is to reduce the fluctuations in oil prices and raw material supply problems in synthetic resins, which are frequently used in the forest products industry.
- Another aim of said invention is to be an alternative to petroleum-based glues and to eliminate material and ecological disadvantages.
- Another aim of the present invention is to provide the use of whey, which is obtained as a by-product in cheese production and which has a negative and harmful effect on the flora-fauna characteristics of the environment it is released, in the forest products industry.
- Another aim of the present invention is to reduce the cost of MDF production caused by the synthetic glues used.
- Figure-1 It shows the MDF-HDF production process workflow.
- Figure-2 It shows the resin unit process workflow.
- Figure-3 It shows laboratory test results of standard UF glue and PASP-based UF glues.
- Figure-4 It shows laboratory test results of standard UF glue and IPASP-based UF glues.
- Figure-5 It shows the production of 10 mm MDF with 35% PASP modified UF glue.
- Figure-6 It shows the production of 10 mm MDF with UF glue modified with Isolated Whey Protein (IPASP). Reference List
- Feeding line (blow line-gluing) (the unit where the fiber is transferred to the drying line and chemicals are added)
- MDF Medium Density Fiberboard
- HDF High Density Fiberboard
- YL Strand Board
- OSB Oriented Strand Board F: Formaldehyde
- WP Whey Protein
- IPASP Isolated Whey Protein
- the resin production process was developed according to the state of the art, and it was used in MDF production by performing whey protein-urea formaldehyde resin synthesis with said invention with the participation of whey protein compounds.
- the resin produced according to the invention comprises the following in solid form;
- Formaldehyde preferably 25-45% by weight
- Whey Protein preferably 1 -14% by weight.
- the amount of PASP and IPASP is preferably 10%.
- Wood-based composite board products produced according to the present invention show basically similar tensile strength, bending strength and swelling resistance with wood-based composite sheet products obtained with urea formaldehyde resin that does not contain whey protein.
- the chip mixes obtained from the chipper (2) are preferably chosen as 50% beech, 30% pine, 20% oak chips and/or preferably 50% fir, 40% pine, 10% beech chips and/or preferably 100% beech chips. Production of the Boards
- Wood type chips in the invention were obtained in ideal chip sizes (thickness 3-5 mm, width 19-20 mm, length 16-25 mm) using a chipping machine. Chips stored in hard and soft wood chip silos (3) were placed in separate feeding chambers. Here, the desired wood mixture was obtained by adjusting the speed of the chips with the discharge helix. The chips were carried by means of the belt conveyor and after separating the fine and coarse chips in the sieve, they were transported to the chip silos by belt conveyor. Preheating was initiated by giving steam to the chips in the silo, suberication process is carried out with the worm screw (helix) underneath and fibration process has started in the cooking boiler.
- the chips are subjected to the cooking process for 3-4 minutes at 7-8 bar steam and at 160-180 °C.
- the chips reach to the refiner segments with the worm screw (helix) located under the cooking vessel.
- the chips are divided into individual fibers such as fixed and mobile between 2 opposing segments. After the individual fibers are removed from the damp, it was kept in the conditioning room at 25 °C, 50% relative humidity until the humidity was 3-5% in the air-conditioning room (13).
- the gluing process was applied by spraying in a laboratory type rotary drum gluing machine.
- the board roughcast was created by laying the glued fibers in a simple laying mold. The boards were obtained by pressing the roughcast test press obtained by laying process.
- Whey protein added urea formaldehyde glue was obtained by adding whey protein (35.15% protein, 54.24% lactose, and 1 % fat), isolated whey protein (87.3% protein, 2% carbohydrate, and 1 .4% fat), urea and formaldehyde.
- NH4CI ammonium chloride
- PASP+UF resins were produced with urea, formaldehyde, PASP and IPASP, preferably at 55-62% solids ratio, with pH:8 PASP, with different UF mixing ratios.
- NH4CI Ammonium Chloride
- Wood fiber mixtures were kept in the conditioning chamber, preferably up to 4% humidity.
- Wood fiber preferably reaching 4% humidity; it is mixed with the fiber in the mixer for 5-10 minutes by adding 12%-14% PASP+UF resin compared to dry fiber and %1 from 20% NH4CI compared to resin solid ratio.
- EXAMPLE-1 Resin Production with Formaldehyde, Urea containing F:U 1.15 molar ratio according to the state of the art:
- Rector begins to be heated. Heating is turned off within approximately 30 minutes. The temperature rises to 80-85 °C due to the exothermic reaction and the pH is 6.5-7.
- the resin solution is adjusted to a temperature of about 98°C by bringing the resin solution from about 80°C to pH 4-6 with formic acid.
- the reaction is followed by measuring the viscosity. After approximately 60 minutes later, the viscosity of the mixture reaches 55-70 cps. The reaction is stopped by adjusting the pH of the mixture to 7-8 with sodium hydroxide.
- the resin mixture is stirred for 60-80 minutes. If necessary, the pH is adjusted to 8, 0-9, 5, then it is sent to the resin stock tank at room temperature with the help of a pump.
- the viscosity of the final product resin is between 230-300 cps at room temperature.
- the total urea required to be taken into the reactor during resin production can be charged to the reactor in two or more stages.
- water can be added according to the recipe, if it is desired to have a high concentration, the water calculated during vacuum cooling according to the recipe can be taken out of the reactor.
- EXAMPLE-2 The inventive Formaldehyde, Urea, Whey Protein, F:U+PASP 1.15 molar ratio Resin Production
- the resin solution is adjusted to a temperature of about 98 °C by bringing the resin solution from about 80°C to pH 4-6 with formic acid.
- the reaction is followed by measuring the viscosity. After approximately 60 minutes later, the viscosity of the mixture reaches 55-70 cps. The reaction is stopped by adjusting the pH of the mixture to 7-8 with sodium hydroxide.
- the resin mixture is stirred for 60-80 minutes. If necessary, the pH is adjusted to 8, 0-9, 5, then it is sent to the resin stock tank at room temperature with the help of a pump.
- the viscosity of the final product resin is between 230-300 cps at room temperature.
- EXAMPLE-3 The inventive Formaldehyde, Urea, Whey Protein, F:ll+PASP 1.15 molar ratio Resin Production
- EXAMPLE-4 The inventive Formaldehyde, Urea, Whey Protein, F:ll+PASP 1.15 molar ratio Resin Production
Abstract
The invention relates to urea formaldehyde resin containing whey protein and wood-based composite board products obtained thereof. The use of protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production.
Description
USING WHEY PROTEIN-BASED NATURAL ADHESIVE IN THE PRODUCTION OF MDF AND COMPOSITE BOARD
FIELD OF THE INVENTION
The present invention relates to the use of protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production.
STATE OF THE ART
Whey proteins are often referred to as waste proteins. In general, it consists of multiple components with a dense spherical structure and low molecular weight. While the biological value of PASP is quite high, this high biological value is shown as a criterion showing that the amount of amino acids is high and almost all of the digested protein will be used by the muscles and the body.
Concentrated whey protein is the fast, isolated whey protein (IPASP) is the faster, and hydrolyzed whey protein is the fastest digested protein. Isolated whey protein (IPASP) is the purest. Isolated whey protein is obtained by ion exchange of concentrated whey protein or cross-stream microfiltering and subsequent complete purification. In this type of whey protein, the carbohydrates and fat ratio is very low and it contains almost no lactose. Isolated whey protein contains around 90-95% protein and almost all of the lactose is destroyed during the application of ionized filtration (ion exchange).
Wood or lignocellulosic fiber materials and chemicals (glue + hardener + paraffin + special chemicals) are used as raw materials in MDF production. Wood is the most important raw material in MDF. The composition of MDF produced by the dry method is as follows;
• 80 - 90% wood and other lignocellulosic materials,
• 10-13% chemicals,
7-10% moisture content.
About 90% or more of urea formaldehyde resins are used in fiberboard production in the world. Urea formaldehyde resins are glues which are cheap, have short hardening time during pressing and are easy to use. Also, this glue is white or colorless. However, this glue is not used in the production of resistant fiberboards for external aims.
In the forest products sector, fiberboard is defined as a composite material that is obtained as a result of utilizing the self-adhesion and felting properties of plant fiber bundles or additionally bringing the roughcast of the board formed by the use of adhesive to certain humidity and pressing.
Synthetic resins such as urea formaldehyde, phenol formaldehyde, and melamine formaldehyde are used in the forest products industry. However, fluctuations arise in the prices of such glues due to oil prices and raw material supply problems.
As a result, due to the abovementioned disadvantages and the insufficiency of the current solutions regarding the subject matter, a development is required to use whey as an adhesive additive in MDF production.
DESCRIPTION OF THE INVENTION
The present invention is related to use whey as an adhesive additive in MDF production which fulfill the abovementioned requirements, eliminate all disadvantages and bring some additional advantages.
Whey protein (PASP) which is a biomass type, is obtained as a by-product during cheese making.
The presence of functional groups (amino, carboxyl) in the structure of proteins, shows that protein-based glues can be used as an adhesive for products such as paper, wood, plastic, etc. With the present invention MDF boards are obtained using UF-containing whey protein (PASP) glue.
The aim of the present invention is to use protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production.
The aim of said invention is to make MDFs produced with PASP-based glue, preferably by using 10% PASP and/or IPASP, suitable for construction materials and wood panels used in open environments
Another aim of said invention is to reduce the fluctuations in oil prices and raw material supply problems in synthetic resins, which are frequently used in the forest products industry.
Another aim of said invention is to be an alternative to petroleum-based glues and to eliminate material and ecological disadvantages.
Another aim of the present invention is to provide the use of whey, which is obtained as a by-product in cheese production and which has a negative and harmful effect on the flora-fauna characteristics of the environment it is released, in the forest products industry.
Another aim of the present invention is to reduce the cost of MDF production caused by the synthetic glues used.
Description of the Figures
Figure-1 : It shows the MDF-HDF production process workflow.
Figure-2: It shows the resin unit process workflow.
Figure-3: It shows laboratory test results of standard UF glue and PASP-based UF glues.
Figure-4: It shows laboratory test results of standard UF glue and IPASP-based UF glues.
Figure-5: It shows the production of 10 mm MDF with 35% PASP modified UF glue.
Figure-6: It shows the production of 10 mm MDF with UF glue modified with Isolated Whey Protein (IPASP).
Reference List
1- Peeler
2- Chipper
3- Chip Storage
4- Sieve
5- Refiner-Defibrator
6- Solution tank (Resin, Liquid Paraffin, Hardener and Other Chemicals)
6a Feeding line (blow line-gluing) (the unit where the fiber is transferred to the drying line and chemicals are added)
7- Drier
8- Fiber shifter
9- Laying station
10- Pre-press
11- Hot press
12- Sizing
13- Conditioned
14- Intermediate warehouse (Lukki Storage)
15- Emery
16- Packaging
17- Energy unit
18- Methanol tank
19- Fresh air fan
20- Blower
21- Methanol evaporator
22- Heat exchanger
23- Formaldehyde reactor (catalyst)
24- Aqueous formaldehyde solution (absorption column)
25- Process water tank
26- Formaldehyde stock tank
27- Resin reactor
28- Urea stock area
29- Base tank
30- Acid tank
31- Steam inlet unit (heating the resin reactor)
32- Other additive chemicals
33- Heat exchanger (reactor cooling)
34- Vacuum water tank
35- Resin stock tank
ABBREVIATIONS AND EXPLANATIONS
%: Percentage pH: Degree of acidity basicity cP: Centipoise
MDF: Medium Density Fiberboard HDF: High Density Fiberboard YL: Strand Board
OSB: Oriented Strand Board F: Formaldehyde
U: Urea
UF: Urea Formaldehyde Resin
PF: Phenol Formaldehyde Resin
WP: Whey Protein
PASP: Whey Protein
IPASP: Isolated Whey Protein
°C: Degrees Celsius (Temperature)
OH': Hydroxyl group
H: Hydrogen
H2O: Water
=NH: Amine group
C=O: Carbonyl group
N/mm2: Newton/square millimeter
TSE: Turkish Standardization Institute
EN: European Standards
DP: Degree of Polymerization
Et.al: And others kg: Kilogram
L: Liter min: Minute m: Meter mm: Millimeter kg/m3: Kilogram/cubic meter
DETAILED DESCRIPTION OF THE INVENTION
The resin production process was developed according to the state of the art, and it was used in MDF production by performing whey protein-urea formaldehyde resin synthesis with said invention with the participation of whey protein compounds.
The resin produced according to the invention comprises the following in solid form;
Formaldehyde preferably 25-45% by weight,
Urea preferably 50-75% by weight,
Whey Protein preferably 1 -14% by weight.
(The amount of PASP and IPASP is preferably 10%.)
It was observed that the physical and mechanical test results gradually decreased with the increase in the amount of PASP and IPASP usage. In addition to changing the press conditions (temperature, pressure, etc.), additional chemicals can be used preferably so as to achieve better results.
Wood-based composite board products produced according to the present invention show basically similar tensile strength, bending strength and swelling resistance with wood-based composite sheet products obtained with urea formaldehyde resin that does not contain whey protein.
In the production of MDF boards, the following are used;
• Pine, beech, oak, fir fibers
• Urea formaldehyde glue
• Ammonium chloride
• Whey protein
A mixture of leafy and needle-leaved chips was used as raw material. The chip mixes obtained from the chipper (2) are preferably chosen as 50% beech, 30% pine, 20% oak chips and/or preferably 50% fir, 40% pine, 10% beech chips and/or preferably 100% beech chips.
Production of the Boards
Wood type chips in the invention were obtained in ideal chip sizes (thickness 3-5 mm, width 19-20 mm, length 16-25 mm) using a chipping machine. Chips stored in hard and soft wood chip silos (3) were placed in separate feeding chambers. Here, the desired wood mixture was obtained by adjusting the speed of the chips with the discharge helix. The chips were carried by means of the belt conveyor and after separating the fine and coarse chips in the sieve, they were transported to the chip silos by belt conveyor. Preheating was initiated by giving steam to the chips in the silo, suberication process is carried out with the worm screw (helix) underneath and fibration process has started in the cooking boiler.
In the cooking boiler, the chips are subjected to the cooking process for 3-4 minutes at 7-8 bar steam and at 160-180 °C. The chips reach to the refiner segments with the worm screw (helix) located under the cooking vessel. The chips are divided into individual fibers such as fixed and mobile between 2 opposing segments. After the individual fibers are removed from the damp, it was kept in the conditioning room at 25 °C, 50% relative humidity until the humidity was 3-5% in the air-conditioning room (13). The gluing process was applied by spraying in a laboratory type rotary drum gluing machine. The board roughcast was created by laying the glued fibers in a simple laying mold. The boards were obtained by pressing the roughcast test press obtained by laying process.
Adhesive Substance
Whey protein added urea formaldehyde glue was obtained by adding whey protein (35.15% protein, 54.24% lactose, and 1 % fat), isolated whey protein (87.3% protein, 2% carbohydrate, and 1 .4% fat), urea and formaldehyde.
Hardening Agents
Preferably, 20% ammonium chloride (NH4CI) solution was used as a hardening agent for urea formaldehyde glue.
Properties of ammonium chloride used as hardening agent for UF glue
Properties Values
Solution (%): 20 ± 1
Density (g/cm3): 0,90
pH (25 °C): 6.30
Whey protein based UF glue and production stages of MDF boards obtained with this glue;
• 2 types of whey protein as PASP containing 35% protein and IPASP containing 85-99% protein are provided for UF resin modification.
• In the laboratory environment, PASP+UF resins were produced with urea, formaldehyde, PASP and IPASP, preferably at 55-62% solids ratio, with pH:8 PASP, with different UF mixing ratios. NH4CI (Ammonium Chloride) was used as hardener.
• PASP ratio was calculated according to the solid urea amount in the resin.
• Wood fiber mixtures were kept in the conditioning chamber, preferably up to 4% humidity.
• Wood fiber, preferably reaching 4% humidity; it is mixed with the fiber in the mixer for 5-10 minutes by adding 12%-14% PASP+UF resin compared to dry fiber and %1 from 20% NH4CI compared to resin solid ratio.
• After the fiber roughcast of the fiber+PASP+UF+NH4CI mixture is formed, it was pressed in a thickness of 10 mm and a density of 750-800 kg/m3, preferably at 200-210 bar pressure, at 185°C for 5-10 minutes.
• A total of 48 MDF boards were obtained as two samples from each glue and wood type mixture for all physical-mechanical and free formaldehyde emission test results.
EXAMPLE-1: Resin Production with Formaldehyde, Urea containing F:U 1.15 molar ratio according to the state of the art:
- According to the recipe calculated for the production of F:U, 1.15 mol, 17.88 kg of aqueous formaldehyde solution with 46% concentration (corresponding to 8.22 kg of solid formaldehyde) is charged into the reactor. The pH is brought to 7-8 with aqueous sodium hydroxide (46%).
- 7.85 kg of 1st part urea is charged into the reactor on the formaldehyde solution. Mixture temperature: 35-40 °C and pH is brought to 7-9.
Rector begins to be heated. Heating is turned off within approximately 30
minutes. The temperature rises to 80-85 °C due to the exothermic reaction and the pH is 6.5-7.
- The resin solution is adjusted to a temperature of about 98°C by bringing the resin solution from about 80°C to pH 4-6 with formic acid.
- The reaction is followed by measuring the viscosity. After approximately 60 minutes later, the viscosity of the mixture reaches 55-70 cps. The reaction is stopped by adjusting the pH of the mixture to 7-8 with sodium hydroxide.
- 2.0 kg of water is taken out of the reactor by means of sucking down with an exchanger. The mixture is cooled below 50 °C.
- The 2nd part of urea (6.49 kg) is slowly charged into the reactor and the pH is adjusted to 6.5-9.
- When 2nd part of the reactor is fully charged with urea, the pH of the mixture is adjusted to 8.0 at the low temperature of the final reaction.
- The resin mixture is stirred for 60-80 minutes. If necessary, the pH is adjusted to 8, 0-9, 5, then it is sent to the resin stock tank at room temperature with the help of a pump. The viscosity of the final product resin is between 230-300 cps at room temperature.
- The total urea required to be taken into the reactor during resin production can be charged to the reactor in two or more stages. When the final solid of the produced glue is desired to have a low concentration, water can be added according to the recipe, if it is desired to have a high concentration, the water calculated during vacuum cooling according to the recipe can be taken out of the reactor.
EXAMPLE-2: The inventive Formaldehyde, Urea, Whey Protein, F:U+PASP 1.15 molar ratio Resin Production
17.88 kg of 46% aqueous formaldehyde solution (corresponding to 8.22 kg of solid formaldehyde) is charged into the reactor. The pH is brought to 7-8
with aqueous sodium hydroxide (46%).
- 7.85 kg of 1st part urea is charged into the reactor on the formaldehyde solution. Mixture temperature: 35-40 °C and pH: is brought to 7-9.
- Reactor begins to be heated. Heating is turned off within approximately 30 minutes. The temperature rises to 80-85 °C due to the exothermic reaction and the pH is 6.5-7.
- The resin solution is adjusted to a temperature of about 98 °C by bringing the resin solution from about 80°C to pH 4-6 with formic acid.
- The reaction is followed by measuring the viscosity. After approximately 60 minutes later, the viscosity of the mixture reaches 55-70 cps. The reaction is stopped by adjusting the pH of the mixture to 7-8 with sodium hydroxide.
- 2.0 kg of water is taken out of the reactor by means of sucking down with an exchanger. The mixture is cooled below 50 °C.
- 1 ,793 kg of PASP, which is made into a solution of 40%, is charged to the reactor in several stages. (Corresponding to 0.717 kg solid PASP). (about 5% of total urea).
- The 2nd part of urea (5.77 kg) is slowly charged into the reactor and the pH is adjusted to 6.5-9.
- When 2nd part of the reactor is fully charged with urea, the pH of the mixture is adjusted to 8.0 at the low temperature of the final reaction.
- The resin mixture is stirred for 60-80 minutes. If necessary, the pH is adjusted to 8, 0-9, 5, then it is sent to the resin stock tank at room temperature with the help of a pump. The viscosity of the final product resin is between 230-300 cps at room temperature.
EXAMPLE-3: The inventive Formaldehyde, Urea, Whey Protein, F:ll+PASP 1.15
molar ratio Resin Production
- 17.88 kg of 46% aqueous formaldehyde solution (corresponding to 8.22 kg of solid formaldehyde).
- 7.85 kg of urea on first charge
- 5.147 kg of urea on second charge
- 3.587 kg PASP (corresponding to 1.435 kg solid PASP) which was made into 40% solution just before the second charge urea. (10% of total urea).
- The same process flow as in Example 2 was applied by using foregoing. (Molecular weight of urea 60 g/mol) (Formaldehyde molecular weight: 30 g/mol)
EXAMPLE-4: The inventive Formaldehyde, Urea, Whey Protein, F:ll+PASP 1.15 molar ratio Resin Production
- 17.88 kg of 46% aqueous formaldehyde solution (corresponding to 8.22 kg of solid formaldehyde).
- 7.85 kg of urea on first charge
- 4.338 kg of urea on second charge
- 5.380 kg PASP (corresponding to 2.152 kg solid PASP) which was made into 40% solution just before the second charge urea. (15% of total urea).
- The same process flow as in Example 2 was applied by using foregoing. (Molecular weight of urea 60 g/mol)
(Formaldehyde molecular weight: 30 g/mol)
Claims
1. Use of protein-intensive waste solution produced as a by-product in cheese production facilities and named as whey together with urea formaldehyde glue, as an adhesive in MDF production, characterized in that; it is a wood-based composite board product produced with urea formaldehyde glue of protein-intensive waste solution called whey.
2. Wood-based composite board products according to claim 1 , characterized in that; wood-based composite boards preferably comprise medium density fiberboard (MDF) and/or high density fiberboard (HDF) and/or particleboard (YL) and/or oriented strand board (OSB).
3. Resin according to claim 1 , characterized in that; said resin comprises the following in solid form; formaldehyde preferably 25-45% by weight, urea preferably 50-75% by weight, whey protein preferably 1-14% by weight.
4. Resin used in wood-based composite board products according to claim 1 , characterized in that, it comprises the following production process steps;
• Charging the aqueous formaldehyde solution to the reactor and giving sodium hydroxide,
• Charging the first portion of urea to the reactor and preferably bringing it to pH 7-9,
• Heating the mixture preferably up to 98 °C and preferably keeping the pH between
4-6,
• Preferably adjusting pH to 7-9 at the end of the polymerization reaction,
• Giving whey protein into the reactor at slightly elevated temperatures in several charges and preferably adjusting to pH 7-8.5,
• Giving the second part of urea, preferably adjusting to pH 6.5-9,
• Mixing and storage until the end of the polymerization reaction.
5. Resin production process according to any of the preceding claims, characterized in that, it comprises the following production process steps;
• Charging the aqueous formaldehyde solution to the reactor and bringing pH of sodium hydroxide to 7, 0-8, 5,
• Charging the first part of urea to the reactor with the initial mole ratio of
formaldehyde urea to 1 .7-3.0 and bringing it to pH 7-9,
• Heating the mixture preferably up to 98 °C and bringing pH to 4-6,
• Adjusting pH to 7-8,5 at the end of the polymerization reaction,
• Cooling the mixture, charging the whey protein in several stages, preferably at a solid weight ratio of 1 -15% according to the total urea weight in the mole calculation (as a 40% solution) and preferably adjusting pH to 7-8,5,
• The second part of urea is given to the reactor such that the molar ratio of the finished product and resin urea formaldehyde is preferably 0.751 ,3 and preferably adjusting pH to 6.5-9,
• Mixing and storing the same until the end of the polymerization reaction.
6. A medium density fiberboard (MDF-HDF) according to claims 1 and 2, characterized in that, it comprises the following production process steps;
• Chipping of wood raw material,
• Cooking the chips in the refiner unit (5) on steam between 180-200 °C, giving paraffin and fibering the same,
• Giving said urea formaldehyde PASP copolymer resin to the fibers,
• Drying the fibers preferably up to a moisture ratio of 8-14%,
• Forming the outline of the plate by laying the fibers,
• Obtaining the plates by pressing under temperature and pressure
7. Wood-based composite board products according to any of the preceding claims, characterized in that; it shows essentially similar tensile strength, bending strength and swelling resistance with wood-based composite sheet products obtained with urea formaldehyde resin that does not contain natural whey protein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2020/20441A TR202020441A2 (en) | 2020-12-14 | 2020-12-14 | USING NATURAL GLUE BASED ON CHEESE WATER PROTEIN IN THE PRODUCTION OF MDF AND COMPOSITE SHEETS |
| TR2020/20441 | 2020-12-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022132077A1 true WO2022132077A1 (en) | 2022-06-23 |
Family
ID=75575812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/TR2021/050862 WO2022132077A1 (en) | 2020-12-14 | 2021-08-27 | Using whey protein-based natural adhesive in the production of mdf and composite board |
Country Status (2)
| Country | Link |
|---|---|
| TR (1) | TR202020441A2 (en) |
| WO (1) | WO2022132077A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115256587A (en) * | 2022-07-21 | 2022-11-01 | 广西扶绥县盛唐矿物材料有限责任公司 | Method for preparing fiberboard by using modified ball clay |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4282119A (en) * | 1978-12-20 | 1981-08-04 | Methanol Chemie Nederland V.O.F. | Manufacture of chipboard having high strength and reduced formaldehyde emission, using a minor amount of protein in combination with low formaldehyde:urea resins |
| US6362275B1 (en) * | 2000-12-12 | 2002-03-26 | Ashland Inc. | Reduction of free formaldehyde in aldehyde resins |
| US20050287282A1 (en) * | 2004-06-29 | 2005-12-29 | The Regents Of The University Of California | Cereal-Based Adhesives and Their Uses |
-
2020
- 2020-12-14 TR TR2020/20441A patent/TR202020441A2/en unknown
-
2021
- 2021-08-27 WO PCT/TR2021/050862 patent/WO2022132077A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4282119A (en) * | 1978-12-20 | 1981-08-04 | Methanol Chemie Nederland V.O.F. | Manufacture of chipboard having high strength and reduced formaldehyde emission, using a minor amount of protein in combination with low formaldehyde:urea resins |
| US6362275B1 (en) * | 2000-12-12 | 2002-03-26 | Ashland Inc. | Reduction of free formaldehyde in aldehyde resins |
| US20050287282A1 (en) * | 2004-06-29 | 2005-12-29 | The Regents Of The University Of California | Cereal-Based Adhesives and Their Uses |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115256587A (en) * | 2022-07-21 | 2022-11-01 | 广西扶绥县盛唐矿物材料有限责任公司 | Method for preparing fiberboard by using modified ball clay |
| CN115256587B (en) * | 2022-07-21 | 2023-03-10 | 广西扶绥县盛唐矿物材料有限责任公司 | Method for preparing fiberboard by using modified ball clay |
Also Published As
| Publication number | Publication date |
|---|---|
| TR202020441A2 (en) | 2021-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NL192377C (en) | Process for the manufacture of chipboard or fiber boards, as well as liquid concentrate to be used in the manufacture thereof. | |
| US7282117B2 (en) | Cellulosic fiber composites using protein hydrolysates and methods of making same | |
| US4828643A (en) | Liquified cellulosic fiber, resin binders and articles manufactured therewith, and method of manufacturing same | |
| CA2526420C (en) | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives | |
| US20050282988A1 (en) | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives | |
| Dunky | Adhesives based on formaldehyde condensation resins | |
| US5520777A (en) | Method of manufacturing fiberboard and fiberboard produced thereby | |
| NO794179L (en) | PROCEDURE FOR MANUFACTURING CARTRIDGES | |
| EP0961813B1 (en) | Adhesive composition and its use | |
| JP2022031549A (en) | Formaldehyde-free wood binder | |
| WO2022132077A1 (en) | Using whey protein-based natural adhesive in the production of mdf and composite board | |
| WO2010102186A1 (en) | Adhesive compositions for bonding composites | |
| WO1998037147A2 (en) | Adhesive composition and its use | |
| WO2023148578A1 (en) | Glue for boards | |
| KR100984800B1 (en) | Urea formaldehyde resin type hardener | |
| CN106189967A (en) | A kind of sheet material glue processing technology | |
| WO2023218343A1 (en) | Glue for boards | |
| Chen | Bonding flakeboards of southern species with copolymer resins of forest and agricultural residue extracts | |
| EP3286236B1 (en) | Production process of the resins containing polyflavonoid and derivatives and their application in the wood based composite board products | |
| SE442101B (en) | PROCEDURE FOR MANUFACTURING FIBER PLATES OF LIGNOCELLULOSALLY MATERIAL | |
| UA127480C2 (en) | Method for producing lignocellulose materials in the presence of caprolactam and oligomers of caprolactam | |
| Shulga et al. | Application of a triple interpolymer complex based on a wood polymer in manufacture of lignocellulosic composites | |
| CS272087B1 (en) | Thermoreactive urea-formaldehyde resin and method of its preparation | |
| ZA200609501B (en) | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21907284 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21907284 Country of ref document: EP Kind code of ref document: A1 |