WO2020032899A1 - Production de liant biologique à base de mélasse et ses applications - Google Patents

Production de liant biologique à base de mélasse et ses applications Download PDF

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Publication number
WO2020032899A1
WO2020032899A1 PCT/TR2019/050647 TR2019050647W WO2020032899A1 WO 2020032899 A1 WO2020032899 A1 WO 2020032899A1 TR 2019050647 W TR2019050647 W TR 2019050647W WO 2020032899 A1 WO2020032899 A1 WO 2020032899A1
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WIPO (PCT)
Prior art keywords
formaldehyde
molasses
resin
resins
acid
Prior art date
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Ceased
Application number
PCT/TR2019/050647
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English (en)
Inventor
Ayse BENK
Abdullah COBAN
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Erciyes Universitesi
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Erciyes Universitesi
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Filing date
Publication date
Application filed by Erciyes Universitesi filed Critical Erciyes Universitesi
Publication of WO2020032899A1 publication Critical patent/WO2020032899A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • 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
    • B27N1/00—Pretreatment of moulding material
    • B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
    • 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
    • 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
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • 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
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres

Definitions

  • the invention is related to a molasses binder production method used for producing isolation materials that are utilized in the entire furniture industry, such as wood panels (chipboard, MDF, plywood) , and in the recent years, rock wool, basalt wool and fibreglass, that can be substituted with formaldehyde based binders.
  • thermosetting resins used commonly, in the woodworking industry. These are,
  • Phenol formaldehyde resins are resins that are obtained as a reaction of the condensation of phenol and formaldehyde. They are durable against water, organic solvents and fungi and pests. This resin is mostly preferred in the production of wood products that are to be used outdoors as they exhibit high durability against environmental air conditions. At the same time, nowadays, this resin is being used in the production of basalt wool.
  • Resorcinol formaldehyde resins are resins which are quite durable against water and are also the most expensive resins. Due to this reason, they are produced in small amounts and are preferred especially when water resistance is necessary.
  • Urea formaldehyde resins are the most commonly used resins, as they are cheap. They are used in the production of wooden plates such as chipboards, MDF, plywood and waszalit. The hardening time in hot pressing is shorter and the colour is transparent. Its resistance against water is quite low in comparison to phenol based resins.
  • Formaldehyde is produced by catalytic oxidation of methanol and it is the smallest member of aldehydes. It is a colourless, strong odored, viscous and toxic fluid which is weak in acidity and which can be mixed with water.
  • the negative effects on formaldehyde against human health are known and in 2004, the Cancer Research Agency which is an affiliate of the World Health Organization has classified formaldehyde as a substance which causes cancer in humans. Due to this reason the formaldehyde emission limit values, standards and test methods have been determined in relation to products that are produced with formaldehyde based resins.
  • the formaldehyde emission limit value in wood based plates and the test methods thereof, which are accepted in Europe have been given in Table 1.
  • the formaldehyde test methods and limit values used for particle board and MDF in our country has been provided in Table 2. Table 1 . European formaldehyde standards
  • the aim of the invention is to produce a high quality, affordable organic resin which does not comprise phenol and formaldehyde and which is not harmful to human health.
  • This resin that is to be produced must be able to be used instead of phenol formaldehyde in production and instead of the rockwool, basalt wool used for insulation and melamine formaldehyde used in coating and urea formaldehyde used as a binder in the wood working industry and it should improve the characteristics of the end product instead of compromising the characteristics thereof.
  • the products such as chipboards, MDF, waszalit, and plywood that are to be obtained with the resin that is to be produced according to the invention shall be much more resilient than those produced with urea formaldehyde resin, the product may not necessitate coating with papers impregnated with melamine formaldehyde [1-4].
  • the main aim of our invention is to determine if these molasses based resins that we have previously produced can be used for this aim or not. It has been determined that the resins produced, as a result of our studies that have been ongoing for many years, can be used instead of the formaldehyde based resins and industrial scaled applications have been carried out in a waszalit factory. The studies that have been carried out and the results obtained have been described in detail below.
  • the hardener is selected from two different groups of compounds.
  • the first group of compounds that can be used as a hardener is one of a heterocyclic functional group compound comprising amine, amide, imine, imide and nitrogen, boron compounds, IA group oxide and hydroxides, IIA group oxide and hydroxides.
  • the second group of compounds that can be used as a hardener can be selected from a reaction product of ethylenediamine and epichlorhydrine reaction product, a reaction product of bis-hexamethylenetriamine and epichlorohydrine or reaction products of hexamethylenediamine and epichlorohydrine.
  • At least three compounds that can constitute a covalent bond with each other are prepared.
  • One of these three compounds is selected from protein and the other two are selected from cross linking compounds.
  • the protein can be selected from vegetable or from animal proteins such as soy protein, maize protein, keratin, gelatine, casein, gluten and albumin.
  • One of the compounds used as a cross linkers a homopolymer and/or copolymer which is one of the polycarboxy polymers that comprises carboxyl.
  • the homopolymer and/or copolymer of carboxylic acid such as acrylic acid which comprises ethylenic non saturated carboxylic acid, metacrylic acid, methyl maleic acid and itaconic acid can be used.
  • carboxylic acid such as acrylic acid which comprises ethylenic non saturated carboxylic acid, metacrylic acid, methyl maleic acid and itaconic acid
  • the second cross linking compound which is to be used must comprise at least two functional groups and must be able to easily react with both the protein and the other polymer based cross linking compound. Poliols, alkanolamines, polyamines can be used for this.
  • a binder is produced from the reaction of alkanolamine comprising at least two hydroxyl groups and the polymer produced with the free radical polymerization of an ethylenic unsaturated acid anhydride or an ethylenic unsaturated dicarboxyl acid.
  • the binder that has been prepared can harden in 15 minutes at 130°C following a drying process for 72 hours at 50°C.
  • Compounds that comprise phosphor are used as reaction catalysts of the polymer and alkanolamine used.
  • an aqueous binder is prepared by means of a binding agent such as starch and a silane derivative.
  • a binding agent such as starch and a silane derivative.
  • it comprises a binder citric acid, polyacrylic acid, a cross linker such as triethanol amine, polyamine, glycerine, a catalyst such as sodium hipophosphite, sodium phosphate and potassium tripolyphosphate.
  • a silane derivative can be used from the compounds of aminosilane, epoxy trialkoxysilane, methacryl trialkoxysilane, methacryl nitrohydroxy silane as a binding agent.
  • starch is used as biopolymer together with isocyanides. It is defined that the mass ratio of biopolymer and isocyanides used, can be within the range of 15:85-50:50 and that urea needs to be present in the aqueous binder that has been prepared.
  • a binder without formaldehyde is produced by adding polycarboxylic acid to the product that has been obtained after polyacid monomer and poliol are mixed until a reaction is formed.
  • All of the monomer or oligomers that comprise at least two carboxylic acid groups having a molecular weight between 50-1000 can be used as a polyacid.
  • Maleic acid, maleic anhydrite, fumaric acid, citric acid, adipic acid, tartaric acid, itoconic acid and compounds thereof can be used as a polyacid monomer.
  • Compounds such as, glycerine, glucose, sorbitol, triethanolamine, monoethanolamine, diethanolamine comprising at least two hydroxyl groups that can form an ester bond with polyacids can be used as poliol.
  • a suitable resin is obtained for mineral wool products (glass fibre, basalt wool, rockwool) following the mixing of carboxylic acid and an alkanolamine under reaction conditions.
  • the obtained resin is reacted with a polymer that comprises a carboxylic acid and its features are being tried to be enhanced.
  • a carboxylic acid such as an adipic acid, citric acid, succinic acid comprising more than two carboxyl groups can be used as carboxylic acid and a compound such as diethanolamine, triethanolamine, n-butyldiethanolamine, can be used as alkanolamine.
  • a polymer such as polyacrylic acid, polymethacr lic acid, polimaleic acid having a molecular weight between 1000-250000 is used as polymer.
  • a carboxylic acid anhydride such as succinic anhydride, maleic anhidric, and phtalic anhydride is used as a carboxylic acid anhydride
  • an alkanolamine such as diethanolamine, diisopropanolamine, methyldiethanolamine, and triethanolamine can be used as alkanolamine
  • a carbohydride such as glucose, fructose, starch, pectin, and xylose can be used as a carbohydrate.
  • binders that have been briefly described above are binders that do not comprise formaldehyde. However some of these binders that have been prepared are either very expensive or some of the chemical agents used in the preparation of these binders are cancerous substances that are much more dangerous that of formaldehyde.
  • the resins subject to our invention can be used in all fields where formaldehyde based binders that lead to cancer in humans, and it does not have any harmful effects on people.
  • our invention has continuous raw material resources, it is a very cheap resin production method and application in comparison to urea formaldehyde and phenol formaldehyde.
  • the raw materials of the resins that have been prepared are molasses, sulphuric acid, phosphoric acid and ammonium nitrate. Molasses have been obtained from sugar factories and its approximate characteristics have been provided in table 3. Ammonium nitrate is ammonium nitrate that is used as fertilizer comprising 33% nitrogen.
  • the solid matter amount that the resin needs to contain has been calculated depending on usage field. 2,5%-5% of the solid matter in molasses that the resin needs to contain depending on the solid matter amount is a hardener constituting sulphuric acid, phosphoric acid and/or ammonium nitrate, wherein aqueous solutions comprising these hardeners are prepared, molasses is added onto these solutions and is slowly mixed until a homogenous mixture is obtained.
  • Example 1 The resin comprising 64% solid matter that can be replaced with urea formaldehyde in the production of waszalit is prepared as follows: 171,25 g water is acquired. 15,75g acids or ammonium nitrate from the acids that are to be used as hardeners are added in the water. A homogenous mixture is obtained after mixing. Onto this aqueous solution 813 g molasses comprising 77,3% solid matter is added and mixed. Mixing is continued until a homogenous mixture is obtained. The obtained resins are ready to be used.
  • Example 2 The resin comprising 50% solid matter that can be used instead of urea formaldehyde in the production of chipboard and MDF is prepared as follows: 355,79 g water is acquired. 12,21g ammonium nitrates or acids that are to be used as hardeners are added in the water. A homogenous mixture is obtained after mixing. Onto this aqueous solution 632 g molasses comprising 77,3% solid matter is added and mixed. Mixing is continued until a homogenous mixture is obtained. The obtained resins are ready to be used.
  • resin is prepared similarly for the production of rockwool, basalt wool, glass fiber and plywood.
  • the solid matter amount is prepared according to processing conditions. For example, after the solid matter is adjusted according to the type of the wood to be used in the production of chipboard the required amount of an adhesive is changed by ⁇ 5% and products with the desired features and quality can be obtained.
  • Standard production in a waszalit factory is performed as follows: After the received woodchips are dried, it is mixed with urea formaldehyde that is used as an adhesive at a ratio of 25%-30% depending on the type of woodchips, and is then shaped in cold press. Following this, impregnated paper is placed on a plate that has been prepared and the product is placed into a hot press. The final product is obtained after pressing for 5-7 minutes at a temperature of 155-160°C.
  • resins suitable for such aims can be obtained using strong acids and ammonium nitrate from all of the products that contain sugar (white sugar, brown sugar, saccharose, fructose, reduced sugar, glucose syrup etc).

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

L'invention concerne un procédé de production de liant à base de mélasse utilisé pour produire des matériaux d'isolation utilisés dans toute l'industrie du meuble, tels que des panneaux de bois (panneau à particules, MDF, contreplaqué), et au cours des dernières années, la laine de roche, la laine de basalte et la fibre de verre, qui peuvent être remplacées par des liants à base de formaldéhyde.
PCT/TR2019/050647 2018-08-07 2019-08-05 Production de liant biologique à base de mélasse et ses applications Ceased WO2020032899A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR201811436 2018-08-07
TR2018/11436 2018-08-07

Publications (1)

Publication Number Publication Date
WO2020032899A1 true WO2020032899A1 (fr) 2020-02-13

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PCT/TR2019/050647 Ceased WO2020032899A1 (fr) 2018-08-07 2019-08-05 Production de liant biologique à base de mélasse et ses applications

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133913A (zh) * 2021-12-24 2022-03-04 南京林业大学 一种废糖蜜基高强度环保无醛胶黏剂及其制备方法和应用
CN114196350A (zh) * 2021-12-30 2022-03-18 南京林业大学 一种废糖蜜基废糖蜜基无醛高性能高导热胶黏剂及其制备方法和应用
PL442188A1 (pl) * 2022-09-02 2024-03-04 Uniwersytet Przyrodniczy W Poznaniu Sposób wytwarzania mokroformowanych płyt wiórowych na bazie spoiwa ekologicznego
US20240309252A1 (en) * 2020-07-22 2024-09-19 Sestec Polska Sp. Z O.O. Binding agent for cellulose-containing materials and a product containing it

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011015946A2 (fr) * 2009-08-07 2011-02-10 Knauf Insulation Liant à base de mélasse
WO2017104134A1 (fr) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Composition de collage aqueuse

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011015946A2 (fr) * 2009-08-07 2011-02-10 Knauf Insulation Liant à base de mélasse
WO2017104134A1 (fr) * 2015-12-18 2017-06-22 Henkel Ag & Co. Kgaa Composition de collage aqueuse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BENK A. ET AL.: "Molasses and air blown coal tar pitch binders for the production of metallurgical quality formed coke from anthracite fines or coke breeze", FUEL PROCESSING TECHNOLOGY, vol. 92, 2011, pages 1078 - 1086, XP028365532, DOI: 10.1016/j.fuproc.2011.01.002 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240309252A1 (en) * 2020-07-22 2024-09-19 Sestec Polska Sp. Z O.O. Binding agent for cellulose-containing materials and a product containing it
CN114133913A (zh) * 2021-12-24 2022-03-04 南京林业大学 一种废糖蜜基高强度环保无醛胶黏剂及其制备方法和应用
CN114133913B (zh) * 2021-12-24 2022-09-30 南京林业大学 一种废糖蜜基高强度环保无醛胶黏剂及其制备方法和应用
CN114196350A (zh) * 2021-12-30 2022-03-18 南京林业大学 一种废糖蜜基废糖蜜基无醛高性能高导热胶黏剂及其制备方法和应用
PL442188A1 (pl) * 2022-09-02 2024-03-04 Uniwersytet Przyrodniczy W Poznaniu Sposób wytwarzania mokroformowanych płyt wiórowych na bazie spoiwa ekologicznego

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