• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD FOR TREATMENT OF LIGNIN AND FOR PRODUCING A BINDER COMPOSITION. The present invention relates to a method for the treatment of lignin, wherein the method comprises the following steps: a) dissolving the lignin in an aqueous composition, which contains a compound selected from the class of phenols and alkali, thereto time maintaining the temperature of the composition at 40 - 85°C, wherein the alkali comprises an alkali metal hydroxide; and b) heating the composition to a temperature, which is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a value pH 6 - 14.
    公开号:BR112016009537B1
    申请号:R112016009537-5
    申请日:2014-11-25
    公开日:2021-05-25
    发明作者:Suvi Pietarinen；Sanna Valkonen；Okko Ringena
    申请人:Upm-Kymmene Corporation；
    IPC主号:
    专利说明:

    [001] FIELD OF INVENTION
    [002] The invention relates to a method for treating lignin and its use for the production of a binder composition, as well as different applications thereof.
    [003] BACKGROUND OF THE INVENTION
    [004] Lignin is a natural polymer, which can be extracted, for example, from wood. As lignin is a natural biopolymer, its use as a component in glues instead of synthetic materials has been investigated in order to obtain a more environmentally friendly adhesive composition. Especially, the ability to substitute synthetic phenol in phenolic resins, such as phenol formaldehyde resin, has been the object of the prior art. Lignin can be used for the purpose of decreasing the amount of synthetic phenol in a resin composition. Lignin has previously been used for phenol replacement during the production of the lignin-phenol-formaldehyde resin.
    [005] Currently known lignin-based resins are not, however, suitable for all applications where traditional phenolic resins are being used. For example, currently known lignin-based resins are not suitable for high pressure laminates. High pressure laminates (HPL), which are also known as plastic laminates, can be produced by fusing together under the influence of heat and pressure, multiple layers of paper, fabrics or other core materials, using resins. thermosetting as binders. The inventors recognized the need for a method that would result in a higher phenol substitution in the resin and therefore a more environmentally friendly binder composition having properties suitable for use in different applications such as high pressure laminates.
    [006] PURPOSE OF THE INVENTION
    [007] The purpose of the invention is to provide a new type of method for the treatment of lignin and to provide a method for producing a binder composition for different applications. The purpose of the invention is to provide a new binder composition and adhesive composition, as well as their uses.
    [008] SUMMARY
    [009] The method for the treatment of lignin according to the present invention is characterized in that it is presented in claim 1.
    [010] The method for producing a binder composition according to the present invention is characterized in that it is set out in claim 10.
    [011] The binder composition that can be obtained by the method according to the present invention is characterized in that it is presented in claim 21.
    [012] The adhesive composition according to the present invention is characterized by what is presented in claim 22.
    [013] The uses according to the present invention are characterized by what is presented in claims 20, 23, 24 and 25.
    [014] BRIEF DESCRIPTION OF THE DRAWINGS
    [015] The accompanying drawings, which are included to provide a greater understanding of the invention and constitute a part of this descriptive report, illustrate embodiments of the invention and together with the description help to explain the principles of the invention. In the drawings:
    [016] Figure 1 is a flow diagram illustration of a method for treating lignin according to an embodiment of the present invention; and
    [017] Figure 2 is a flow diagram illustration of a method for producing a binder composition according to an embodiment of the present invention.
    [018] DETAILED DESCRIPTION OF THE INVENTION
    [019] The present invention relates to a method for the treatment of lignin, which method comprises the following steps: a) dissolving the lignin in an aqueous composition, which contains a compound selected from the class of phenols and alkali metals while maintaining the temperature of the composition at 40 - 85°C, wherein the alkali comprises an alkali metal hydroxide; and b) heating the composition to a temperature that is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a value of pH 6 - 14.
    [020] The present invention further relates to a method for producing a binder composition, wherein the method comprises the following steps: a) dissolving the lignin in an aqueous composition, which contains a compound selected from the class of phenols and alkali metals, while maintaining the temperature of the composition at 40 - 85°C, wherein the alkali comprises an alkali metal hydroxide; b) heating the composition to a temperature, which is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a value pH 6 - 14; and c) mixing the composition formed in step b) with a crosslinking agent and heating the composition to a temperature of 60 - 100 °C, while maintaining the pH of the composition at a pH value of 6 - 14.
    [021] In an embodiment of the present invention, the compound selected from the class of phenols is selected from a group consisting of phenol, cresol, resorcinol and combinations thereof. In one embodiment of the present invention, the compound selected from the class of phenols is phenol.
    [022] In an embodiment of the present invention, lignin is dissolved in a composition, which consists of water, at least one compound selected from the class of phenols, and alkali, in step a). In one embodiment of the present invention lignin is dissolved in an aqueous composition of a compound selected from the class of phenols and alkali.
    [023] In an embodiment of the present invention, the temperature of the composition is maintained, in step a), at a temperature of 65 - 80, and preferably at a temperature of 70 - 75 °C.
    [024] In an embodiment of the present invention step b) comprises heating the composition to a temperature which is at least 5 °C, preferably at least 10 °C, and more preferably at least 20 °C plus higher than the temperature of the composition in step a).
    [025] In an embodiment of the present invention, the composition is heated, in step b), to a temperature of 60 - 100 °C, preferably to a temperature of 70 - 95 °C, and more preferably to a temperature 75 - 90 °C.
    [026] In an embodiment of the present invention step b) is performed to allow lignin to react with the compound selected from the class of phenols and alkali.
    [027] In one embodiment of the present invention more alkali is added to the composition in step b). In one embodiment of the present invention alkali is added to the composition in step a) and step b).
    [028] The inventors of the present invention surprisingly found that dissolving the lignin in a composition of, for example, phenol, alkali and water, at the specific temperature used, advantageously affects the time needed to dissolve the lignin in the composition. The inventors of the present invention have found that the treatment of lignin according to step a) and step b) allows the production of a binder composition with a low pH value, if desired. The inventors of the present invention have found that by the method of the present invention, it has been possible to produce a lignin-based binder composition which is suitable for, for example, the production of structural wood panel products and impregnated coating materials. The inventors have also found that different types of lignin, such as dry or condensed lignin which are generally challenging and slow to dissolve, can be more easily dissolved by the method according to the present invention. Furthermore, the inventors noted that the alkali used to activate the lignin was not consumed during the lignin dissolution step, so less chemical is needed, thus with lower total chemical costs.
    [029] In an embodiment of the present invention step b) is performed by alkylation of lignin. The alkylation step results in the activation of lignin. Without limiting the invention to any specific theory as to why the alkylation of lignin results in the formation of a more activated or more reactive lignin compared to unalkylated lignin, it must be considered that the alkylation opens up the macromolecular structure of lignin whereby steric hindrances that normally deactivate reactive groups on lignin structures are removed. Alkylation can also add charged groups to the lignin macromolecule. In one embodiment of the present invention the treatment of lignin with the method according to the present invention activates the lignin. The advantage of using, for example, alkylated lignin, for example, to produce a binder composition is that the reaction and compatibility behavior is much better than in a normal case, where untreated lignin was used in the stage cooking or polymerization of the production process.
    [030] In this specification, unless otherwise indicated, the term "lignin" is to be understood as lignin from any suitable lignin source.
    [031] The lignin used may be essentially pure lignin. By the expression "essentially pure lignin" is to be understood as lignin at least 90% pure, preferably lignin at least 95% pure. In one embodiment of the present invention, the essentially pure lignin comprises at most 10%, preferably at most 5%, of other components. Extracts and carbohydrates such as hemicelluloses can be mentioned as examples of such other components. In one embodiment of the present invention the lignin contains less than 10% by weight, preferably less than 6% by weight, and more preferably less than 4% by weight of carbohydrates. The amount of carbohydrates present in lignin can be measured by high-performance anion exchange chromatography with pulsed amperometric detector (HPAE-PAD) according to standard SCAN-CM 71.
    [032] In an embodiment of the present invention, the percentage of lignin ash is less than 7.5% by weight, preferably less than 5% by weight, and more preferably less than 3% by weight. Ash content can be determined by carbonification and rapid burning of a lignin sample so that alkali salts are not melted before the organic matter has been burnt (eg 20 - 200 °C for 30 minutes, after which the temperature is adjusted to 200 - 600 °C for 1 h, and then it is adjusted to the temperature of 600 - 700 °C for 1 hour) and finally the lignin sample is ignited at 700 °C for 1 h. The ash content of a lignin sample refers to the remaining mass of the sample after burning and ignition, and is presented as percentages of the sample's dry matter content.
    [033] In an embodiment of the present invention, the weight average molecular weight (Mw) of lignin is 1000 - 15000 g/mol, preferably 2000 - 10000 g/mol, and more preferably 3000 - 8000 g/mol. The molecular weight of lignin can be determined using high performance size exclusion chromatography as follows: Two parallel measurements are performed. 0.1 M NaOH is used as an eluent. Calibration is done using Na-polystyrene sulfonate standards having a molecular weight of 1100 - 73900 g/mol. For quality control, standard grade kraft lignin and standard molecular weight PSS are used. Columns used are PSS MCX precolumns, 1000 Á and 100,000 separação separation columns filled with sulfonated styrene-divinylbenzene copolymer matrix. The isocratic execution program is used. Runtime is 45 minutes. The injection volume is 50 μl. Flow is 0.5 ml per minute. The temperature is 25 °C. As a result of the chromatography, the number average molecular weight (Mn), the weight average molecular weight (Mw), the peak molecular weight (Mp) and the polydispersion index (PDI) values can be reported.
    [034] In an embodiment of the present invention, the number average molecular weight (Mn) of lignin is 700 - 4000, preferably 800 - 3000 and more preferably 1000 - 2500.
    [035] In an embodiment of the present invention, the polydispersity of lignin is 1.0 - 7, preferably 1.2 - 6, and more preferably 1.4 - 4.5.
    [036] In one embodiment of the present invention, the normalized radical scavenging index (NRSI) of lignin is 0.01 - 20, preferably 0.05 - 10, and more preferably 0.1 - 6. The antioxidant activity of the extracts can be evaluated using the DPPH method on methanol extracts. The basis of the radical scavenging method is described in Malterud et al. (Pharmacol. Toxicol. 1996, 78: 111-116). The method is based on the ability of extracts and pure components to react with 1,1,-diphenylpicryl-2-hydrazyl radical (DPPH•)- molecules when DPPH loses its radical characteristic. The form of radical decline can be observed with a spectrophotometer as a color change of the solution from violet to yellow (absorbance is measured at a wavelength of 515 nm). The RSI (radical scavenging index) is defined as the inverse of the concentration that produced 50% inhibition of DPPH absorbance at 515 nm. The results can then be "normalized" (NRSI) by dividing the sample's RSI by the RSI value for the butyl hydroxytoluene (BHT) control.
    [037] In an embodiment of the present invention, the dry solids content of lignin is below 98%, preferably 40 - 80%, and more preferably 50 - 70%. The dry solids content can be measured by drying a 1 - 5 g lignin sample at a temperature of 60°C or above and in a vacuum oven for four hours.
    [038] In an embodiment of the present invention, the lignin has an amount of 0.1 - 6 mmol, preferably 0.3 - 3.5 mmol of aliphatic hydroxyl groups per gram of dry lignin.
    [039] In an embodiment of the present invention, the lignin has an amount of 0.1 - 5 mmol, preferably 1.5 - 4.5 mmol of phenolic hydroxyl groups per gram of dry lignin. The phenolic and aliphatic hydroxyl groups can be determined by characterization of a lignin sample with31P NMR spectroscopy after phosphitylation and after which the aliphatic hydroxyl groups can be quantitatively determined. For 31P NMR analysis 40 mg of lignin can be weighed out and dissolved in 300 µL of N,N-dimethylformamide. After total dissolution of 200 μL of pyridine, 400 μL (0.05 M) of an internal standard (ISTD) solution of Endo-N-hydroxy-5-norbornene-2,3-dicarboximide in pyridine/CDCl3 and 100 μL of solution of Cr(acac)3 in pyridine/CDCl3 are added. Then, 200 µL of 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane phosphitylation reagent is added dropwise. Finally, 600 CDCl3 phospholane is added to the solution and a light brown to black solution is obtained. Freshly prepared samples can then be measured with 31P NMR at room temperature. The 500 MHz Bruker NMR spectrometer can be used for the measurement. The 31P NMR measurement is based on the method developed by Grannata and Argyropoulos (Grannata A. and Argyropoulos DS, 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins. J. Agric. Food Chem, 1995, 43:1538-1544. Results are calculated in mmol/g lignin.
    [040] In an embodiment of the present invention, lignin is selected from a group consisting of kraft lignin, steam explosion lignin, biorefinery lignin, supercritical separation lignin, hydrolysis lignin, flash precipitation lignin, lignin from biomass, lignin from an alkaline pulping process, lignin from a sodium process, lignin from pulping with organsolvents and combinations thereof. In one embodiment of the present invention, the lignin is wood-based lignin. Lignin can be sourced from softwood, hardwood, annual plants or a combination of these.
    [041] The different components of lignin can have different properties, for example, molecular weight, molar mass, polydispersity, hemicellulose and extractive contents and compositions.
    [042] By "kraft lignin" is meant in this specification, unless otherwise indicated, lignin originating from kraft black liquor. Black liquor is an aqueous alkaline solution of lignin residues, hemicellulose and inorganic chemicals used in a kraft pulping process. The black liquor from the pulping process comprises components that originate from different species of softwood and hardwood in various proportions. Lignin can be separated from black liquor by different techniques, including, for example, precipitation and filtration. Lignin usually starts to precipitate at pH values below 11 - 12. Different pH values can be used in order to precipitate lignin fractions with different properties. These lignin fractions differ from each other by a molecular weight distribution, eg Mw and Mn, polydispersity, hemicellulose contents and extractives. The molar mass of lignin precipitated at a higher pH value is greater than the molar mass of lignin precipitated at a lower pH value. Furthermore, the molecular weight distribution of the lignin fraction precipitated at a lower pH value is broader than that of the lignin fraction precipitated at a higher pH value.
    [043] Precipitated lignin can be purified from inorganic impurities, hemicellulose and wood extractives using acidic washing steps. Further purification can be achieved by filtration.
    [044] In an embodiment of the present invention the lignin is flash precipitation lignin. The term "flash precipitation lignin" is to be understood in this specification as lignin that has been precipitated from black liquor in a continuous process of lowering the pH of a black liquor stream, under the influence of an overpressure of 200 - 1000 kPa, up to the lignin precipitation level using an acidifying agent based on carbon dioxide, preferably carbon dioxide, and by sudden release of pressure for lignin precipitation. The method for producing flash precipitation lignin is disclosed in FI patent application 20106073. The residence time in the above method is less than 300 seconds. Flash precipitating lignin particles, which have a particle diameter of less than 2 µm, form agglomerates, which can be separated from the black liquor, for example, using filtration. The advantage of flash precipitation lignin is its greater reactivity compared to normal kraft lignin. Flash precipitation lignin can be purified and/or activated if necessary for further processing.
    [045] In an embodiment of the present invention, lignin is separated from pure biomass. The separation process can start with dissolution of the biomass with strong acid or strong alkali followed by a neutralization process. After treatment with alkali the lignin can be precipitated in a similar manner as shown above. In one embodiment of the present invention the separation of lignin from biomass comprises an enzyme treatment step. The enzyme treatment modifies the lignin to be extracted from the biomass. Lignin separated from pure biomass is sulfur free and therefore valuable in further processing.
    [046] In an embodiment of the present invention, the lignin is steam explosion lignin. Steam blasting is a pulping and extraction technique that can be applied to wood and other fibrous organic materials.
    [047] By "biorefinery lignin" is to be understood in this specification, unless otherwise indicated, lignin that can be recovered from a refining facility or process where biomass is converted into fuel, chemicals and other materials.
    [048] By "supercritical separation lignin" is to be understood in this specification, unless otherwise indicated, lignin that can be recovered from biomass using supercritical fluid separation or extraction techniques. Supercritical conditions correspond to the temperature and pressure above the critical point for a given substance. Under supercritical conditions there are no distinct liquid and gas phases. Supercritical liquid or water extraction is a method of decomposing and converting biomass into cellulosic sugar by employing water or liquid under supercritical conditions. The water or liquid, acting as a solvent, extracts sugars from the cellulosic plant material and the lignin remains as a solid particle.
    [049] In an embodiment of the present invention, the lignin is hydrolyzed lignin. Hydrolyzed lignin can be recovered from chemical wood or paper pulp processes.
    [050] In an embodiment of the present invention, lignin originates from an organosolv process. Organosolv is a pulping technique that uses an organic solvent to solubilize lignin and hemicellulose.
    [051] The pH value of the composition in step a) and in step b) can be selected depending on the final application of the binder composition to be produced.
    [052] In an embodiment of the present invention, the pH of the composition is maintained, in step a), with a pH value of 4 - 10, preferably with a pH value of 4.5 - 9.5, with more preferably, with a pH value of 5 - 9, and even more preferably, with a pH value of 5.5 - 8.5. In one embodiment of the present invention, the pH of the composition is maintained, in step b), preferably at a pH value of 6 - 10, more preferably at a pH value of 6.5 - c.5. and even more preferably with a pH value of 7 - 9. These types of pH ranges can be used in step a) and step b) when producing a binder composition for high pressure laminates.
    [053] In an embodiment of the present invention, the pH of the composition is maintained, in step a), with a pH value of 4 - 14, preferably with a pH value of 7 - 13.5, and with more preferably, at a pH value of 8.5 - 13. In one embodiment of the present invention, the pH of the composition is maintained, in step b), preferably at a pH value of 7 - 14, more preferably, with a pH value of 9 - 13.5, and even more preferably with a pH value of 10 - 13. These types of pH ranges can be used in step a) and step b) when producing a Binder composition for plywood.
    [054] In an embodiment of the present invention step b) is carried out for 10 minutes - 2 hours, preferably for 1 hour - 1.5 hours.
    [055] In an embodiment of the present invention, the alkali is sodium hydroxide, potassium hydroxide or a combination thereof.
    [056] In an embodiment of the present invention, the alkali concentration is 0.1 - 11% by weight and preferably 0.5 - 9% by weight based on the total weight of the composition in step b). In one embodiment of the present invention, the alkali concentration is 0.1 - 5% by weight and preferably 0.5 - 2% by weight based on the total weight of the composition in step b). In one embodiment of the present invention, the alkali concentration is 3 - 15% by weight, preferably 5 - 12, and more preferably 6 - 10% by weight based on the total weight of the composition in step b).
    [057] In an embodiment of the present invention, the concentration of lignin in step a) is 10 - 40% by weight and preferably 20 - 30% by weight based on the total weight of the composition in step a).
    [058] In an embodiment of the present invention, the concentration of the compound selected from the class of phenols in step a) is 10 - 50% by weight, preferably 20 - 50% by weight, and more preferably 20 - 45% by weight based on the total weight of the composition in step a).
    [059] The step of heating the composition formed in step c) is performed by polymerizing the reactant components, i.e., lignin, the compound selected from the class of phenols and the crosslinking agent, such that the viscosity of the composition of binder is increased. Heating can be continued until a predetermined viscosity value is formed. The determined viscosity value of the final binder composition may vary depending on the specific application in which the binder composition is to be used.
    [060] In an embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 40 cP, preferably at least 50 cP, and more preferably at least 80 cP. In one embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 40 cP but not greater than 250 cP, preferably at least 50 cP, but not greater than 150 cP, and more preferably by the minus 80, but not more than 120 cP.
    [061] In an embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 250 cP, preferably at least 300 cP and more preferably at least 500 cP. In one embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 250 cP, but not greater than 1500 cP, preferably at least 300 cP, but not greater than 1200 cP, and more preferably , at least 500, but not more than 1000 cP.
    [062] Viscosity is measured at 25 °C using a rotary viscometer.
    [063] In an embodiment of the present invention, step c) comprises heating the composition, preferably at a temperature of 65 - 95 °C, more preferably at a temperature of 70 - 90 °C, and still with more preferably at a temperature of 75 - 85°C.
    [064] In an embodiment of the present invention, the crosslinking agent is selected from a group consisting of an aldehyde, a derivative of an aldehyde, an aldehyde-forming compound and combinations thereof. In one embodiment of the present invention, the derivative of an aldehyde is hexamethylenetetramine, paraformaldehyde or trioxane. In one embodiment of the present invention, the crosslinking agent is selected from the group consisting of an aromatic aldehyde, glyoxal, furfuryl alcohol, caprolactam and glycol compounds. The aldehyde can be formaldehyde. The aromatic aldehyde can be furfuryl aldehyde. In one embodiment of the present invention, the cross-linking agent is an aldehyde and preferably formaldehyde, para-formaldehyde or a combination thereof.
    [065] In an embodiment of the present invention step c) is performed in the presence of a catalyst. In one embodiment of the present invention, the catalyst is selected from a group consisting of sodium hydroxide, potassium hydroxide and any mixture thereof.
    [066] In an embodiment of the present invention, the pH of the composition is maintained, in step c), preferably at a pH value of 6 - 10, more preferably at a pH value of 6.5 - 9 .5, and even more preferably with a pH value of 7 - 9.
    [067] In an embodiment of the present invention, the pH of the composition is maintained, in step c), preferably with a pH value of 7 - 14, more preferably with a pH value of 9 - 13.5 , and even more preferably, with a pH value of 10 - 13.
    [068] The present invention further relates to the use of lignin treated by the method according to the present invention for the production of a binder composition.
    [069] The present invention further relates to a binder composition that can be obtained by the method according to the present invention.
    [070] The present invention further relates to an adhesive composition comprising the binder composition according to the present invention. The adhesive composition may further comprise one or more adhesive components selected from the group consisting of other binders, diluents, additives, catalysts and fillers.
    [071] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained in step a) at a value of 4 - 10 and in step b) at a value of 6 - 10, for the production of a laminate, and preferably a high pressure laminate.
    [072] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained in step c) at a value of 6 - 10 for the production of a laminate and preferably a high pressure laminate.
    [073] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained in step a) at a value of 4 - 10 and in step b) at a value of 6 - 10, for the production of a casting material, a protective coating, a friction material, an abrasive material, glass wool, rock wool, a prepreg (prepreg) , a formwork film, an overlay, a molding component or a fiber reinforced composite.
    [074] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained in step c) at a value of 6 - 10 , for the production of a casting material, a coating protector, a friction material, an abrasive material, glass wool, rock wool, a prepreg, a formwork film, an overlay, a molding component or a fiber reinforced composite.
    [075] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained in step a) at a value of 4 - 14 and in step b) at a value of 7 - 14, to produce a particle board, an oriented filament board, a chip board, an intrallam, a gluelam, a hardboard board, a waferboard board, a fiber board, a plywood, or a wood adhesive.
    [076] The present invention further relates to the use of a binder composition that can be obtained by the method according to the present invention, in which the pH of the composition is maintained, in step c), preferably with the pH value of 7 - 14, for the production of a particle board, an oriented filament board, a chip board, an intrallam, a gluelam, a hardboard board, a waferboard board, a fiber board, a plywood or a wooden sticker.
    [077] The embodiments of the invention described hereinbefore can be used in any combination with each other. Several of the embodiments can be combined together to form an additional embodiment of the invention. A method, composition or use to which the invention is concerned may comprise at least one of the embodiments of the invention described hereinbefore.
    [078] An advantage of the method according to the present invention is that the time required to dissolve the lignin in the aqueous composition is reduced when using the specified temperature.
    [079] An advantage of the method according to the present invention is that it is possible to treat the lignin in a way that allows the production of a low pH binder composition, that is, a binder composition with a neutral pH range or acid. Lignin treated with the method according to the present invention has an open structure making it more reactive whereby production of low pH binder composition is possible with lignin.
    [080] An advantage of the present invention is that a bio-based binder composition suitable to be used for the production of high pressure laminates can be produced by the method according to the present invention. An advantage of the present invention is that a more environmentally friendly binder composition can be produced for high pressure laminates.
    [081] EXAMPLES
    [082] Reference will now be made in detail to embodiments of the present invention, an example of which is illustrated in the accompanying drawings.
    [083] The description that follows describes some embodiments of the invention in detail such that a person skilled in the art is able to use the present invention based on the description. Not all modalities steps are discussed in detail, as many of the steps will be obvious to the person skilled in the art based on this descriptive report.
    [084] Figure 1 illustrates a method according to an embodiment of the present invention for the treatment of lignin.
    [085] Before lignin treatment is started, the source of lignin is chosen. Furthermore, other components and their amounts to be used in the method according to the present invention are selected. If necessary, the components used in the method of Figure 1 can be pretreated to be suitable for lignin treatment processes.
    [086] After the various preparations and pretreatments, in one of the modalities of the present invention shown in Figure 1, step a) is performed. Step a) comprises dissolving lignin in an aqueous composition containing a compound selected from the class of phenols and alkali. Alkali is a hydroxide of an alkali metal. The temperature of the composition is maintained at 40 - 85 °C.
    [087] After the step of dissolving the lignin, the composition formed in step a) is heated to a temperature that is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a pH value of 6 - 14. During step b) the lignin is allowed to react with compounds selected from the class of phenols and alkali.
    [088] Step a) and step b) result in lignin being suitable for other production steps and being suitable to be covalently bonded with, for example, formaldehyde.
    [089] Figure 2 illustrates a method according to an embodiment of the present invention for producing a binder composition.
    [090] The method illustrated in Figure 2 starts with the treatment of lignin in step a) and in step b) according to the method described above for Figure 1.
    [091] After step b) the composition formed in step b) is mixed with a crosslinking agent in step c). The formed composition is heated to a temperature of 60 - 100 °C to allow the reactant components, i.e. lignin, the compound selected from the class of phenols and the crosslinking agent, in the composition to react with each other to form a binder composition. The pH of the composition is maintained, in step c), at a pH value of 6 - 14. Heating of the composition is continued until a desired predetermined viscosity value of the binder composition is reached.
    [092] As a result of step c) a binder composition that has desired properties and especially has a high ratio of bio-based components is produced. This binder composition can be used as such for bonding applications or it can be further treated with other adhesive components to produce an adhesive composition.
    [093] EXAMPLE 1 - Activation of lignin and the use of activated lignin for the production of a binder composition.
    [094] In this example the lignin was first treated with phenol and sodium hydroxide. The following components and their values were used:


    [095] First, lignin was mixed with water and then sodium hydroxide was added to the formed composition. The pH was raised to a value of about 13.8. For this composition, phenol was added. The temperature of the composition was maintained at about 45°C while dissolving the lignin in the composition.
    [096] Then the temperature was increased to about 75 °C and heating was maintained for about 1 h. The pH of the composition was maintained at a value of 10 - 11 during heating of the composition.
    [097] The lignin treated as described above was then used for the production of a binder composition. 490 g of formaldehyde was added to the above formed composition in a gradual manner. The composition formed was heated to a temperature of about 83 - 85°C and until the viscosity increased to 315 cP as measured at 25°C using a rotary viscometer.
    [098] The composition of binder formed was further analyzed. The results of the analysis can be seen in Table 1.
    [099] Table 1. Analysis results

    [0100] In Table 1 MR stands for the molecular ratio, that is, the ratio of mol(formaldehyde)/mol(phenol + Lignin).
    [0101] The gel time was determined by adding 0.5 ml of sample to a test tube with a rod. The sample was not shaken. The test tube was heated to 100 °C in an oil or glycerin bath without mixing. The time until the sample becomes pasty (molten solid) was measured after which the measurement was completed.
    [0102] From the results indicated in Table 1 it can be seen that the solids content is at a suitable level for the binder composition to be used for wood panel products such as plywood or oriented filament boards.
    [0103] EXAMPLE 2 - Activation of lignin and the use of activated lignin for the production of a binder composition.
    [0104] In this example the lignin was first treated with phenol and sodium hydroxide. The following components and their quantities were used:

    [0105] First, an aqueous composition was formed by mixing water, phenol and sodium hydroxide. To this aqueous composition lignin was added. The temperature of the composition was maintained at about 70 - 75°C while dissolving the lignin in the composition.
    [0106] Then the temperature was raised to about 90 °C and heating was maintained for about 10 minutes. The pH of the composition was maintained at a value of 8 - 8.3 during heating of the composition.
    [0107] The lignin treated as described above was then used for the production of a binder composition. 568 g of para-formaldehyde was added to the composition formed above in a stepwise manner. The formed composition was heated to a temperature of about 78 - 90°C and until the viscosity was about 94 cP as measured at 25°C using a rotary viscometer.
    [0108] The composition of binder formed was further analyzed. The results of the analysis can be seen in Table 2.
    [0109] Table 2. Analysis results

    [0110] In Table 2 MR stands for the molecular ratio, that is, the ratio of mol(para-formaldehyde)/mol(phenol + lignin).
    [0111] The gel time was determined by adding 0.5 ml of sample to a test tube with a rod. The sample was not shaken. The test tube was heated to 100 °C in an oil or glycerin bath without mixing. The time until the sample turned pasty (molten solid) was measured after which the measurement was completed.
    [0112] From the results indicated in Table 2 it can be seen that the solids content is at a suitable level for the binder composition to be used for laminates such as high pressure laminates and for coatings. Water tolerance is better than for phenol-formaldehyde binder compositions traditionally used for laminates such as high pressure laminates and for formwork films.
    [0113] EXAMPLE 3 - Plywood Production
    [0114] The binder composition produced in Example 1 was used for the production of an adhesive composition. The binder composition has been mixed with diluents, fillers, catalysts, additives, for example of which, for example, starch, wood flour and hardener (for example tannin or carbonates) can be mentioned, thus forming the adhesive composition. Then wood veneers having a thickness below 1.5 mm were glued together with the produced adhesive composition to produce a plywood-9. After 8 min, the cold pressed panels were hot pressed at 130 °C. The results showed that the effective bonding was good enough for bonding wood veneers.
    [0115] EXAMPLE 4 - Production of formwork films
    [0116] The binder composition produced in Example 2 was used for the production of formwork films. Kraft papers weighing 42 g/m2 were impregnated with the binder composition and dried at 130°C. The impregnated paper was pressed onto one side of the plywood at 145 °C for 6 min. The results showed that the formwork film was performing well enough; no bubbles or delamination on the surface were observed.
    [0117] EXAMPLE 5 - Activation of lignin and the use of activated lignin for the production of a binder composition
    [0118] In this example the lignin was first treated with phenol and sodium hydroxide. The following components and their values were used:

    [0119] First, an aqueous composition was formed by mixing water, phenol and sodium hydroxide. To this aqueous composition lignin was added. The temperature of the composition was maintained at about 70 - 75°C while dissolving the lignin in the composition.
    [0120] Then the temperature was raised to about 90 °C and heating was maintained for about 10 minutes. The pH of the composition was maintained at a value of 8 - 8.3 during heating of the composition.
    [0121] The lignin treated as described above was then used for the production of a binder composition. 568 g of para-formaldehyde was added to the composition formed above in a stepwise manner. The composition formed was heated to a temperature of about 76°C until the viscosity was about 930 cP as measured at 25°C using a rotary viscometer.
    [0122] The composition of binder formed was further analyzed. The results of the analysis can be seen in Table 3.
    [0123] Table 3. The results of the analysis

    [0124] In Table 3 MR stands for the molecular ratio, that is, the ratio of mol(para-formaldehyde)/mol(phenol + lignin).
    [0125] The gel time was determined by adding 0.5 ml of sample to a test tube with a rod. The sample was not shaken. The test tube was heated to 130 °C in a bath of glycerin or oil without mixing. The time until the sample turned pasty (molten solid) was measured after which the measurement was completed.
    [0126] The formed binder composition was used to produce a prepreg by adding to the cooled binder composition first about 2% by weight, based on the weight of the binder composition, of diethylene glycol (DEG) and then , below 1% by weight, based on the weight of the binder composition, of glycolic acid.
    [0127] EXAMPLE 6 - Formation of rock wool
    [0128] In this example the rock wool was formed. First, lignin was treated with phenol and sodium hydroxide. The following components and their quantities were used:


    [0129] First, lignin was added to a composition of water, phenol and sodium hydroxide. For this composition 45.4 g of borax were added in a gradual manner. Borax is a product commonly used in rock wool to enhance fire resistance and to act as an anti-molding agent. Borax does not participate in reactions in which lignin is dissolved and allows it to react with phenol and NaOH. Borax can be added to the composition early in the process to ensure even distribution in the polymer matrix, but it can also be added only after the formation of the binder composition.
    [0130] The temperature of the composition was maintained at about 42 °C and the pH of the composition was about 9 - 10, allowing the lignin to dissolve.
    [0131] Thereafter, the temperature of the composition was raised to 50 °C and the lignin was allowed to react with phenol and sodium hydroxide in the composition for about one hour. The pH of the composition was about 9.3.
    [0132] After the lignin was activated by the process described above, 1093.5 g of formaldehyde was added to the composition and the composition was heated at 65 °C for about 2.5 hours. The pH was maintained at about 8.8. Then, the composition was cooled to a temperature of 40°C, about 1% by weight, based on the weight of the composition, of boric acid was added followed by about 4 - 5% by weight, based on the weight of the composition, of urea.
    [0133] It is obvious to a person skilled in the art that, with the advancement of technology, the basic idea of the invention can be implemented in various ways. The invention and its embodiments, therefore, are not limited to the examples described above; rather, they may vary within the scope of the claims.
    权利要求:
    Claims (24)
    [0001]
    1. Method for treating lignin, the method characterized by comprising the following steps: a) dissolving at least 90% pure lignin in an aqueous composition, which contains alkali and a compound selected from the class of phenols, maintaining the temperature of the composition at 40-85°C and the pH of the composition at a pH value of 4-10, wherein the alkali comprises an alkali metal hydroxide; and b) alkalinize the lignin by heating the composition to a temperature, which is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a pH value of 6-10, wherein the heating of step b) is carried out for 10 minutes and 2 hours, the heating allowing the dissolved lignin to react with the alkali and the compound selected from the phenol class, and wherein lignin is selected from a group consisting of kraft lignin, steam explosion lignin, biorefinery lignin, supercritical separation lignin, hydrolysis lignin, instantaneous precipitated lignin, lignin from biomass, lignin from the alkaline pulping process lignin process, soda lignin, organosolv pulping lignin or any combination thereof.
    [0002]
    Method according to claim 1, characterized in that the compound selected from the class of phenols is selected from a group consisting of phenol, cresol, resorcinol and combinations thereof.
    [0003]
    Method according to claim 1, characterized in that the temperature of the composition is maintained, in step a), at a temperature of 6580°C.
    [0004]
    A method according to claim 1, characterized in that step b) comprises heating the composition to a temperature which is at least 5°C higher than the temperature of the composition in step a).
    [0005]
    Method according to claim 1, characterized in that the pH of the composition is maintained, in step a), at a pH value of 4.5-9.5.
    [0006]
    Method according to claim 5, characterized in that the pH of the composition is maintained, in step b), at a pH value of 6.5-9.5.
    [0007]
    Method according to claim 1, characterized in that the pH of the composition is maintained, in step a), at a pH value of 5-9.
    [0008]
    Method according to claim 7, characterized in that the pH of the composition is maintained, in step b), at a pH value of 7-9.
    [0009]
    Method according to claim 1, characterized in that the composition is heated, in step b), to a temperature of 60-100°C.
    [0010]
    10. Method for the production of a binding composition, the method characterized by comprising the following steps: a) dissolving at least 90% pure lignin in an aqueous composition, which contains alkali and a compound selected from the class of phenols, keeping the temperature of the composition at 40-85°C and the pH of the composition at a pH value of 4-10, wherein the alkali comprises an alkali metal hydroxide; b) alkalinize the lignin by heating the composition to a temperature, which is higher than the temperature of the composition in step a), with the proviso that the temperature of the composition does not exceed 100 °C, while maintaining the pH of the composition at a pH value of 6-10; and c) mixing the composition formed in step b) with a crosslinking agent and heating the composition to a temperature of 60-100 °C, while maintaining the pH of the composition at a pH value of 6-10, wherein the heating of step b) is carried out for 10 minutes and 2 hours, the heating allowing the dissolved lignin to react with the alkali and the compound selected from the class of phenols, and wherein the lignin is selected from a group consisting of lignin kraft, steam explosion lignin, biorefinery lignin, supercritical separation lignin, hydrolysis lignin, instantly precipitated lignin, lignin originating from biomass, lignin from the alkaline pulping process, soda lignin process, organosolv pulping lignin or any combination thereof, wherein the viscosity of the binding composition is about 40-250 cP.
    [0011]
    The method of claim 10, characterized in that step b) comprises heating the composition to a temperature which is at least 5 °C higher than the temperature of the composition in step a).
    [0012]
    The method of claim 10, characterized in that step c) comprises heating the composition to a temperature of 6595 °C.
    [0013]
    Method according to claim 10, characterized in that the pH of the composition is maintained, in step a), at a pH value of 4.5-9.5.
    [0014]
    Method according to claim 13, characterized in that the pH of the composition is maintained, in step b), at a pH value of 6.5-9.5.
    [0015]
    A method according to claim 10, characterized in that the pH of the composition is maintained, in step a), at a pH value of 5-9.
    [0016]
    The method of claim 15, characterized in that the pH of the composition is maintained, in step b), at a pH value of 7-9.
    [0017]
    The method of claim 10, characterized in that the pH of the composition is maintained, in step c), at a pH value of 6.5-9.5.
    [0018]
    The method of claim 17, characterized in that the pH of the composition is maintained, in step c), at a pH value of 7-9.
    [0019]
    The method of claim 10, characterized in that the crosslinking agent is an aldehyde.
    [0020]
    Binder composition characterized in that it can be obtained by the method according to claim 10.
    [0021]
    21. Adhesive composition characterized in that it comprises the binder composition according to claim 20 and one or more adhesive components selected from a group consisting of other binders, extenders, additives, catalyst and/or fillers.
    [0022]
    The method of claim 1, characterized in that the act of alkalizing the lignin by heating the composition of step b) results in the formation of a binder composition.
    [0023]
    A method according to claim 1, characterized in that the pH of the composition from step a) is maintained at a pH value of 5.5-8.5.
    [0024]
    The method according to claim 1, characterized in that the pH of the composition from step b) is maintained at a pH value of 7-9.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112016009537B1|2021-05-25|method for treating lignin and for producing a binder composition
    US20200040022A1|2020-02-06|Method for treating lignin and for producing a binder composition
    US10894855B2|2021-01-19|Method for increasing the reactivity of lignin
    BR112014023873B1|2021-02-02|method for producing phenol-formaldehyde binder composition using low molecular weight lignin together with lignin
    BR112014010004B1|2020-12-01|method to increase the reactivity of lignin
    US20190160703A1|2019-05-30|Fiber based product
    FI127750B|2019-01-31|Method for producing a binder composition
    同族专利:
    公开号 | 公开日
    DE202014011173U1|2018-05-16|
    CA2927313A1|2015-06-04|
    FI126737B|2017-04-28|
    CA2927313C|2018-04-24|
    US10301437B2|2019-05-28|
    EP3074410A1|2016-10-05|
    EP3074410B1|2020-11-11|
    FI20136178A|2015-05-27|
    CN111647171A|2020-09-11|
    EP3783008A1|2021-02-24|
    US20160257791A1|2016-09-08|
    WO2015079107A1|2015-06-04|
    JP2016539216A|2016-12-15|
    JP6538674B2|2019-07-03|
    CN105793272A|2016-07-20|
    FI12008U1|2018-03-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4017430A|1975-06-23|1977-04-12|Georgia-Pacific Corporation|Coating composition|
    US4306999A|1979-11-23|1981-12-22|American Can Company|High solids, low viscosity lignin solutions|
    CA1185238A|1981-06-16|1985-04-09|Stephen Y. Lin|Sulfonated lignin dispersants and dyestuffs andmethods utlizing the same|
    DE3142047A1|1981-10-23|1983-05-11|Skf Kugellagerfabriken Gmbh, 8720 Schweinfurt|DEVICE FOR DIE CASTING A ROLLER BEARING CAGE|
    US4476193A|1982-09-14|1984-10-09|Westinghouse Electric Corp.|Sulfur containing lignin modified alkaline earth treated phenolic impregnating resins for core layers of humidity resistant laminates|
    CA1229334A|1983-09-29|1987-11-17|Ronnie S. Roberts|Biomass fractionation process|
    CA1284637C|1987-08-24|1991-06-04|George S. Faass|Biomass fractionation process|
    US5010156A|1988-05-23|1991-04-23|Eastman Kodak Company|Organosolv lignin-modified phenolic resins and method for their preparation|
    CA2043313A1|1989-04-03|1992-11-28|Herbert A. Schroeder|Method for recovering and using lignin in adhesive resins|
    US5196460A|1990-05-29|1993-03-23|Repap Technologies Inc.|Rubber compositions containing high purity lignin derivatives|
    CA2070500C|1991-06-13|1997-10-14|Ted Mcvay|Reactive phenolic resin modifier|
    CA2551418C|1997-09-12|2010-09-28|Kabushiki Kaisha Maruto|Novel lignin derivatives, molded products using the same and processes for making the same|
    CA2355808A1|2001-08-24|2003-02-24|3926044 Canada Inc.|Process for preparing a black liquor-phenol formaldehyde thermoset resin|
    JP2003159703A|2001-11-27|2003-06-03|Kono Shinsozai Kaihatsu Kk|Board manufacturing method|
    US6689737B2|2002-01-17|2004-02-10|The Procter & Gamble Company|Household cleaning and/or laundry detergent compositions comprising lignin-derived materials|
    US20070135622A1|2003-10-31|2007-06-14|Hideaki Hayashi|Method and apparatus for manufacturing lignophenol derivative|
    JP4316536B2|2005-06-07|2009-08-19|独立行政法人科学技術振興機構|Method for separating and recovering lignin derivatives|
    CN101440170B|2008-12-17|2012-02-22|中国林业科学研究院林产化学工业研究所|Preparation of biomass modified phenolic foam plastic|
    CN101492522B|2009-02-27|2010-09-01|中国林业科学研究院林产化学工业研究所|Method of preparing alkali lignin modified phenolic resin|
    EP2435453B1|2009-05-28|2022-03-02|Suzano Canada Inc.|Derivatives of native lignin|
    US9580454B2|2009-11-13|2017-02-28|Fpinnovations|Biomass fractionation process for bioproducts|
    BR112012014895A2|2009-12-16|2015-09-15|Domsjö Fabriker Ab|lignosulfonate of a certain quality and method of preparation of lignosulfonate of a certain quality|
    WO2011097721A1|2010-02-15|2011-08-18|Lignol Innovations Ltd.|Carbon fibre compositions comprising lignin derivatives|
    US20130183227A1|2010-09-23|2013-07-18|Toho Tenax Europe Gmbh|Thermoplastic lignin for producing carbon fibers|
    FI125991B|2010-10-15|2016-05-13|Upm Kymmene Corp|Method and apparatus for continuous precipitation of lignin from black liquor|
    AT510812A1|2010-10-29|2012-06-15|Annikki Gmbh|METHOD OF OBTAINING LIGNIN|
    BR112013015581A2|2010-12-20|2019-09-24|Shell Int Research|method, e.g. system|
    US8692041B2|2010-12-20|2014-04-08|Shell Oil Company|Process to produce biofuels from biomass|
    CN103314079B|2010-12-20|2016-04-13|国际壳牌研究有限公司|The method of biofuel is produced from biomass|
    US20150159061A1|2011-02-11|2015-06-11|Lamfeddal KOUISNI|Phenol-formaldehyde and lignin phenol-formaldehyde adhesive polymers with carbon black, and method of making same|
    FI124944B|2011-04-08|2015-03-31|Upm Kymmene Corp|A method of making a binder composition, a binder composition, an adhesive composition, a layered composite structure, and uses of the binder composition and the adhesive composition|
    CN102268833B|2011-07-26|2013-08-21|中国科学院过程工程研究所|Method for preparing dissolving pulp by carrying out steam explosion on crop straw and adopting prehydrolysis for sulfate|
    WO2013162881A1|2012-04-26|2013-10-31|Archer Daniels Midland Company|Liquid/liquid separation of lignocellulosic biomass to produce sugar syrups and lignin fractions|
    FI123934B|2012-03-29|2013-12-31|Upm Kymmene Corp|Use of low molecular weight lignin for the preparation of a binder composition|
    FI20125362A|2012-03-29|2013-09-30|Upm Kymmene Corp|Lignin and a method and system for treating lignin|
    FI123936B2|2012-03-29|2019-03-29|Upm Kymmene Corp|A method for increasing the reactivity of lignin|
    FI127816B|2012-06-06|2019-03-15|Upm Kymmene Corp|A method for fractionating lignin|
    CN102936323A|2012-12-03|2013-02-20|山东圣泉化工股份有限公司|Preparation method of lignin-phenol-formaldehyde resin and preparation method of lignin-phenol-formaldehyde resin foam|
    JP2014133817A|2013-01-10|2014-07-24|Sumitomo Bakelite Co Ltd|Method for manufacturing a lignin derivative and lignin resin molded article|
    WO2014142289A1|2013-03-15|2014-09-18|出光興産株式会社|Method for manufacturing lignin degradation product|
    CA2940516C|2013-03-15|2021-06-01|Sandia Corporation|Synthesis of novel ionic liquids from lignin-derived compounds|
    CA2913852A1|2013-05-29|2014-12-04|Kiram Ab|A method for the treatment of spent pulping liquor for the removal and production of a lignin containing product|
    US20150045543A1|2013-08-12|2015-02-12|Melvin Mitchell|Isolation method for water insoluble components of a biomass and products provided therefrom|
    HUE041358T2|2013-09-27|2019-05-28|Stora Enso Oyj|A composition comprising lignin and epoxy compound for coating and method for the manufacturing thereof and use thereof|
    FI20135972A|2013-09-30|2015-03-31|Upm Kymmene Corp|Process for increasing the reactivity of lignin|
    FI126737B|2013-11-26|2017-04-28|Upm-Kymmene Corp|A process for treating lignin and preparing a binder composition|
    FI126736B|2013-11-26|2017-04-28|Upm-Kymmene Corp|Process for treating lignin and preparing a binder composition|
    AU2014361863B2|2013-12-12|2018-05-31|Solenis Technologies, L.P.|Lignin nanoparticle dispersions and methods for producing and using the same|
    FI126195B|2014-01-28|2016-08-15|Upm-Kymmene Corp|Fiber-based product|
    JP6687594B2|2014-07-09|2020-04-22|ヴァーディア， インコーポレイテッド|Method for separating and purifying lignin from black liquor and composition thereof|
    SE539887C2|2014-10-03|2018-01-02|Stora Enso Oyj|A method to purify lignin from Sulfur by using an electric field|
    SE538572C2|2014-12-22|2016-09-20|Innventia Ab|Method of producing lignin with reduced amount of odorous substances|FI123936B2|2012-03-29|2019-03-29|Upm Kymmene Corp|A method for increasing the reactivity of lignin|
    FI126737B|2013-11-26|2017-04-28|Upm-Kymmene Corp|A process for treating lignin and preparing a binder composition|
    FI126736B|2013-11-26|2017-04-28|Upm-Kymmene Corp|Process for treating lignin and preparing a binder composition|
    SE539761C2|2016-03-21|2017-11-21|Stora Enso Oyj|Liquid lignin composition, lignin-based resin, and method ofincreasing the solubility of ligning|
    SE541735C2|2016-07-11|2019-12-03|Stora Enso Oyj|Method of manufacturing an oriented strand board product using a lignin-based phenolic resin|
    CN106279874A|2016-08-10|2017-01-04|吴迪|A kind of preparation method of lignin-base polythene material|
    NL2018722B1|2017-04-14|2018-10-24|Trespa Int Bv|A method for preparing an activated lignin composition|
    SE541439C2|2017-07-18|2019-10-01|Stora Enso Oyj|Liquid lignin composition|
    US11033867B2|2017-09-27|2021-06-15|Sustainable Fiber Technologies, LLC|Aqueous lignin and hemicellulose dispersion|
    US11066588B2|2017-11-21|2021-07-20|Sustainable Fiber Technologies, LLC|Deicing composition comprising lignocellulosic byproducts|
    US11091697B2|2017-11-29|2021-08-17|Sustainable Fiber Technologies, LLC|Dust suppressant and soil stabilization composition comprising lignocellulosic byproducts|
    WO2021133733A1|2019-12-22|2021-07-01|Sweetwater Energy, Inc.|Methods of making specialized lignin and lignin products from biomass|
    WO2021182542A1|2020-03-11|2021-09-16|株式会社ブリヂストン|Adhesive composition, rubber-organic fiber cord composite, and tire|
    法律状态:
    2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-10-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/11/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-12-07| B17A| Notification of administrative nullity (patentee has 60 days time to reply to this notification)|Free format text: REQUERENTE DA NULIDADE: OTTO BANHO LICKS - 870210109227 - 25/11/2021 |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20136178A|FI126737B|2013-11-26|2013-11-26|A process for treating lignin and preparing a binder composition|
    FI20136178|2013-11-26|
    PCT/FI2014/050902|WO2015079107A1|2013-11-26|2014-11-25|A method for treating lignin and for producing a binder composition|
    [返回顶部]