Low chloride mineral wool product

Abstract

The invention relates to a mineral fiber product having a low water-leachable chloride content, which is suitable for use as a non-corrosive heat and / or sound insulating material.

Description

[0001] This application is a divisional application of the Chinese patent application (PCT / EP2020 / 059671) with an application date of April 3, 2020, application number 202080100991.4, and invention name “Low Chloride Mineral Wool Product”. Field of the Invention

[0002] The present invention relates to mineral fiber products and uses of mineral fiber products. Background of the Invention

[0004] Mineral fiber products (also called mineral wool products) generally contain mineral fibers (also called man-made vitreous fibers (MMVF)) such as glass fibers, ceramic fibers, basalt fibers, slag fibers and stone fibers (rock fibers), which are bonded together by a cured thermosetting polymer binder material. For use as thermal or acoustic insulation products, bonded mineral fiber mats are generally produced by converting a melt made of suitable raw materials into fibers in a conventional manner, for example by a spinning cup process or by a cascade rotor process. The fibers are blown into a forming chamber and, pneumatically and while still hot, sprayed with a binder solution and randomly deposited on a moving conveyor belt in the form of a mat or web. The fiber mat is then transferred to a curing oven, where heated air is blown through the mat to cure the binder and firmly bond the mineral fibers together.

[0005] In the past, the binder resin of choice was phenolic resin, which can be produced economically and can be augmented with urea before use as a binder. However, existing and proposed legislation aimed at reducing or eliminating formaldehyde emissions has led to the development of formaldehyde-free binders such as binder compositions based on polycarboxyl polymers and polyols or polyamines (for example, the binder compositions disclosed in EP-A-583086, EP-A-990727, EP-A-1741726, US-A-5,318,990 and US-A-2007 / 0173588).

[0006] Another group of non-phenolic binders are addition / elimination reaction products of aliphatic and / or aromatic anhydrides with alkanolamines, such as disclosed in WO 99 / 36368, WO 01 / 05725, WO 01 / 96460, WO 02 / 06178, WO 2004 / 007615 and WO 2006 / 061249. These binder compositions are water-soluble and exhibit excellent bonding properties in terms of cure speed and cure density. WO 2008 / 023032 discloses urea-modified binders of the type providing a mineral wool product with reduced hygroscopicity.

[0007] Since some of the starting materials used to produce these adhesives are relatively expensive chemicals, there is an ongoing need to provide formaldehyde-free adhesives that can be produced economically.

[0008] Another effect associated with previously known aqueous binder compositions from mineral fibers is that at least a large portion of the starting materials used to produce these binders originate from fossil fuels. Consumers have been preferring products that are produced completely or at least partially from renewable materials, and there is therefore a need to provide binders for mineral wool that are produced at least partially from renewable materials.

[0009] One of the main problems with using mineral fiber products as thermal or acoustic insulation for industrial equipment or pipelines is corrosion. Corrosion under insulation (CUI) is therefore the external corrosion of pipelines or equipment that occurs under the outer insulation layer due to water or moisture penetration. The corroded surface is mostly hidden by the insulation system and will not be observed until the insulation is removed for inspection or metal failure and / or leakage occurs, resulting in a health and safety incident. CUI occurs especially under the insulation layer used for steel structures that experience cyclic temperature changes, such as pipelines in the oil and gas industry.

[0010] Corrosion occurs in the presence of water and oxygen. If the equipment or piping under the insulation, such as steel structures, is kept dry, corrosion problems will not occur. However, keeping the insulation dry can be difficult. Water-soluble chlorides can cause or support certain types of corrosion. Prior art binder compositions for mineral fibers may include significant amounts of water-soluble chlorides. Therefore, the mineral fiber product itself can cause corrosion of the insulated components.

[0011] The risk of CUI is considered high for carbon steel in the temperature range of 50 to 175°C, and extremely high for carbon steel in cyclic temperature service between -20 and 320°C. The most common types of CUI are general corrosion and pitting corrosion of carbon steel (which can occur if wet insulation is in contact with carbon steel), and external stress corrosion tracking (ESCT) of austenitic stainless steels (which is a specific type of corrosion caused primarily by the action of water-soluble chlorides). SUMMARY OF THE INVENTION

[0013] It is therefore an object of the present invention to provide a mineral fibre product for insulation which has reduced corrosiveness to the objects to be insulated and which can be produced economically using renewable materials as starting products for the preparation of the aqueous binder composition used to produce said mineral fibre product.

[0014] Another object of the present invention is to provide the use of such a mineral fiber product.

[0015] According to a first aspect of the present invention there is provided a mineral fibre product comprising mineral fibres bonded by a cured binder composition, the uncured binder composition comprising one or more oxidised lignins, wherein the mineral fibre product has a water leachable chloride content of less than 10 mg / kg, measured in accordance with EN 13468:2001.

[0016] According to a second aspect of the present invention, there is provided the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition as a thermal and / or acoustic insulation material, in particular a non-corrosive thermal and / or acoustic insulation material, the uncured binder composition comprising one or more oxidized lignins, wherein the mineral fiber product optionally has a water-leachable chloride content of less than 10 mg / kg, determined according to EN 13468:2001.

[0017] According to a third aspect of the present invention, there is provided a method for producing a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the mineral fiber product optionally has a water leachable chloride content of less than 10 mg / kg, determined in accordance with EN 13468:2001,

[0018] The method comprises the following steps:

[0019] a) providing an uncured aqueous binder composition comprising one or more oxidized lignins and water,

[0020] b) contacting mineral fibers with said uncured aqueous binder composition, and

[0021] c) curing the binder composition in contact with the mineral fibers,

[0022] At least a portion of the water or all of the water contained in the uncured aqueous binder composition is added non-purified water, wherein the non-purified water is preferably selected from tap water, rainwater, production water or a combination thereof.

[0023] According to a fourth aspect of the present invention, there is provided a hollow article covered with a mineral fiber product as thermal and / or acoustic insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the mineral fiber product optionally has a water-leachable chloride content of less than 10 mg / kg, determined in accordance with EN 13468:2001.

[0024] The present inventors have found that when a binder composition based on oxidized lignin is used for mineral fiber products, the mineral fiber products can be used as low-corrosive or even non-corrosive thermal and / or acoustic insulation materials. Such binder compositions have surprisingly low water-leachable chloride content. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A portion of a possible lignin structure is shown.

[0027] Figure 2 Some lignin precursors and some shared interunit connections are shown.

[0028] Figure 3 Schematic preparation procedures of four groups of industrial lignins are shown.

[0029] Figure 4 The properties of four groups of industrial lignins are shown.

[0030] DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] The mineral fiber product of the present invention comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the mineral fiber product has a water-extractable chloride content of less than 10 mg / kg, determined according to EN 13468:2001, wherein the water-extractable chloride content is preferably less than 6 mg / kg, determined according to EN 13468:2001.

[0032] For the purposes of this application, the water-leachable chloride content of the mineral fiber product is measured in accordance with EN 13468:2001. Said standard EN 13468:2001 relates in particular to the determination of trace amounts of water-soluble chloride in thermal insulation products for building equipment and industrial installations. This standard specifies the equipment and procedure for the determination of trace amounts of water-soluble chloride in an aqueous extract of a product. For details, see this standard.

[0033] The water leachable chloride content is given in mg chloride per kg mineral fiber product. With reference to Table 1 in the EN standard, leaching conditions of 100°C and 0.5 h were used. Samples were prepared in accordance with section 7.2.1 of EN 13468. Analysis was performed in accordance with section 7.2.2.2 of EN 13468 (ion chromatography determination).

[0034] The inventors have found that the mineral fiber products of the present invention have surprisingly low water leachable chloride content. This is even true when non-purified water, such as tap water or process water, is used to prepare the uncured binder composition. As known to those skilled in the art, non-purified water can contain considerable amounts of chloride.

[0035] Without wishing to be bound by any particular theory, the inventors believe that the low water-leachy chloride content of the mineral fiber product of the present invention is based at least in part on the capture of chloride ions within the oxidized lignin-based binder matrix, even when tap water or process water is used to prepare the binder composition. This capture prevents the leaching of chloride, making it unavailable for corrosive activity.

[0036] Typically, the uncured cement composition is an aqueous cement composition. The water contained in the aqueous cement composition may be purified water, non-purified water, or a combination of purified water and added non-purified water.

[0037] In a preferred embodiment, the uncured binder composition is an aqueous binder composition, wherein at least a portion of the water or all of the water contained in the aqueous binder composition is non-purified water, and the other portion of the water (if any) is purified water. This is surprising, because purified water is usually used in common prior art binders to avoid considerable chloride content. Examples of purified water are permeate water, deionized water or distilled water, and are further mentioned below.

[0038] Purified water is generally water that has been mechanically filtered or treated to remove impurities and make it suitable for use. Distilled water is the most common form of purified water, but in recent years water has more often been purified by other methods, including capacitive deionization, reverse osmosis, carbon filtration, microfiltration, ultrafiltration, ultraviolet oxidation, or electrodeionization. Purified water preferably used in the uncured binder composition has a chloride content of less than 10 mg / L, preferably less than 5 mg / L.

[0039] Examples of suitable non-purified water are tap water, rainwater, process water or a combination thereof. The chloride content of tap water and rainwater is generally in the range of 10-200 mg / L. The chloride content of process water is generally in the range of 25-200 mg / L chloride. Preferably, the non-purified water used in the uncured cement composition may have a chloride content of at least 10 mg / L, for example, a chloride content in the range of 10-200 mg / L.

[0040] The proportion of non-purified water added may be in the range of 0-100 wt %, preferably 30-100 wt %, most preferably 50-100 wt %, based on the total weight of water contained in the uncured cement composition, the remainder being purified water, if any.

[0041] In the production plant, the binder composition is usually produced in concentrated form, i.e. the water content is kept at a low level. After delivery, the concentrated binder composition is diluted to a suitable viscosity by adding water at the mineral fiber production site. The diluted binder composition is contacted with the mineral fibers and cured to produce a mineral fiber product. One benefit of the present invention is that non-purified water such as tap water, rainwater or process water can be used to dilute the concentrated binder composition, but still obtain a product with a low water-leachy chloride content.

[0042] In a preferred embodiment, the adhesive of the present invention is formaldehyde-free.

[0043] For the purposes of this application, the term "formaldehyde-free" is defined as a term characterizing a mineral wool product wherein the formaldehyde released from the mineral wool product is less than 5 μg / m 2 / h, preferably less than 3 μg / m 2 / h of mineral wool product. Preferably, the test is carried out in accordance with ISO 16000 for testing aldehyde emission.

[0044] The uncured binder composition used for preparing the mineral fiber product of the present invention comprises one or more oxidized lignins as component (i).

[0045] Component (i)

[0046] Component (i) is in the form of one or more oxidized lignins.

[0047] Lignin, cellulose and hemicellulose are the three main organic compounds in plant cell walls. Lignin can be thought of as the glue that holds the cellulose fibers together. Lignin contains hydrophilic and hydrophobic groups. It is the second most abundant natural polymer in the world, after cellulose, and is estimated to account for as much as 20-30% of the total carbon contained in biomass, which exceeds 1 billion tons worldwide.

[0048] Figure 1 A portion of a possible lignin structure is shown.

[0049] There are at least four groups of industrial lignins available on the market. These four groups of industrial lignins are shown in Figure 3 A possible fifth group, biorefined lignin, is a bit different because it is not described by extraction method but by process source such as biorefining, so it can be similar or different to any of the other groups mentioned. Each group is different from the other and each is suitable for different applications. Lignin is a complex, heterogeneous material consisting of up to three different phenylpropane monomers, depending on the source. Softwood lignin consists mainly of coniferyl alcohol units (see Figure 2 ), and therefore they are more homogeneous than hardwood lignins, which have a higher syringol content (cf. Figure 2). The appearance and consistency of lignin varies greatly and depends largely on the process.

[0050] A summary of the properties of these industrial lignins is shown in Figure 4 middle.

[0051] Lignosulfonates from the sulfite pulping process remain the largest commercially available source of lignin, with a capacity of 1.4 million tonnes. But leaving that aside, the kraft process is currently the most used pulping process and is gradually replacing the sulfite process. It is estimated that 78 million tonnes of lignin are produced globally each year through the kraft pulping process, but most of this is burned for steam and energy. The current kraft recovery capacity is estimated at 160,000 tonnes, but sources indicate that current recovery is only about 75,000 tonnes. Kraft lignin is developed from black liquor, which is the waste liquor from the kraft or kraft process. Currently, 3 well-known processes are used to produce kraft lignin: LignoBoost, LignoForce and SLRP. The 3 processes are similar in that they involve the addition of CO2 to reduce the pH to 9-10, followed by acidification to further reduce the pH to about 2. The final step involves some combination of washing, leaching and filtering to remove ash and other contaminants. All three processes are at different stages of commercialization worldwide.

[0052] The kraft process introduces thiol groups, stilbene, while retaining some carbohydrates. Sodium sulfate is also present as an impurity because the lignin is precipitated from the liquor with sulfuric acid, but this could potentially be avoided by changing the way the lignin is isolated. The kraft process results in a large number of phenolic hydroxyl groups, and this lignin is soluble in water when these groups are ionized (at pH values ​​above about 10).

[0053] Commercial kraft lignin is usually purer than lignin sulfonate and has a molecular weight of 1000-3000 g / mol.

[0054] Alkali lignin is derived from the sodium hydroxide pulping process used primarily for wheat straw, bagasse, and flax. g In terms of alkali lignin, the performance is similar to that of kraft lignin. This process does not use sulfur and there is no covalently bound sulfur. The ash level is very low. Alkali lignin has low solubility in neutral and acidic media, but is completely soluble at pH 12 or higher.

[0055] The lignin sulfonate process introduces a large number of sulfonate groups, making the lignin soluble in water, but also soluble in acidic aqueous solutions. Lignin sulfonates have up to 8% sulfur in the form of sulfonates, while kraft lignin has 1-2% sulfur, which is mainly bonded to the lignin. The molecular weight of lignin sulfonates is 15,000-50,000 g / mol. Compared with other types of lignin, this lignin contains more residual carbohydrates and has a higher average molecular weight. The typical hydrophobic core of lignin together with the large number of ionized sulfonate groups makes this lignin attractive as a surfactant, and it is often used in dispersing cement, etc.

[0056] Another group of lignins that are becoming available is the lignin produced by the biorefining process, in which carbohydrates are separated from the lignin by a chemical or biochemical process to produce a carbohydrate-rich fraction. This remaining lignin is called biorefining lignin. Biorefineries focus on producing energy and alternatives to products obtained from fossil fuels and petrochemicals as well as lignin. Lignin from this process is generally considered a low-value product or even a waste that is primarily used for thermal combustion or used as a low-grade feed or otherwise disposed of.

[0057] The availability of organosolv lignin is still being considered on a pilot scale. This process involves extracting lignin using water and various organic solvents (most commonly ethanol) and some organic acids. One advantage of this process is that the lignin obtained is of higher purity, but the cost is much higher than other industrial lignins and it has solubility in organic solvents but not in water.

[0058] Previous attempts to use lignin as a base compound for binder compositions for mineral fibers have failed because it has proven difficult to find a suitable crosslinker that is able to achieve the desired mechanical properties of the cured mineral wool product while avoiding harmful and / or corrosive components. Currently, lignin is used to replace petroleum-derived chemicals, such as phenol in phenolic resins in binder applications or in asphalt. It is also used as a cement and concrete additive and as a dispersant in some applications.

[0059] The crosslinking of polymers will provide improved performances usually, such as mechanical, chemical and thermal tolerance etc. Lignin has particularly abundant phenolic hydroxyl groups and aliphatic hydroxyl groups, which can react and cause the crosslinked structure of lignin. Different lignins will also have other available functional groups, which can potentially be utilized. The existence of these other groups depends to a great extent on the mode (sulfonate radical in the mercaptan in the kraft lignin, the lignin sulfonate etc.) of lignin and cellulose and hemicellulose separation, depending on the source.

[0060] It has been found that by using oxidized lignin, binder compositions for mineral fibers can be prepared which allow the production of mineral fiber products having excellent properties.

[0061] In one embodiment, the component (i) is in the form of one or more oxidized kraft lignins.

[0062] In one embodiment, the component (i) is in the form of one or more oxidized alkali lignins.

[0063] In one embodiment, the component (i) is in the form of one or more ammonia oxidized lignins. For the purposes of the present invention, the term "ammonia oxidized lignin" is to be understood as lignin which has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia oxidized lignin" is abbreviated as AOL.

[0064] In an alternative embodiment, the ammonia is partially or completely replaced by an alkali metal hydroxide, in particular sodium hydroxide and / or potassium hydroxide.

[0065] A typical oxidizing agent used to prepare the oxidized lignin is hydrogen peroxide.

[0066] In one embodiment, the ammonia-oxidized lignin comprises one or more compounds selected from ammonia, amines, hydroxides or any salts thereof.

[0067] In one embodiment, the component (i) has a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i).

[0068] In the binder composition, preferably the aqueous binder composition, used according to the present invention, component (i), i.e. the one or more oxidized lignins, may be present in an amount of 25-95% by weight, such as 30-90% by weight, such as 35-85% by weight, based on the dry weight of the binder composition.

[0069] In one embodiment, the component (i) has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), such as more than 2.5 groups per macromolecule of component (i).

[0070] It is believed that the carboxylic acid group content of the oxidized lignin plays an important role in the surprising advantages of the binder composition for mineral fibers, preferably aqueous binder compositions, of the present invention. In particular, it is believed that the carboxylic acid groups of the oxidized lignin improve the crosslinking properties and thus allow the cured mineral fiber product to have better mechanical properties.

[0071] In a preferred embodiment, the uncured binder composition, preferably an aqueous binder composition, used to prepare the mineral fiber product of the present invention comprises:

[0072] - component (i) in the form of one or more oxidized lignins;

[0073] - component (ii) in the form of one or more crosslinking agents;

[0074] - Optionally, component (iii) in the form of one or more plasticizers.

[0075] Component (ii)

[0076] Optional component (ii) is in the form of one or more cross-linking agents.

[0077] In one embodiment, component (ii) comprises one or more crosslinking agents selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

[0078] β-Hydroxyalkylamide crosslinking agents are curing agents for acid-functional macromolecules. They provide hard, durable, corrosion-resistant and solvent-resistant crosslinked polymer networks. It is believed that β-hydroxyalkylamide crosslinking agents cure via an esterification reaction to form multiple ester bonds. The hydroxyl functionality of the β-hydroxyalkylamide crosslinking agents should average at least 2, preferably greater than 2, and more preferably 2-4, to obtain the best curing response.

[0079] The oxazoline group-containing crosslinking agent is a polymer containing one or more oxazoline groups in each molecule, and generally the oxazoline-containing crosslinking agent can be easily obtained by polymerizing oxazoline derivatives. Patent US6818699 B2 provides a disclosure on such a method.

[0080] In one embodiment, the component (ii) is an epoxidized oil based on fatty acid triglycerides.

[0081] It is noted that epoxidized oils based on fatty acid triglycerides are not considered hazardous and therefore the use of these compounds in the cement compositions of the present invention does not render these compositions unsafe to handle.

[0082] In one embodiment, the component (ii) is a molecule having three or more epoxy groups.

[0083] In one embodiment, the component (ii) is one or more flexible oligomers or polymers, such as low Tg acrylic polymers, such as low Tg vinyl polymers, such as low Tg polyethers, which contain reactive functional groups, such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0084] In one embodiment, component (ii) is selected from the group consisting of a crosslinking agent that participates in the curing reaction, such as hydroxyalkylamides, alkanolamines, and reaction products of alkanolamines and polycarboxylic acids. Reaction products of alkanolamines and polycarboxylic acids can be found in US Pat. No. 6,706,853 B1.

[0085] Without wishing to be bound by any particular theory, it is believed that the very advantageous properties of the binder composition, preferably the aqueous binder composition, used according to the present invention are due to the interaction of the oxidized lignin used as component (i) and the crosslinking agent mentioned above. It is believed that the presence of carboxylic acid groups in the oxidized lignin enables the oxidized lignin to crosslink very effectively.

[0086] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyfunctional organic amines, such as alkanolamines, diamines such as 1,6-hexanediamine, and triamines.

[0087] In one embodiment, the component (ii) is one or more crosslinking agents selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0088] In one embodiment, the component (ii) is one or more fatty amides.

[0089] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid.

[0090] In one embodiment, the component (ii) is one or more crosslinking agents selected from polyester polyols such as polycaprolactone.

[0091] In one embodiment, the component (ii) is one or more cross-linking agents selected from the group consisting of starch, modified starch, and CMC.

[0092] In one embodiment, the component (ii) is one or more crosslinking agents in the form of aliphatic multifunctional carbodiimides.

[0093] In one embodiment, the component (ii) is one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents.

[0094] Examples of such compounds are Picassian XL 701, 702, 725 (Stahl Polymers), e.g. XL-29SE (Angus Chemical Company), for example CX300 (DSM), for example Carbodilite V-02-L2 (Nisshinbo Chemical Inc.).

[0095] In one embodiment, component (ii) is Primid XL552, which has the following structure:

[0096]

[0097] Component (ii) may also be any mixture of the above mentioned compounds.

[0098] In one embodiment, the binder composition, preferably the aqueous binder composition used according to the present invention comprises component (ii) in an amount of 1 to 40 wt. %, such as 4 to 20 wt. %, such as 6 to 12 wt. %, based on the dry weight of component (i).

[0099] Component (iii)

[0100] Optional component (iii) is in the form of one or more plasticizers.

[0101] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of polyols, e.g. carbohydrates, hydrogenated sugars, e.g. sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids, e.g. adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0102] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of carbonates, e.g. ethylene carbonate, propylene carbonate, lactones, lactams, lactides, compounds having a structure similar to lignin, e.g. vanillin, acetosyringone, solvents used as coalescing agents, e.g. alcohol ethers, polyvinyl alcohol.

[0103] In one embodiment, component (iii) is in the form of one or more non-reactive plasticizers selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or other esters, solvents used as coalescing agents such as alcohol ethers, acrylic polymers, polyvinyl alcohol.

[0104] In one embodiment, component (iii) is one or more reactive plasticizers selected from the group consisting of carbonates, such as ethylene carbonate, propylene carbonate, lactones, lactams, lactides, di- or tricarboxylic acids, such as adipic acid, or lactic acid, and / or vanillic acid and / or ferulic acid, polyurethane dispersions, acrylic acid-based polymers with free carboxyl groups, compounds with a structure similar to lignin such as vanillin, acetosyringone.

[0105] In one embodiment, component (iii) is in the form of one or more plasticizers selected from the group consisting of fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol.

[0106] In one embodiment, component (iii) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers.

[0107] Another particularly surprising aspect of the present invention is that the use of plasticizers with a boiling point above 100°C, in particular with a boiling point of 140 to 250°C, greatly improves the mechanical properties of the mineral fiber products of the present invention, even though, given their boiling point, these plasticizers are likely to at least partially evaporate during the curing of the binder, preferably an aqueous binder, in contact with the mineral fibers.

[0108] In one embodiment component (iii) comprises one or more plasticizers having a boiling point in excess of 100°C, for example from 110 to 280°C, more preferably from 120 to 260°C, more preferably from 140 to 250°C.

[0109] It is believed that the effectiveness of these plasticizers in the binder composition, preferably aqueous binder composition, used according to the present invention is related to the effect of increasing the fluidity of the oxidized lignin during the curing process. It is believed that the increased fluidity of the lignin or oxidized lignin during the curing process promotes effective crosslinking.

[0110] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 150 to 50000 g / mol, in particular 150 to 4000 g / mol, more specifically 150 to 1000 g / mol, preferably 150 to 500 g / mol, more preferably 200 to 400 g / mol.

[0111] In one embodiment, component (iii) comprises one or more polyethylene glycols having an average molecular weight of 4000 to 25000 g / mol, in particular 4000 to 15000 g / mol, more particularly 8000 to 12000 g / mol.

[0112] In one embodiment, component (iii) is capable of forming covalent bonds with component (i) and / or component (ii) during the curing process. Such a component will not evaporate and remain as part of the composition, but will be effectively modified so as not to introduce unwanted side effects such as water absorption of the cured product. Non-limiting examples of such components are caprolactone and acrylic acid-based polymers with free carboxyl groups.

[0113] In one embodiment, component (iii) is selected from the group consisting of fatty alcohols, monohydric alcohols, such as amyl alcohol, stearyl alcohol.

[0114] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkoxides, such as ethoxides, for example butanol ethoxides such as butoxytriglycol.

[0115] In one embodiment, component (iii) is selected from one or more propylene glycols.

[0116] In one embodiment, component (iii) is selected from one or more glycol esters.

[0117] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates.

[0118] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols.

[0119] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of silanols, siloxanes.

[0120] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkylarylsulfonates, for example alkylsulfonates, phosphates such as tripolyphosphates; for example tributyl phosphate.

[0121] In one embodiment, component (iii) is selected from one or more hydroxy acids.

[0122] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of monomeric amides, such as acetamide, benzamide, fatty acid amides, such as tall oil amide.

[0123] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of quaternary ammonium compounds, such as trimethylglycine, distearyldimethylammonium chloride.

[0124] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of vegetable oils, such as castor oil, palm oil, linseed oil, tall oil, soybean oil.

[0125] In one embodiment, component (iii) is in the form of tall oil.

[0126] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils.

[0127] In one embodiment, component (iii) is selected from one or more fatty acid methyl esters.

[0128] In one embodiment, component (iii) is selected from one or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters.

[0129] It has surprisingly been found that the inclusion of a plasticizer in the binder composition, preferably an aqueous binder composition, used according to the invention greatly improves the mechanical properties of the mineral fiber product of the invention.

[0130] The term "plasticizer" refers to a substance added to a material to make the material softer, more flexible (by lowering the glass transition temperature, Tg), and easier to process.

[0131] Component (iii) may also be any mixture of the above mentioned compounds.

[0132] In one embodiment, component (iii) is present in an amount of 0.5 to 50 wt%, preferably 2.5 to 25 wt%, more preferably 3 to 15 wt%, based on the dry weight of component (i).

[0133] A binder composition for mineral fibers, preferably an aqueous binder composition, comprising components (i) and (iia)

[0134] In one embodiment, the present invention relates to a binder composition for mineral fibers, preferably an aqueous binder composition, comprising:

[0135] - component (i) in the form of one or more oxidized lignins;

[0136] - component (iia) in the form of one or more modifiers.

[0137] The inventors have found that the excellent binder properties can also be achieved by a two-component system comprising component (i) in the form of one or more oxidized lignins and component (iia) in the form of one or more modifiers, and optionally any other components mentioned above and below.

[0138] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of epoxidized oils based on fatty acid triglycerides.

[0139] In one embodiment, component (iia) is a modifier in the form of one or more compounds selected from the group consisting of molecules having three or more epoxy groups.

[0140] In one embodiment, component (iia) is a modifier in the form of one or more of the following: a flexible oligomer or polymer, such as a low Tg acrylic polymer, such as a low Tg vinyl polymer, such as a low Tg polyether, which contains reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups.

[0141] In one embodiment, component (iia) is one or more modifiers selected from the group consisting of polyethyleneimine, polyvinylamine, and fatty amine.

[0142] In one embodiment, component (iia) is one or more modifying agents selected from the group consisting of aliphatic multifunctional carbodiimides.

[0143] Component (iia) may also be any mixture of the above mentioned compounds.

[0144] Without wishing to be bound by any particular theory, the inventors believe that the excellent binder properties achieved by the binder composition for mineral fibers comprising components (i) and (iia) and optionally further components are at least partly due to the effect of the modifier acting as component (iia) functioning at least partly as a plasticizer and cross-linking agent.

[0145] In one embodiment, the cement composition, preferably an aqueous cement composition, comprises component (iia) in an amount of 1 to 40 wt%, such as 4 to 20 wt%, such as 6 to 12 wt%, based on the dry weight of component (i).

[0146] Additional components

[0147] In some embodiments, the cement composition, preferably an aqueous cement composition, used according to the present invention comprises additional components.

[0148] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, comprises a catalyst selected from: an inorganic acid, such as sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or any salt thereof, such as sodium hypophosphite, and / or ammonium salts such as ammonium salts of sulfuric acid, aminosulfonic acid, nitric acid, boric acid, hypophosphorous acid and / or phosphoric acid, and / or sodium polyphosphate (STTP), and / or sodium metaphosphate (STMP), and / or phosphorus oxychloride. The presence of such a catalyst can improve the curing properties of the binder composition used according to the present invention, preferably an aqueous binder composition.

[0149] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, comprises a catalyst selected from Lewis acids that can accept an electron pair from a donor compound forming a Lewis adduct, such as ZnCl2, Mg(ClO4)2, Sn[N(SO2-n-C8F 17 )2]4.

[0150] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a catalyst selected from metal chlorides, such as KCl, MgCl2, ZnCl2, FeCl3 and SnCl2.

[0151] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention comprises a catalyst selected from metal organic compounds, such as titanate-based catalysts and tin-based catalysts.

[0152] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a catalyst selected from chelating agents, such as transition metals, such as iron ions, chromium ions, manganese ions, copper ions.

[0153] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention further comprises a further component (iv) in the form of one or more silanes.

[0154] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention comprises a further component (iv) in the form of one or more coupling agents, such as organofunctional silanes.

[0155] In one embodiment, component (iv) is selected from the group consisting of organofunctional silanes, such as primary or secondary amino-functionalized silanes, epoxy-functionalized silanes such as polymeric or oligomeric epoxy-functionalized silanes, methacrylate-functionalized silanes, alkyl- and aryl-functionalized silanes, urea-functionalized silanes or vinyl-functionalized silanes.

[0156] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises component (v) in the form of one or more components selected from ammonia, amines or any salts thereof.

[0157] It has been found that when oxidized lignin which has not been oxidized in the presence of ammonia is used in component (i), it may be particularly useful to include ammonia, an amine or any of their salts as a further component.

[0158] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the invention further comprises a further component in the form of urea, in particular in an amount of 5 to 40% by weight, for example 10 to 30% by weight, 15 to 25% by weight, based on the dry weight of component (i).

[0159] In one embodiment, the binder composition used according to the present invention, preferably an aqueous binder composition, further comprises an additional component, which is in the form of one or more carbohydrates selected from the following group: sucrose, reducing sugars, especially dextrose, polysaccharides, and mixtures thereof, preferably dextrin and maltodextrin, more preferably glucose syrup, more preferably glucose syrup with a dextrose equivalent value DE of 30 to less than 100, for example, DE of 60 to less than 100, for example DE=60-99, for example DE=85-99, for example DE=95-99.

[0160] In one embodiment, the binder composition, preferably an aqueous binder composition, used according to the present invention further comprises an additional component in the form of one or more carbohydrates selected from sucrose and reducing sugars in an amount of 5 to 50% by weight, such as 5 to less than 50% by weight, such as 10-40% by weight, such as 15-30% by weight, based on the dry weight of component (i).

[0161] In the context of the present invention, a binder composition having a sugar content of 50% by weight or more based on the total dry weight of the binder components is considered to be a sugar-based binder. In the context of the present invention, a binder composition having a sugar content of less than 50% by weight based on the total dry weight of the binder components is considered to be a non-sugar-based binder.

[0162] In one embodiment, the adhesive composition used according to the present invention, preferably an aqueous adhesive composition, further comprises an additional component in the form of one or more surfactants in the form of nonionic and / or ionic emulsifiers, such as polyoxyethylene (4) lauryl ether, soy lecithin, sodium lauryl sulfate.

[0163] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0164] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0165] - component (ii) in the form of one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinkers selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0166] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more particularly 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40 wt.-%, for example 4 to 20 wt.-%, 6 to 12 wt.-% of component (ii), based on the dry weight of component (i), and component (iii) is present in an amount of 0.5 to 50 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).

[0167] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0168] - component (i) in the form of one or more ammonia-oxidized lignins having a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (i);

[0169] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0170] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0171] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), such as more than 2.5 groups per macromolecule of component (i);

[0172] - component (ii) in the form of one or more crosslinkers selected from β-hydroxyalkylamide crosslinkers and / or oxazoline crosslinkers and / or one or more crosslinkers selected from the group consisting of polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines;

[0173] - component (iii) in the form of one or more polyethylene glycols having an average molecular weight of 150 to 50,000 g / mol, in particular 150 to 4,000 g / mol, more particularly 150 to 1,000 g / mol, preferably 150 to 500 g / mol, more particularly 150 to 300 g / mol, or having an average molecular weight of 4,000 to 25,000 g / mol, in particular 4,000 to 15,000 g / mol, more particularly 8,000 to 12,000 g / mol; wherein preferably the binder composition, preferably an aqueous binder composition, comprises 1 to 40 wt.-%, for example 4 to 20 wt.-%, 6 to 12 wt.-% of component (ii), based on the dry weight of component (i), and component (iii) is present in an amount of 0.5 to 50 wt.-%, preferably 2.5 to 25 wt.-%, more preferably 3 to 15 wt.-%, based on the dry weight of component (i).

[0174] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention comprises:

[0175] - component (i) in the form of one or more ammonia-oxidized lignins having an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (i), such as more than 2 groups per macromolecule of component (i), such as more than 2.5 groups per macromolecule of component (i);

[0176] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides.

[0177] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0178] - component (i) in the form of one or more oxidized lignins;

[0179] - component (ii) in the form of one or more crosslinking agents;

[0180] - component (iii) in the form of one or more plasticizers;

[0181] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0182] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0183] - optional components in the form of urea;

[0184] - optional components in the form of more reactive or non-reactive silicones;

[0185] - optionally a hydrocarbon oil;

[0186] - optionally one or more surfactants;

[0187] -water.

[0188] In one embodiment, the adhesive composition, preferably an aqueous adhesive composition, used according to the present invention consists essentially of the following components:

[0189] - component (i) in the form of one or more oxidized lignins;

[0190] - component (iia) in the form of one or more modifiers chosen from epoxidized oils based on fatty acid triglycerides;

[0191] - component (iv) in the form of one or more coupling agents such as organofunctional silanes;

[0192] - optional components in the form of one or more compounds selected from ammonia, amines or any salts thereof;

[0193] - optional components in the form of urea;

[0194] - optional components in the form of more reactive or non-reactive silicones;

[0195] - optionally a hydrocarbon oil;

[0196] - optionally one or more surfactants;

[0197] -water.

[0198] Method for producing mineral fiber products

[0199] The mineral fiber product of the present invention can be prepared by conventional methods for producing mineral fiber products by binding mineral fibers with a binder composition. Therefore, the mineral fiber product of the present invention is preferably prepared by a method comprising the steps of contacting mineral fibers with an uncured and preferably aqueous binder composition comprising one or more oxidized lignins.

[0200] In particular, the present invention also relates to a method for producing a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the mineral fiber product optionally has a water leachable chloride content of less than 10 mg / kg determined according to EN 13468:2001, the method comprising the following steps:

[0201] a) providing an uncured aqueous binder composition comprising one or more oxidized lignins and water,

[0202] b) contacting mineral fibers with said uncured aqueous binder composition, and

[0203] c) curing the binder composition in contact with the mineral fibers,

[0204] At least a portion of the water or all of the water contained in the uncured aqueous binder composition is added non-purified water, wherein the non-purified water is preferably selected from tap water, rainwater, production water or a combination thereof.

[0205] In a preferred embodiment of the method of the present invention, the proportion of non-purified water added is in the range of 30-100 wt %, more preferably 50-100 wt %, based on the total weight of water contained in the uncured cement composition.

[0206] In another preferred embodiment of the method of the present invention, the water content of the uncured aqueous binder composition is in the range of 40-90 wt %, preferably 60-85 wt %, based on the total weight of the uncured aqueous binder composition.

[0207] The mineral fiber product obtained in the process of the invention may have all the features described herein for the mineral fiber product of the invention, reference is therefore made to said description.

[0208] In a preferred embodiment, the uncured aqueous binder composition comprises:

[0209] - component (i) in the form of one or more oxidized lignins;

[0210] - component (ii) in the form of one or more crosslinking agents;

[0211] - optional component (iii) in the form of one or more plasticizers.

[0212] As mentioned above, in a preferred embodiment, the uncured cement composition used is prepared by diluting a concentrated form of the cement composition by adding non-purified water.

[0213] Curing

[0214] The uncured binder composition in a mineral fiber product precursor, such as a web in which the mineral fibers are in contact with the binder composition, is cured by chemical and / or physical reaction of the binder components.

[0215] In one embodiment, the curing is performed in a curing unit.

[0216] In one embodiment, the curing is carried out at a temperature of 100-300°C, such as 170-270°C, such as 180-250°C, such as 190-230°C.

[0217] In one embodiment the curing is carried out in a conventional curing oven used for mineral wool production, operating at a temperature of 150 to 300°C, such as 170 to 270°C, such as 180 to 250°C, such as 190 to 230°C.

[0218] In one embodiment, the curing is performed for a period of 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes.

[0219] In a typical embodiment, curing is performed at a temperature of 150 to 250° C. for a time of 30 seconds to 20 minutes.

[0220] The curing process may begin immediately after the binder is applied to the fibers. Curing is defined as a process in which the binder composition undergoes a physical and / or chemical reaction (curing in the case of a chemical reaction generally increases the molecular weight of the compounds in the binder composition) and thereby increases the viscosity of the binder composition, generally until the binder composition reaches a solid state.

[0221] In one embodiment, the curing process comprises drying by pressure.Pressure may be applied by blowing air or gas through / over the mixture of mineral fibres and binder.

[0222] Mineral fiber products of the invention

[0223] The present invention relates to a mineral fibre product comprising mineral fibres in contact with a cured binder composition as described above, ie in contact with a cured binder resulting from the curing of a binder composition, preferably an aqueous binder composition, as described above.

[0224] The mineral fibers used can be any one of man-made vitreous fibers (MMVF), glass fibers, ceramic fibers, basalt fibers, slag fibers, rock fibers, stone fibers, etc. These fibers can be present in the form of velvet products such as asbestos products. In a preferred embodiment, the mineral fibers are stone fibers or asbestos, respectively.

[0225] Fiber / melt composition

[0226] Man-made vitreous fibers (MMVF) may have any suitable oxide composition. The fibers may be glass fibers, ceramic fibers, basalt fibers, slag fibers, or rock or stone fibers. The fibers are preferably of the type commonly referred to as rock fibers, stone fibers or slag fibers, most preferably stone fibers.

[0227] Stone fibers usually contain the following oxides, expressed in weight percentage:

[0228] SiO2:30-51

[0229] CaO: 8-30

[0230] MgO: 2-25

[0231] FeO (including Fe2O3): 2-15

[0232] Na2O+K2O: not more than 10

[0233] CaO+MgO: 10-30

[0234] In some preferred embodiments, the MMVF has the following elemental levels, calculated as oxides and expressed in weight %:

[0235] SiO2: at least 30, 32, 35 or 37; not more than 51, 48, 45 or 43

[0236] Al2O3: at least 12, 16 or 17; not more than 30, 27 or 25

[0237] CaO: at least 8 or 10; not more than 30, 25 or 20

[0238] MgO: at least 2 or 5; no more than 25, 20 or 15

[0239] FeO (including Fe2O3): at least 4 or 5; not more than 15, 12 or 10

[0240] FeO+MgO: at least 10, 12 or 15; not more than 30, 25 or 20

[0241] Na2O+K2O: 0 or at least 1; not more than 10

[0242] CaO+MgO: at least 10 or 15; not more than 30 or 25

[0243] TiO2: 0 or at least 1; not more than 6, 4 or 2

[0244] TiO2+FeO: at least 4 or 6; not more than 18 or 12

[0245] B2O3: 0 or at least 1; not more than 5 or 3

[0246] P2O5: 0 or at least 1; not more than 8 or 5

[0247] Others: 0 or at least 1; no more than 8 or 5

[0248] The MMVF prepared by the method of the present invention preferably has the following composition (expressed in wt%):

[0249] SiO2: 35-50

[0250] Al2O3: 12-30

[0251] TiO2: up to 2

[0252] Fe2O3: 3-12

[0253] CaO: 5-30

[0254] MgO: up to 15

[0255] Na2O: 0-15

[0256] K2O: 0-15

[0257] P2O5: up to 3

[0258] MnO: up to 3

[0259] B2O3: up to 3

[0260] Another preferred composition of MMVF is as follows (expressed in wt%):

[0261] SiO2: 39-55%, preferably 39-52%

[0262] Al2O3: 16-27%, preferably 16-26%

[0263] CaO: 6-20%, preferably 8-18%

[0264] MgO: 1-5%, preferably 1-4.9%

[0265] Na2O: 0-15%, preferably 2-12%

[0266] K2O: 0-15%, preferably 2-12%

[0267] R2O (Na2O + K2O): 10-14.7%, preferably 10-13.5%

[0268] P2O5: 0-3%, preferably 0-2%

[0269] Fe2O3 (total iron): 3-15%, preferably 3.2-8%

[0270] B2O3: 0-2%, preferably 0-1%

[0271] TiO2: 0-2%, preferably 0.4-1%

[0272] Others: 0-2.0%

[0273] Glass fibers usually contain the following oxides (expressed in wt%):

[0274] SiO2: 50-70

[0275] Al2O3: 10-30

[0276] CaO: not more than 27

[0277] MgO: not more than 12

[0278] Glass fibers may also contain the following oxides (expressed in wt%):

[0279] Na2O+K2O: 8-18, especially Na2O+K2O is greater than CaO+MgO

[0280] B2O3: 3-12

[0281] Certain glass fiber compositions may contain less than 2% Al2O3.

[0282] In a preferred embodiment, the mineral fiber is a hydrophobic treated mineral fiber, preferably hydrophobic treated asbestos. Hydrophobic treatment is a common treatment and can be performed, for example, by adding at least one hydrophobic agent such as mineral oil, siloxane or silicone resin during the mineral fiber manufacturing process to form a hydrophobic film around the fiber. Therefore, the hydrophobic treated mineral fiber preferably has a hydrophobic film on its surface.

[0283] Suitable fiber formation methods and subsequent production steps for making mineral fiber products are those conventional in the art. Typically, the binder is sprayed onto the airborne mineral fibers immediately after the mineral melt is fibrillated. The amount of uncured and preferably aqueous binder composition applied is typically 0.1 to 18% by weight, preferably 0.2 to 8% by weight, of the bonded mineral fiber product, calculated on a dry weight basis.

[0284] The sprayed mineral fiber web is usually cured in a curing oven using a hot air stream which can be introduced into the mineral fiber web from below or above or from alternating directions in different zones along the length of the curing oven.

[0285] Typically, the curing oven is operated at a temperature of about 150° C. to about 300° C., such as 170 to 270° C., such as 180 to 250° C., such as 190 to 230° C. Typically, the curing oven residence time is 30 seconds to 20 minutes, such as 1 to 15 minutes, such as 2 to 10 minutes, depending on, for example, product density.

[0286] In a typical embodiment, the mineral fiber product of the invention is cured at a temperature of from 150°C to 250°C for a period of from 30 seconds to 20 minutes.

[0287] If desired, the mineral fiber web may be subjected to a shaping process prior to curing. The bonded mineral fiber product emerging from the curing oven may be cut into a desired form, for example in the form of a batt.

[0288] In a preferred embodiment the mineral fibre product of the invention is a thermal and / or acoustic insulation product, preferably a thermal insulation product.

[0289] The mineral fibre product may be in the form of preformed tube sections, mats or slabs.

[0290] The preformed pipe section may be in the form of a hollow cylinder or a portion thereof. The dimensions of the preformed pipe section should be suitable for the pipe to be insulated. The wire mat is a lightly bonded mineral fiber mat stitched with galvanized wire to a galvanized steel wire mesh.

[0291] In a preferred embodiment, the mineral fibre product of the invention is a thermal and / or acoustic insulation material for pipes, tanks, boilers, containers or columns, preferably pipes.

[0292] In a preferred embodiment, the mineral fiber product of the invention has a thickness in the range of 20 mm to 500 mm or 25 mm to 300 mm, preferably 30 mm to 300 mm, for example 50 mm to 150 mm, wherein typically the mineral fiber product is in the form of a sheet.

[0293] The mineral fiber products of the present invention generally have a density of 6-250 kg / m 3 , preferably 20-200kg / m 3 The mineral fiber product typically has a loss on ignition (LOI) in the range of 0.3-18.0%, preferably 0.5-8.0%.

[0294] Use of the mineral fiber product of the invention

[0295] One use of the mineral fiber product according to the invention is its use as a thermal and / or acoustic insulation material, in particular as a non-corrosive thermal and / or acoustic insulation material.

[0296] The term "non-corrosive" herein means that the thermal and / or acoustic insulation material does not cause increased corrosion. "Non-corrosive" does not mean that corrosion will not occur, but rather that the corrosion is caused by factors other than the thermal and / or acoustic insulation material itself.

[0297] The invention therefore also relates to the use of a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, as a thermal and / or acoustic insulation material, in particular a non-corrosive thermal and / or acoustic insulation material. It is generally preferred that the mineral fiber product has a water-leachable chloride content of less than 10 mg / kg, determined according to EN 13468:2001.

[0298] In a preferred embodiment of the use according to the invention, the mineral fiber product is used as thermal and / or acoustic insulation material, in particular non-corrosive thermal and / or acoustic insulation material, for an object selected from pipes, tanks, boilers, containers or columns, preferably pipes. The pipe or duct system also comprises an exhaust pipe, respectively.

[0299] In a preferred embodiment of the use according to the invention, the mineral fiber product is used as thermal and / or acoustic insulation for objects made of metal, wherein the objects are generally hollow articles, examples of which are given above. The metal is preferably selected from copper or steel, with steel being preferred. The steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel. In a particularly preferred embodiment, the object is a steel pipe.

[0300] In a preferred embodiment of the use according to the invention, the use is preferably at a temperature in the range of -20°C to 320°C, more preferably 0°C to 200°C, for example 50°C to 175°C. The temperature refers to the temperature of the object insulated by the mineral fiber product, i.e. the operating temperature. The operation can be continuous or cyclic in terms of temperature. In the case of cyclic operation, the above temperature range generally refers to the maximum temperature of the operation.

[0301] Articles covered by the mineral fibre product as thermal and / or acoustic insulation, in particular non-corrosive thermal and / or acoustic insulation, typically comprise a medium which may be selected from a gas, a vapour or a fluid.

[0302] The mineral fiber product for the use according to the invention may have all the features described above for the mineral fiber product according to the invention, to which description reference is therefore made.

[0303] Hollow article having the heat-insulating and / or sound-insulating material of the present invention

[0304] The invention also relates to a hollow article covered with a mineral fiber product as thermal and / or acoustic insulation material, wherein the mineral fiber product comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins.

[0305] Preferably, the mineral fibre product has a water leachable chloride content of less than 10 mg / kg, measured according to EN 13468:2001.

[0306] In a preferred embodiment, the hollow object is selected from a tube, a tank, a boiler, a container or a column, preferably a tube. The tube or the piping system further comprises an exhaust pipe, respectively.

[0307] In a preferred embodiment, the hollow article is made of metal. The metal is preferably selected from copper or steel, wherein steel is preferred. The steel is preferably carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low alloy steel. In a particularly preferred embodiment, the article is a steel pipe.

[0308] The mineral fibre product covering the hollow objects of the invention may have all the features described above for the mineral fibre product of the invention, to which description reference is therefore made.

[0309] Oxidized lignin useful as a component of a binder composition for mineral fibers, preferably an aqueous binder composition, according to the invention, and a method for preparing such an oxidized lignin

[0310] In the following, we describe oxidized lignins that can be used as components of binder compositions and their preparation.

[0311] Method for preparing oxidized lignin I

[0312] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0313] The following components were contacted:

[0314] - component (a) comprising one or more lignins;

[0315] - component (b) comprising ammonia, one or more amine components and / or any salts thereof;

[0316] - component (c) comprising one or more oxidizing agents.

[0317] Component (a)

[0318] Component (a) comprises one or more lignins.

[0319] In one embodiment of the process of the present invention, component (a) comprises one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

[0320] In one embodiment, component (a) comprises one or more kraft lignins.

[0321] Component (b)

[0322] In one embodiment of the present invention, component (b) comprises ammonia, one or more amino components and / or any of their salts. Without wishing to be bound by any particular theory, the inventors believe that replacing the alkali metal hydroxides used in previously known lignin oxidation processes with ammonia, one or more amino components and / or any of their salts plays an important role in improving the properties of the oxidized lignin prepared according to the process of the present invention.

[0323] The present inventors have surprisingly found that lignin oxidized by an oxidizing agent in the presence of ammonia or an amine contains a significant amount of nitrogen as part of the oxidized lignin structure. Without wishing to be bound by any particular theory, the present inventors believe that the improved fire resistance of the oxidized lignin when used in a product in which the oxidized lignin prepared by the process of the present invention is included in a binder composition is at least partially due to the nitrogen content of the structure of the oxidized lignin.

[0324] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0325] Without wishing to be bound by any particular theory, the inventors believe that the improved stability properties of the derivatized lignin prepared according to the present invention are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused. In contrast, it has proven difficult to remove residual amounts of alkali metal hydroxides used in previously known oxidation processes.

[0326] However, it may be advantageous in the process according to the invention for component (b) to comprise, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0327] In embodiments where component (b) comprises an alkali metal and / or alkaline earth metal hydroxide such as sodium hydroxide and / or potassium hydroxide as a component other than ammonia, one or more amino components and / or any salts thereof, the amount of the alkali metal and / or alkaline earth metal hydroxide is generally small, for example 5 to 70 parts by weight, such as 10 to 20 parts by weight, of the alkali metal and / or alkaline earth metal hydroxide, based on ammonia.

[0328] Component (c)

[0329] In the process of the present invention, component (c) comprises one or more oxidizing agents.

[0330] In one embodiment, component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0331] In the initial steps of the oxidation, the active free radical from the oxidant will usually abstract a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Due to the potential of lignin to stabilize free radicals through intermediation, multiple pathways are opened to continue (but also terminate) the reaction and obtain various intermediates and final products. Due to this complexity (and the conditions chosen), the average molecular weight can both increase and decrease, and in the inventors' experiments the inventors have generally seen a modest increase in average molecular weight of about 30%.

[0332] In one embodiment, component (c) comprises hydrogen peroxide.

[0333] Hydrogen peroxide is probably the most commonly used oxidant due to its low price, high efficiency and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0334]

[0335]

[0336] The present inventors have found that the derivatized lignin prepared using the process of the present invention contains an increased amount of carboxylic acid groups as a result of the oxidation process. Without wishing to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process of the present invention plays an important role in the desired reactive properties of the derivatized lignin prepared by the process of the present invention.

[0337] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can increase solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0338] Additional components

[0339] In one embodiment, the process of the invention comprises further components, in particular component (d) in the form of an oxidation catalyst, for example one or more transition metal catalysts, for example iron sulfate, for example catalysts containing manganese, palladium, selenium, tungsten.

[0340] Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignin prepared by the method of the present invention.

[0341] The mass ratio of the components

[0342] One skilled in the art will use the components (a), (b) and (c) in relative amounts to achieve the desired degree of lignin oxidation.

[0343] In one embodiment,

[0344] - component (a) comprises one or more lignins,

[0345] - component (b) comprises ammonia,

[0346] - component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide,

[0347] wherein the mass ratio of lignin, ammonia and hydrogen peroxide is such that the amount of ammonia is 0.01 to 0.5 parts by weight, such as 0.1 to 0.3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia, based on the dry weight of lignin, and wherein the amount of hydrogen peroxide is 0.025 to 1.0 parts by weight, such as 0.05 to 0.2 parts by weight, such as 0.075 to 0.125 parts by weight of hydrogen peroxide, based on the dry weight of lignin.

[0348] method

[0349] There is more than one possibility for contacting the components (a), (b) and (c) to achieve the desired oxidation reaction.

[0350] In one embodiment, the method comprises the following steps:

[0351] - a step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, the aqueous solution having a lignin content of 1 to 50 wt %, such as 5 to 25 wt %, such as 15 to 22 wt %, such as 18 to 20 wt %, based on the total weight of the aqueous solution;

[0352] - a pH adjustment step by adding component (b) comprising an aqueous solution of ammonia, one or more amine components and / or any of their salts;

[0353] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0354] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0355] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value in the range of 10.5 to 12.

[0356] In one embodiment the pH adjustment step is performed such that the temperature is allowed to rise to > 25°C and then controlled in the range of 25 to 50°C, such as 30 to 45°C, such as 35 to 40°C.

[0357] In one embodiment, during the oxidation step, the temperature is allowed to rise > 35°C and then controlled in the range of 35 to 150°C, such as 40 to 90°C, such as 45 to 80°C.

[0358] In one embodiment, the oxidation step is performed for a period of from 1 second to 48 hours, such as from 10 seconds to 36 hours, such as from 1 minute to 24 hours, such as from 2 to 5 hours.

[0359] Method for preparing oxidized lignin II

[0360] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0361] The following components were contacted:

[0362] - a component (a) comprising one or more lignins,

[0363] a component (b) comprising ammonia and / or one or more amine components and / or any of their salts and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide,

[0364] - component (c) comprising one or more oxidizing agents,

[0365] - component (d) in the form of one or more plasticizers.

[0366] Component (a)

[0367] Component (a) comprises one or more lignins.

[0368] In one embodiment of the process of the present invention, component (a) comprises one or more kraft lignins, one or more alkali lignins, one or more lignosulfonate lignins, one or more organosolv lignins, one or more lignins from a biorefining process of a lignocellulosic raw material, or any mixture thereof.

[0369] In one embodiment, component (a) comprises one or more kraft lignins.

[0370] Component (b)

[0371] In one embodiment of the present invention, component (b) comprises ammonia, one or more amino components and / or any salts thereof, and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide.

[0372] "Ammonia oxidized lignin" is to be understood as lignin which has been oxidized by an oxidizing agent in the presence of ammonia. The term "ammonia oxidized lignin" is abbreviated as AOL.

[0373] In one embodiment, component (b) comprises ammonia and / or any salts thereof.

[0374] Without wishing to be bound by any particular theory, the inventors believe that the improved stability properties of the derivatized lignin prepared according to the present invention using ammonia and / or any salts thereof as component (b) are at least partly due to the fact that ammonia is a volatile compound and therefore evaporates from the final product or can be easily removed and reused.

[0375] However, it may be advantageous in this embodiment of the process of the invention that component (b) comprises, in addition to ammonia, one or more amino components and / or any salts thereof, relatively small amounts of alkali metal and / or alkaline earth metal hydroxides, such as sodium hydroxide and / or potassium hydroxide.

[0376] In embodiments where component (b) comprises an alkali metal and / or alkaline earth metal hydroxide such as sodium hydroxide and / or potassium hydroxide as a component other than ammonia, one or more amino components and / or any salts thereof, the amount of the alkali metal and / or alkaline earth metal hydroxide is generally small, for example 5 to 70 parts by weight, such as 10 to 20 parts by weight, of the alkali metal and / or alkaline earth metal hydroxide, based on ammonia.

[0377] Component (c)

[0378] In the process of the present invention, component (c) comprises one or more oxidizing agents.

[0379] In one embodiment, component (c) comprises one or more oxidizing agents in the form of hydrogen peroxide, an organic or inorganic peroxide, molecular oxygen, ozone, air, a halogen-containing oxidizing agent, or any mixture thereof.

[0380] In the initial steps of the oxidation, the active free radical from the oxidant will usually abstract a proton from the phenolic group, since this bond has the lowest dissociation energy in lignin. Due to the potential of lignin to stabilize free radicals through intermediation, multiple pathways are opened to continue (but also terminate) the reaction and obtain various intermediates and final products. Due to this complexity (and the conditions chosen), the average molecular weight can both increase and decrease, and in the inventors' experiments the inventors have generally seen a modest increase in average molecular weight of about 30%.

[0381] In one embodiment, component (c) comprises hydrogen peroxide.

[0382] Hydrogen peroxide is probably the most commonly used oxidant due to its low price, high efficiency and relatively low environmental impact. When hydrogen peroxide is used in the absence of a catalyst, alkaline conditions and temperature are important due to the following reactions that lead to the formation of free radicals:

[0383]

[0384] The present inventors have found that the derivatized lignin prepared using the process of the present invention contains an increased amount of carboxylic acid groups as a result of the oxidation process. Without wishing to be bound by any particular theory, the present inventors believe that the carboxylic acid group content of the oxidized lignin prepared in the process of the present invention plays an important role in the desired reactive properties of the derivatized lignin prepared by the process of the present invention.

[0385] Another advantage of the oxidation process is that the oxidized lignin is more hydrophilic. Higher hydrophilicity can increase solubility in water and promote adhesion to polar substrates such as mineral fibers.

[0386] Component (d)

[0387] Component (d) comprises one or more plasticizers.

[0388] In one embodiment of the present invention, component (d) comprises one or more plasticizers in the form of polyols, for example carbohydrates, hydrogenated sugars, for example sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyethylene glycol ethers, polyethers, phthalates and / or acids, for example adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0389] The present inventors have found that the inclusion of component (d) in the form of one or more plasticizers provides a reduction in the viscosity of the reaction mixture which makes the process for producing oxidised lignin very efficient.

[0390] In one embodiment of the present invention, component (d) comprises one or more plasticizers in the form of polyols, such as carbohydrates, hydrogenated sugars, such as sorbitol, erythritol, glycerol, monoethylene glycol, polyethylene glycol, polyvinyl alcohol, acrylic acid-based polymers with free carboxyl groups and / or polyurethane dispersions with free carboxyl groups, polyamides, amides such as urea / urea, or any mixtures thereof.

[0391] In one embodiment of the present invention, component (d) comprises one or more plasticizers selected from the group consisting of polyethylene glycol, polyvinyl alcohol, urea or any mixture thereof.

[0392] Additional components

[0393] In one embodiment, the process of the invention comprises further components, in particular component (v) in the form of an oxidation catalyst, for example one or more transition metal catalysts, for example iron sulfate, for example catalysts containing manganese, palladium, selenium, tungsten.

[0394] Such oxidation catalysts can increase the reaction rate, thereby improving the properties of the oxidized lignin produced by the method.

[0395] The mass ratio of the components

[0396] One skilled in the art will use the components (a), (b), (c) and (d) in relative amounts to achieve the desired degree of lignin oxidation.

[0397] In one embodiment, the method of the present invention is performed such that the method comprises

[0398] - a component (a) comprising one or more lignins,

[0399] - a component (b) comprising ammonia,

[0400] - component (c) comprising one or more oxidizing agents in the form of hydrogen peroxide,

[0401] - component (d) comprising one or more plasticizers selected from polyethylene glycols,

[0402] wherein the mass ratio of lignin, ammonia, hydrogen peroxide and polyethylene glycol is such that the amount of ammonia is 0.01 to 0.5 parts by weight, such as 0.1 to 0.3 parts by weight, such as 0.15 to 0.25 parts by weight of ammonia (25% by weight aqueous solution), based on the dry weight of lignin, and wherein the amount of hydrogen peroxide (30% by weight aqueous solution) is 0.025 to 1.0 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.15 to 0.30 parts by weight of hydrogen peroxide, based on the dry weight of lignin, and wherein the amount of polyethylene glycol is 0.03 to 0.60 parts by weight, such as 0.07 to 0.50 parts by weight, such as 0.10 to 0.40 parts by weight of polyethylene glycol, based on the dry weight of lignin.

[0403] For the purposes of the present invention, "dry weight of lignin" is preferably defined as the weight of lignin in the provided form.

[0404] method

[0405] There is more than one possibility for contacting the components (a), (b), (c) and (d) to achieve the desired oxidation reaction.

[0406] In one embodiment, the method comprises the following steps:

[0407] - a step of providing component (a) in the form of an aqueous solution and / or dispersion of one or more lignins, the aqueous solution having a lignin content of 5 to 90% by weight, such as 10 to 85% by weight, such as 15 to 70% by weight, based on the total weight of the aqueous solution;

[0408] - a pH adjustment step by adding component (b);

[0409] - a step of adding component (d);

[0410] - an oxidation step by adding component (c) comprising an oxidizing agent.

[0411] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value of ≥ 9, such as ≥ 10, such as ≥ 10.5.

[0412] In one embodiment, the pH adjustment step is performed such that the resulting aqueous solution and / or dispersion has a pH value in the range of 9.5 to 12.

[0413] In one embodiment the pH adjustment step is performed such that the temperature is allowed to rise to > 25°C and then controlled in the range of 25 to 50°C, such as 30 to 45°C, such as 35 to 40°C.

[0414] In one embodiment, during the oxidation step, the temperature is allowed to rise to > 35°C and then controlled in the range of 35 to 150°C, such as 40 to 90°C, such as 45 to 80°C.

[0415] In one embodiment, the oxidation step is performed for a period of from 1 second to 24 hours, such as from 1 minute to 12 hours, such as from 10 minutes to 8 hours, such as from 5 minutes to 1 hour.

[0416] The inventors have found that the process of the invention allows the production of a reaction mixture with a high dry matter content and that therefore a high throughput is possible in the process of the invention, which allows the reaction product in the form of oxidized lignin to be used as a component for the industrial scale production of products such as mineral fibre products.

[0417] In one embodiment, the process of the invention is carried out such that the dry matter content of the reaction mixture is from 20 to 80 wt%, such as from 40 to 70 wt%.

[0418] In one embodiment, the method of the present invention is carried out so that the viscosity of the oxidized lignin has a value of 100 cP to 100,000 cP, such as a value of 500 cP to 50,000 cP, such as a value of 1,000 cP to 25,000 cP.

[0419] For the purposes of the present invention, viscosity is dynamic viscosity and is defined as the resistance of a liquid / paste to a change in shape or movement of adjacent parts relative to each other. Viscosity is measured in centipoise (cP), which is equivalent to 1 mPa·s (milliPascal seconds). Viscosity is measured using a viscometer at 20°C. For the purposes of the present invention, dynamic viscosity can be measured at 20°C by a cone-plate Wells Brookfield viscometer.

[0420] In one embodiment, the method of the present invention is implemented such that it comprises a rotor-stator apparatus.

[0421] In one embodiment, the process of the present invention is implemented such that the process is performed as a continuous or semi-continuous process.

[0422] Device for carrying out the method

[0423] The invention also relates to an apparatus for carrying out the method described above.

[0424] In one embodiment, the apparatus for carrying out the method comprises:

[0425] - Rotor-stator equipment,

[0426] - a premixing device for components (a), (b), (d),

[0427] - one or more inlets for water, components (a), (b), (c) and (d),

[0428] - One or more outlets for oxidized lignin.

[0429] In one embodiment, the apparatus is constructed in such a way that an inlet for the premix of components (a), (b) and (d) is located at the rotor-stator device and the apparatus further comprises a chamber having an inlet for component (c) and an outlet for the oxidized lignin.

[0430] A rotor-stator device is a device for processing materials, which comprises a stator constructed as an inner cone provided with a toothed ring. The stator cooperates with a rotor having arms protruding from a hub. Each of these arms carries teeth that mesh with the teeth of the toothed ring of the stator. With each rotation of the rotor, the material to be processed is conveyed a little further outwards, while being subjected to strong shearing, mixing and redistribution. The rotor arms of the upright device and the container chamber below allow the material to be permanently rearranged from the inside out and provide multiple treatments of dry and / or highly viscous substances, so that the device is very useful for thorough mixing, kneading, fibrillation, disintegration and similar processes that are important in industrial production. The upright arrangement of the housing helps the material to fall back from the periphery to the center of the device.

[0431] In one embodiment, the rotor-stator device used in the method of the invention comprises a stator with a toothed ring and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following characteristics: Between the arms of the rotor protrude a guide funnel, which concentrates the material flow coming from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided for feeding the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates an increased material pressure in the center.

[0432] For more details on the rotor-stator apparatus used in one embodiment of the method of the present invention, reference is made to US 2003 / 0042344 A1, which is incorporated herein by reference.

[0433] In one embodiment, the method is carried out so that the method uses one rotor-stator apparatus. In this embodiment, the mixing of the components and the reaction of the components are carried out in the same rotor-stator apparatus.

[0434] In one embodiment, the method is carried out such that it uses two or more rotor-stator devices, wherein at least one rotor-stator device is used for mixing of the components and at least one rotor-stator device is used for reacting the components.

[0435] This method can be divided into two steps:

[0436] 1. Preparation of lignin substances (a) + (b) + (d), and

[0437] 2. Oxidation of lignin.

[0438] Typically, two different types of rotor / stator motors are used:

[0439] 1. Open rotor / stator motor suitable for mixing lignin powder into water at very high concentrations (30 to 50 wt%). The mixing intensity is low, but special auxiliary equipment (inlet funnel, screw, etc.) is required to handle highly viscous materials. Low peripheral speed (up to 15 m / s). The machine can be used as a batch or continuous system.

[0440] 2. In-line rotor / stator motors, which have much higher shear forces (circumferential speeds up to 55 m / s) and create favorable conditions for very fast chemical reactions. The machine should be used continuously.

[0441] In the open rotor / stator system, a high concentrate of lignin / water (45 to 50 wt%) is prepared. The lignin powder is slowly added to warm water (30 to 60°C) to which appropriate amounts of ammonia and / or alkali metal base are added. This can be done in batch mode or the materials are added intermittently / continuously to create a continuous stream for the next step.

[0442] The resulting mass should be kept at a temperature of about 60 degrees to keep the viscosity as low as possible and thus keep the material pumpable. The hot mass of lignin / water at a pH of 9 to 12 is then transferred to the oxidation step using a suitable pump such as a screw pump or other positive displacement pump.

[0443] In one embodiment, the oxidation is carried out as a continuous on-line reaction in a closed rotor / stator system. An aqueous solution of ammonia and / or alkali metal base is metered into the rotor / stator chamber at the highest turbulence / shear point using a metering pump. This ensures a rapid oxidation reaction. The oxidized material (AOL) leaves the on-line reactor and is collected in a suitable tank.

[0444] Reaction products

[0445] The present inventors have surprisingly found that the prepared oxidized lignins have highly desirable reactivity properties while showing improved fire resistance when used in products in which they are included in a binder composition and showing improved long term stability compared to previously known oxidized lignins.

[0446] The oxidized lignin also exhibits improved hydrophilicity.

[0447] An important parameter for the reactivity of the prepared oxidized lignin is the carboxylic acid group content of the oxidized lignin.

[0448] In one embodiment, the prepared oxidized lignin has a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 2.0 mmol / g, such as 0.40 to 1.5 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of component (a).

[0449] Another way to describe the carboxylic acid group content is to use the average carboxylic acid group content per lignin macromolecule calculated according to the following formula:

[0450]

[0451] In one embodiment, the oxidized lignin produced has an average carboxylic acid group content of more than 1.5 groups per macromolecule of component (a), such as more than 2 groups per macromolecule of component (a), such as more than 2.5 groups per macromolecule of component (a).

[0452] Method III for preparing oxidized lignin

[0453] Oxidized lignin that can be used as a component of the binder used in the present invention can be prepared by a method comprising the following steps:

[0454] The following components are contacted:

[0455] - a component (a) comprising one or more lignins,

[0456] a component (b) comprising ammonia and / or one or more amine components and / or any of their salts and / or alkali and / or alkaline earth metal hydroxides such as sodium hydroxide and / or potassium hydroxide,

[0457] - component (c) comprising one or more oxidizing agents,

[0458] - optional component (d) in the form of one or more plasticizers,

[0459] and allowing to proceed to a mixing / oxidation step in which an oxidized mixture is produced, followed by an oxidation step in which the oxidized mixture is allowed to continue reacting for a residence time of 1 second to 10 hours, such as 10 seconds to 6 hours, such as 30 seconds to 2 hours.

[0460] Components (a), (b), (c) and (d) are as defined above in process II for preparing oxidized lignin.

[0461] In one embodiment of the invention, the process comprises a premixing step, wherein the components are brought into contact with one another.

[0462] In the premixing step, the following components may be brought into contact with each other:

[0463] - component (a) and component (b), or

[0464] - component (a), component (b) and component (c), or

[0465] - component (a), component (b) and component (d), or

[0466] - component (a), component (b), component (c) and component (d).

[0467] In one embodiment of the invention, the premixing step can be carried out as a separate step and the mixing / oxidation step can be carried out after the premixing step. In this embodiment of the invention, it is particularly advantageous to bring components (a) and (b) and optionally (d) into contact with one another in the premixing step. Component (c) is then added to the premix produced in the premixing step in a subsequent mixing / oxidation step.

[0468] In another example of the present invention, the premixing step may correspond to the mixing / oxidation step. In this embodiment of the present invention, components such as component (a), component (b) and component (c) are mixed and the oxidation process is started at the same time. The subsequent residence time can be carried out in the same equipment used to carry out the mixing / oxidation step. This embodiment of the present invention is particularly advantageous if component (c) is air.

[0469] The inventors have found that by carrying out an oxidation step after the mixing / oxidation step, preferably without further mixing of the reaction mixture, the oxidation rate can be controlled in a very effective manner. At the same time, because the oxidation step after the mixing / oxidation step requires less complex equipment, the cost of carrying out the process is reduced.

[0470] Another advantage is that the oxidized lignin produced is particularly stable. Another surprising advantage is that the oxidized lignin produced can be well adjusted with respect to viscosity. Another surprising advantage is that the concentration of the oxidized lignin can be very high.

[0471] In one embodiment, the residence time is selected to allow the oxidation reaction to reach a desired degree of completion, preferably complete completion.

[0472] System I for carrying out said method III

[0473] In one embodiment, a system for performing the method comprises:

[0474] - at least one rotor-stator device,

[0475] - one or more inlets for water and components (a) and (b),

[0476] - one or more outlets of the rotor-stator device,

[0477] - At least one reaction device, in particular at least one reaction tube, which is arranged downstream of at least one or more outlets in the process flow direction.

[0478] In one embodiment, the system comprises one or more inlets for component (c) and / or component (d).

[0479] In one embodiment, the system comprises a premixing device.

[0480] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0481] In one embodiment of the present invention, the premixing device comprises inlets for water and components (a) and (b).

[0482] It is also possible that component (c) is mixed with the above three ingredients (water, component (a) and component (b)) in the premixing step. The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) is already in contact with the other components (water, component (a) and component (b)) through the opening of the container. Moreover, in this embodiment of the invention, the premixing device may optionally comprise an inlet for component (d).

[0483] In one embodiment, the system is constructed in such a way that the inlet for components (a), (b) and (d) is the inlet of a premixing device, in particular an open rotor-stator device, whereby the system also comprises an additional rotor-stator device having an inlet for component (c) and the additional rotor-stator device having an outlet for the oxidized lignin.

[0484] The premixing step and the mixing / oxidation step may be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device, ie a rotor-stator device.

[0485] In one embodiment, a rotor-stator device used in the method of the invention comprises a stator with a toothed ring and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: Between the arms of the rotor protrude a guide funnel, which concentrates the material flow coming from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided that feeds the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates an increased material pressure in the center.

[0486] System II for carrying out said method III

[0487] In one embodiment, a system for performing the method comprises:

[0488] - one or more inlets for water, components (a) and (b),

[0489] - at least one mixing and oxidation device having one or more outlets, and

[0490] - At least one mixer / heat exchanger arranged downstream of at least one or more outlets in the process flow direction, wherein the mixer / heat exchanger comprises a temperature control device.

[0491] In one embodiment, the system comprises an additional inlet or inlets for component (c) and / or component (d).

[0492] In one embodiment, the system comprises a premixing device.

[0493] The premixing device may comprise one or more inlets for water and / or component (a) and / or component (b) and / or component (c) and / or component (d).

[0494] In one embodiment, the premixing device comprises inlets for water and components (a) and (b).

[0495] It is also possible that component (c) is mixed with the above three ingredients (water, component (a) and component (b)) in the premixing step. The premixing device may then also have an inlet for component (c). If component (c) is air, the premixing device may be formed by an open mixing container, so that in this case component (c) is already in contact with the other components (water, component (a) and component (b)) through the opening of the container. Moreover, in this embodiment of the invention, the premixing device may optionally comprise an inlet for component (d).

[0496] In one embodiment, the system is constructed in such a way that the inlets for components (a), (b) and (d) are inlets of an open rotor-stator apparatus, whereby the system also comprises a mixer / heat exchanger having an inlet for component (c) and an outlet for oxidized lignin.

[0497] The premixing step and the mixing / oxidation step may be performed simultaneously. In this case, the premixing device and the mixing / oxidation device are a single device.

[0498] In one embodiment, a rotor-stator device used in the method of the invention comprises a stator with a toothed ring and a rotor with teeth meshing with the teeth of the stator. In this embodiment, the rotor-stator device has the following features: Between the arms of the rotor protrude a guide funnel, which concentrates the material flow coming from above into the central area of ​​the container. The outer surface of the guide funnel defines an annular gap that restricts the material flow. At the rotor, a feed screw is provided that feeds the working area of ​​the device. The guide funnel retains the product in the active area of ​​the device, and the feed screw generates an increased material pressure in the center.

[0499] Of course, other equipment can also be used as premixing equipment. Moreover, the premixing step can be carried out in a mixing and oxidation device.

[0500] In one embodiment, the mixing and oxidation device is a static mixer. A static mixer is a device for continuous mixing of fluid materials without moving parts. One design of a static mixer is a plate mixer, and another common device type consists of a mixer element contained in a cylindrical (tube) or square housing.

[0501] In one embodiment, the mixer / heat exchanger is constructed as a multi-tube heat exchanger with mixing elements. The mixing elements are preferably fixed devices through which the mixture must flow, whereby mixing occurs by flowing through them. The mixer / heat exchanger can be constructed as a plug flow reactor.

[0502] Embodiment 1

[0503] Example IA - Oxidation of Lignin by Hydrogen Peroxide in Aqueous Ammonia Solution:

[0504] The amounts of the ingredients used in accordance with Example IA are provided in Tables IA 1.1 and IA 1.2.

[0505] Although kraft lignin is soluble in water at higher pH values, it is known that the viscosity of the solution increases greatly at a certain weight percentage. It is generally believed that the reason for the increase in viscosity is a combination of strong hydrogen bonding and π-electron interactions of the numerous aromatic rings present in lignin. For kraft lignin, a sudden increase in viscosity is observed at about 21-22 wt% in water, and 19 wt% kraft lignin is used in the examples presented.

[0506] Aqueous ammonia solution was used as base in the pH adjustment step. The amount was fixed at 4 wt %, based on the total reaction weight. The pH at the start of oxidation after the pH adjustment step was 10.7.

[0507] Table IA2 shows the results of CHNS elemental analysis of kraft lignin before and after oxidation. Prior to analysis, the samples were heat treated at 160° C. to remove adsorbed ammonia. The analysis showed that a certain amount of nitrogen became part of the structure of the oxidized lignin during the oxidation process.

[0508] During batch experimental testing, it has been determined that adding the entire amount of hydrogen peroxide in small time intervals is beneficial to oxidation, as opposed to adding the peroxide in multiple small portions over a long period of time. In this example, 2.0 wt % H2O2 based on the total reaction weight was used.

[0509] The oxidation is an exothermic reaction and a temperature increase will be noted after the addition of the peroxide. In this example, the temperature was maintained at 60°C during the three hour reaction.

[0510] After oxidation, 31 The amount of lignin functional groups per gram of sample was determined by P NMR and water titration. 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphosphacyclopentane (TMDP) was used as the phosphitylation reagent and cholesterol was used as the internal standard. 31 P Preparation of Samples for NMR NMR spectra were obtained for kraft lignin before and after oxidation and the results are summarized in Table IA3.

[0511] The change in COOH groups was determined by water titration using the following formula:

[0512]

[0513] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the empty volume. C 酸 In this case it is 0.1M HCl, and m sis the weight of the sample. The values ​​obtained from the water titration before and after oxidation are shown in Table IA4.

[0514] The average COOH functionality can also be quantified by the saponification value, which represents the number of milligrams of KOH required to saponify 1 g of lignin. Such a method can be found in AOCS Official Method Cd 3-25.

[0515] The average molecular weight was also determined before and after oxidation using a PSS PolarSil column (9:1 (v / v) dimethyl sulfoxide / water eluent, containing 0.05 M LiBr) and a UV detector at 280 nm. The combination of COOH concentration and average molecular weight also allowed the calculation of the average carboxylic acid group content per lignin macromolecule, and these results are shown in Table IA5.

[0516] Example IB - Scaling up lignin oxidation by hydrogen peroxide in ammonia to pilot scale

[0517] Lignin oxidation with hydrogen peroxide is an exothermic process and even at laboratory scale a significant temperature increase can be observed after the addition of peroxide. This is a natural problem when scaling up a chemical process, since the heat generated is related to the size to the cube (volume), while cooling generally only increases with the square of the size (area). Furthermore, due to the high viscosity of the adhesive intermediate, the process equipment must be carefully selected or designed. Therefore, the scale-up is carefully designed and carried out in several steps.

[0518] The first scale-up step used a specialized stainless steel mixer with very efficient mechanical mixing from 1 L (laboratory scale) to 9 L. The scale-up resulted in only slightly higher final temperatures than those obtained in the laboratory scale, which was attributed to the efficient air cooling of the reactor and the slow addition of hydrogen peroxide.

[0519] The next scale-up step was carried out in a closed 200 L reactor with an efficient water jacket and an efficient propeller stirrer. This time the scale was 180 liters and the hydrogen peroxide was added in two steps, approximately 30 minutes apart. This scale-up went relatively smoothly, although considerable foaming was a problem, partly due to the high degree of reactor filling. To control the foaming, a small amount of food grade defoamer was sprayed onto the foam. Most importantly, a controllable temperature and a final temperature below 70°C were obtained using external water cooling.

[0520] The pilot scale reaction was carried out in an 800 L reactor with a water-cooled jacket and a two-blade propeller. 158 kg of lignin (UPM LignoBoost™ BioPiva 100) with a dry matter content of 67 wt% was deblocked and suspended in 224 kg of water and stirred to form a uniform suspension. Under continued stirring, 103 kg of 25% ammonia water was pumped into the reactor and stirred for another 2 hours to form a dark, viscous lignin solution.

[0521] To the stirred lignin solution was added 140 kg of 7.5 wt% hydrogen peroxide at 20-25° C. over 15 minutes. The temperature and foam level were carefully monitored during and after the addition of hydrogen peroxide, and cooling water was added to the cooling jacket to maintain acceptable foam levels and a temperature rise below 4° C. / minute and a final temperature below 70° C. After the temperature rise ceased, cooling was stopped and the product mixture was stirred for an additional 2 hours before being transferred to a shipping container.

[0522] Based on the scale-up run it can be concluded that even though the reaction is exothermic, most of the heat of reaction is actually balanced by the heat capacity of water from room temperature to about 60°C, and only the last part must be removed by cooling. It should be noted that due to this and due to the short reaction time, this process is ideal for scale-up and process intensification using continuous reactors such as in-line mixers, tubular reactors or CSTR type reactors. This will ensure good temperature control and a clearer reaction process.

[0523] Testing of the scaled-up batches showed that the oxidized lignin produced had properties consistent with laboratory produced batches.

[0524] Table IA 1.1 - Quantities of materials used in supplied form:

[0525]

[0526]

[0527] Table IA 1.2 - Amounts of active materials used:

[0528] Table IA 2 - Elemental analysis of kraft lignin before and after oxidation:

[0529]

[0530] Table IA 3 - Pass 31 Functional group distribution of kraft lignin before and after oxidation obtained by P NMR:

[0531]

[0532] Table IA 4 - COOH group content determined by water titration (in mmol / g):

[0533]

[0534] Table IA 5 - Number-average molar mass (Mn) and weight-average molar mass (Mw) (expressed in g / mol) and average carboxylic acid group content per lignin macromolecule before and after oxidation determined by size exclusion chromatography

[0535]

[0536] Example II

[0537] In the following examples, several oxidized lignins were prepared.

[0538] The following properties were determined for the oxidized lignin:

[0539] Solid content of components:

[0540] The amount of each component in a given oxidized lignin solution is based on the water-free mass of the component or as described below.

[0541] Kraft lignin is produced by UPM as BioPival TM Supplied in the form of dry powder. 25% NH4OH was supplied by Sigma-Aldrich and used in the form provided. 30% H2O2 (Cas No. 7722-84-1) was supplied by Sigma-Aldrich and used in the form provided or diluted with water. PEG 200 was supplied by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as is. PVA (Mw 89,000-98,000, Mw 85,000-124,000, Mw 130,000, Mw146,000-186,000) (Cas No. 9002-89-5) was supplied by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as is. Urea (Cas No. 57-13-6) was supplied by Sigma-Aldrich and used in the form provided or diluted with water. Glycerol (Cas No. 56-81-5) was supplied by Sigma-Aldrich and was assumed to be anhydrous for simplicity and used as received.

[0542] Oxidized lignin solid content

[0543] The content of oxidized lignin after heating to 200°C for 1 h is called the "dry solids content" and is expressed as a percentage of the weight remaining after heating.

[0544] A disc-shaped asbestos sample (5 cm in diameter; 1 cm in height) was cut from the asbestos and heat treated at 580°C for at least 30 minutes to remove all organic matter. The solid content of the binder mixture was measured by distributing a sample of the binder mixture (approximately 2 g) onto a heat-treated asbestos disc in a tinfoil container. The weight of the tinfoil container containing the asbestos disc was weighed immediately before and after the addition of the binder mixture. Two asbestos discs loaded with this binder mixture in a tinfoil container were produced and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the dry solid content was calculated as the average of the two results.

[0545] COOH group content

[0546] The change in the COOH group content was also determined by water titration and using the following formula:

[0547]

[0548] Where V 2s and V 1s is the endpoint volume of the sample, and V 2b and V 1b is the blank sample volume. C 酸 In this case it is 0.1M HCl, and m s,g is the weight of the sample.

[0549] Method for producing oxidized lignin:

[0550] 1) Mix water and lignin in a three-necked glass bottom flask in a water bath at room temperature (20-25°C), the flask is connected to a condenser and a temperature recording device during stirring. Stir for 1 hour.

[0551] 2) Add ammonia all at once during stirring.

[0552] 3) If the slightly exothermic reaction with ammonia does not raise the temperature, raise the temperature to 35°C by heating.

[0553] 4) Measure pH.

[0554] 5) Add plasticizer PEG200 and stir for 10 minutes.

[0555] 6) After about 1 hour when the lignin is completely dissolved, slowly add 30% H2O2 in one go.

[0556] 7) The exothermic reaction of adding H2O2 increases the temperature in the glass bottom flask - if the reaction temperature is below 60°C, increase the temperature to 60°C and place the sample at 60°C for 1 hour.

[0557] 8) The round bottom flask was then removed from the water bath and cooled to room temperature.

[0558] 9) Samples were taken for determination of dry solids content, COOH, viscosity, density and pH.

[0559] Oxidized lignin composition

[0560] In the following, the entry numbers of the oxidized lignin examples correspond to the entry numbers used in Table II.

[0561] Example IIA

[0562] 71.0 g of lignin UPM Biopiva 100 was dissolved in 149.0 g of water at 20° C., 13.3 g of 25% NH4OH was added and stirred for 1 h by a magnetic stirrer, after which 16.8 g of 30% H2O2 was slowly added thereto under stirring. The temperature was raised to 60° C. in a water bath. After 1 hour of oxidation, the water bath was cooled and the reaction was thus stopped. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

[0563] Example IIE

[0564] 71.0 g of lignin UPM Biopiva 100 was dissolved in 88.8 g of water at 20° C., 13.3 g of 25% NH4OH was added and stirred for 1 h by a magnetic stirrer. 22.8 g of PEG 200 was added and stirred for 10 min, after which 16.7 g of 30% H2O2 was slowly added thereto under stirring. The temperature was raised to 60° C. in a water bath. After 1 hour of oxidation, the water bath was cooled and the reaction was thus stopped. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

[0565] Example IIC

[0566] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20° C., 13.3 g of 25% NH4OH was added and stirred for 1 h by a magnetic stirrer, after which 16.6 g of 30% H2O2 was slowly added thereto under stirring. The temperature was raised to 60° C. in a water bath. After 1 hour of oxidation, the water bath was cooled and the reaction was thus stopped. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

[0567] Example IIF

[0568] 71.0 g of lignin UPM Biopiva 100 was dissolved in 57.1 g of water at 20° C., 13.3 g of 25% NH4OH was added and stirred for 1 h by a magnetic stirrer. 19.0 g of PEG 200 was added and stirred for 10 min, after which 16.6 g of 30% H2O2 was slowly added thereto under stirring. The temperature was raised to 60° C. in a water bath. After 1 hour of oxidation, the water bath was cooled and the reaction was thus stopped. The resulting material was analyzed for COOH, dry solids content, pH, viscosity and density.

[0569]

[0570] Example III:

[0571] 8.5 liters of hot water (50° C.) and 1.9 liters of NH 4 OH (24.7%) were mixed, and then 9.0 kg of lignin (UPM biopiva 100) was slowly added thereto over 10 minutes under high-speed stirring (660 rpm, 44 Hz).

[0572] The temperature increased due to the high shear forces. After 30 minutes, 4 liters of hot water were added and the material was stirred for another 15 minutes before the remaining portion of hot water (5 liters) was added. Samples were taken for analysis of undissolved lignin and pH measurement using a Hegman Scale.

[0573] The premix was then transferred to a rotor-stator apparatus and a reaction apparatus, in which oxidation was carried out by using H2O2 (17.5 vol%). The reaction apparatus used in this case at least partially comprises a reaction tube and a reaction vessel. The dosage of the premix was 150 l / h and the dosage of H2O2 was 18 l / h. In this case, a Cavitron CD1000 rotor-stator apparatus was used for the mixing / oxidation step. The rotor-stator apparatus was operated at 250 Hz (55 m / s peripheral speed) with a back pressure of 2 bar. The residence time in the reaction tube was 3.2 minutes and the residence time in the reaction vessel was 2 hours.

[0574] The temperature of the premix was 62°C and the oxidation step raised the temperature to 70°C.

[0575] The final products were analyzed for COOH group content, dry solids content, pH, viscosity and residual H2O2.

[0576] Table III:

[0577]

[0578] Example IV:

[0579] 484 liters of hot water (70°C) and 47.0 liters of NH4OH (24.7%) were mixed, and then 224.0 kg of lignin (UPM biopiva 100) was slowly added thereto over 15 minutes with high-speed stirring. Samples were taken for analysis of undissolved lignin and pH measurement using a Hegman Scale.

[0580] The premix was then transferred to a static mixer and a mixer / heat exchanger, where oxidation was carried out using H2O2 (35 vol%). The dosage of the premix was 600 l / h, the dosage of H2O2 was 17.2 l / h. The residence time in the mixer / heat exchanger was 20 minutes.

[0581] The temperature of the mixture was increased to 95°C during the oxidation step.

[0582] The final products were analyzed for COOH group content, dry solids content, pH, viscosity and residual H2O2.

[0583] A binder was prepared based on this AOL: 49.3 g AOL (19.0% solids), 0.8 g primid XL552 (100% solids) and 2.4 g PEG200 (100% solids) were mixed with 0.8 g water to give a solids content of 19%; this binder was then used to test mechanical properties in a strip test.

[0584] Strip test

[0585] The mechanical strength of the adhesives was tested in a strip test. For each adhesive, 16 strips were produced from a mixture of adhesive and asbestos balls from an asbestos spinning production.

[0586] The binder solution sample (16.0 g) with 15% dry solids content is thoroughly mixed with asbestos balls (80.0 g). The resulting mixture is then filled into four slots of a heat-resistant silicone model to make small strips (4x5 slots per model; slot top dimensions: length = 5.6 cm, width = 2.5 cm; slot bottom dimensions: length = 5.3 cm, width = 2.2 cm; slot height = 1.1 cm). The mixture placed in the slot is then pressed with a flat metal strip of appropriate size to produce a flat strip surface. 16 strips are prepared from each binder in this way. The resulting strips are then cured at 200 ° C. The curing time is 1 hour. After cooling to room temperature, the strips are carefully taken out of the container. Five of the strips are aged in a water bath at 80 ° C for 3 hours.

[0587] After drying for 1-2 days, the aged strips and 5 unaged strips were broken in a 3-point bending test on a Bent Tram machine (test speed: 10.0 mm / min; break level: 50%; nominal strength: 30 N / mm 2 ; Support distance: 40 mm; Maximum deviation: 20 mm; Nominal e-modulus: 10000 N / mm 2 ) to study their mechanical strength. The strips were placed in the machine with the "top side" (ie the side with the dimensions length = 5.6 cm, width = 2.5 cm) facing upwards.

[0588]

[0589] The following examples are intended to further illustrate the present invention without limiting its scope. Example

[0590] In the following examples, several binders falling within the scope of the present invention were prepared and compared with binders according to the prior art.

[0591] The following properties were measured for the adhesive of the present invention and the adhesive of the prior art:

[0592] Determination of water leachable chloride content of mineral fiber products

[0593] The water-leachable chloride content of mineral fiber products is measured in accordance with EN 13468: 2001. Said standard specifies the equipment and procedure for the determination of trace amounts of water-soluble chlorides in aqueous extracts of products. Reference is made to this standard. The water-leachable chloride content is given in milligrams of chloride per kilogram of mineral fiber product.

[0594] Determination of loss on ignition (LOI) of mineral fiber products

[0595] The amount of organic material (loss on ignition) is determined as the weight loss of the specimen obtained by burning off the organic material. This is done as specified in EN 13820. The binder content is taken as LOI. The binder includes oil and other binder additives, if present.

[0596] Determination of dry solid content of binders

[0597] The content of the binder after curing is called "binder solid content".

[0598] A disc-shaped asbestos sample (5 cm in diameter; 1 cm in height) was cut from the asbestos and heat treated at 580°C for at least 30 minutes to remove all organic matter. The solid content of the binder mixture was measured by distributing a sample of the binder mixture (approximately 2 g) onto a heat-treated asbestos disc in a tinfoil container. The weight of the tinfoil container containing the asbestos disc was weighed immediately before and after the addition of the binder mixture. Two asbestos discs loaded with this binder mixture in a tinfoil container were produced and then heated at 200°C for 1 hour. After cooling and storing at room temperature for 10 minutes, the sample was weighed and the dry solid content was calculated as the average of the two results.

[0599] Unless otherwise specified, the following reagents were used as received:

[0600] Lignin UPM BioPiva 100: Kraft lignin supplied by UPM, BioPiva 100 TM Dry powder.

[0601] PEG 200: Supplied by Sigma-Aldrich, assumed to be anhydrous for simplicity and used as received.

[0602] Primid XL552: Hydroxyalkylamide crosslinker supplied by EMS-CHEMIE AG

[0603] Preparation of Ammonia Oxidized Lignin (AOL) Resin

[0604] 3267 kg of water were added to a 6000 liter reactor, followed by 287 kg of ammonia (24.7%). Then, 1531 kg of lignin UPM BioPiva 100 was slowly added over a period of 30 to 45 minutes. The mixture was heated to 40°C and kept at this temperature for 1 hour. After 1 hour, the undissolved lignin was checked. This can be done by checking the solution on a glass plate or Hegman gauge. The undissolved lignin can be seen as small particles in the brown binder. The color of the lignin solution will change from brown to bright black during the dissolution step.

[0605] After the lignin was completely dissolved, 1 liter of defoamer (obtained from The batch temperature was maintained at 40°C.

[0606] Then the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[0607] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0608] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.2 mmol / g solid was thus obtained.

[0609] Preparation of the final binder (uncured binder composition suitable for preparing the mineral fiber product of the present invention)

[0610] A binder was formulated from the above AOL resin by adding 270 kg polyethylene glycol 200 (PEG 200) and 433 kg of a 31% solution of Primid XL-552 in water.

[0611] Analysis of the final adhesive showed the following data:

[0612] Solid content: 18.9%

[0613] pH: 9.7

[0614] Viscosity: 25.5mPas·s

[0615] Density: 1.066kg / l

[0616] Binder Examples - Reference Binders A1, A2 and A5 (phenolic resin PUF-resol modified with urea and dextrose)

[0617] The adhesive is a phenolic resin PUF-resol modified with urea.

[0618] A phenolic resin was prepared by reacting 37% aqueous formaldehyde (606 g) and phenol (189 g) in the presence of 46% aqueous potassium hydroxide (25.5 g) at 84° C. with a heating rate of about 1° C. / min to the reaction temperature. The reaction was continued at 84° C. until the acid resistance of the resin was 4 and most of the phenol was converted. Urea (241 g) was then added and the mixture was cooled.

[0619] The acid tolerance (AT) indicates how many times a given volume of binder can be diluted with acid without the mixture becoming cloudy (precipitation of the binder). Sulfuric acid is used to determine the stop criterion in the production of binders, and an acid tolerance below 4 indicates that the binder reaction is finished.

[0620] To measure AT, prepare a titrant by diluting 2.5 ml of concentrated sulfuric acid (>99%) with 1 L of ion-exchanged water. Then titrate 5 ml of the binder to be investigated with this titrant at room temperature while keeping the binder in motion by manual shaking; if preferred, a magnetic stirrer and magnetic bar can be used. The titration is continued until a slight turbidity appears in the binder, which does not disappear when the binder is shaken.

[0621] The acid tolerance (AT) was calculated by dividing the amount of acid used for titration (mL) by the amount of sample (mL):

[0622] AT = (titration volume used (mL)) / (sample volume (mL))

[0623] Using the obtained urea-modified phenolic resin, a binder was prepared by adding 25% ammonia water (90 mL) and ammonium sulfate (13.2 g), and then adding water (1.30 kg).

[0624] To the above mixture was added 18% dextrose (127.5 g) based on the dry matter of the above binder and dextrose. The binder solids content was then measured as described above and the mixture was diluted with the required amount of water and silane (15% binder solids solution, 0.5% silane on binder solids) to produce the insulation product.

[0625] Depending on the type of dilution water used, reference binders A1 (rainwater), A2 (process water), A5 (permeate water) were obtained.

[0626] Binder Examples A3 and A4:

[0627] Prepared as described in Example A1, but without the addition of dextrose. For Binder Example A3, process water was used, and for Binder Example A4, osmotic water was used.

[0628] Binder Example - Reference Binder B

[0629] A mixture of 75.1% aqueous glucose syrup (19.98 kg, thus effectively equal to 15.0 kg glucose syrup), 50% aqueous hypophosphorous acid (0.60 kg, thus effectively equal to 0.30 kg / 4.55 mol hypophosphorous acid) and sulfamic acid (0.45 kg, 4.63 mol) in water (30.0 kg) was stirred at room temperature until a clear solution was obtained. Then 28% aqueous ammonia (0.80 kg, thus effectively equal to 0.22 kg / 13.15 mol ammonia) was added dropwise until pH = 7.9. The binder solids content was then measured (21.2%). For mechanical strength studies (solution with 15% binder solids content, 0.5% silane of binder solids), the binder mixture was diluted with water (0.403 kg / kg binder mixture) and 10% aqueous silane (0.011 kg / kg binder mixture, Momentive VS-142). The final binder mixture had a pH of 7.9 and was used to produce insulation products.

[0630] Binder Examples 1-6

[0631] 3267 kg of water were added to a 6000 liter reactor, followed by 287 kg of ammonia (24.7%). Then, 1531 kg of lignin UPM BioPiva 100 was slowly added over a period of 30 to 45 minutes. The mixture was heated to 40°C and kept at this temperature for 1 hour. After 1 hour, the undissolved lignin was checked. This can be done by checking the solution on a glass plate or Hegman gauge. The undissolved lignin can be seen as small particles in the brown binder. The color of the lignin solution will change from brown to bright black during the dissolution step.

[0632] After the lignin was completely dissolved, 1 liter of defoamer (obtained from The batch temperature was maintained at 40°C.

[0633] Then the addition of 307.5 kg of 35% hydrogen peroxide was started. The hydrogen peroxide was added at a rate of 200-300 liters / hour. The first half of the hydrogen peroxide was added at a rate of 200 liters / hour, after which the addition rate was increased to 300 liters / hour.

[0634] During the addition of hydrogen peroxide, the temperature of the reaction mixture was controlled by heating or cooling to achieve a final reaction temperature of 65°C.

[0635] After reacting at 65° C. for 15 minutes, the reaction mixture was cooled to a temperature below 50° C. A resin having a COOH value of 1.2 mmol / g solid was thus obtained.

[0636] The AOL used was prepared as described in the above paragraph using the raw material amounts specified in Table 1. The raw materials specified in Table 1 were used to mix the AOL resin into a binder.

[0637] Asbestos products with reference binders A1-A5, B (reference products) and asbestos products with binders 1-6 (inventive products) were prepared in a standard asbestos plant using the water types specified in Table 1.

[0638] The binder dry solid content, ignition loss, chloride content and pH value of the obtained asbestos product were tested according to the above-described methods. The results are also shown in Table 1.

[0639]

Claims

1. A preformed pipe section which is a mineral fibre product comprising mineral fibres bonded by a cured binder composition, the uncured binder composition comprising one or more oxidised lignins.

2. The pipe section of claim 1, wherein the pipe section has a water leachable chloride content of less than 10 mg / kg, such as less than 6 mg / kg, as determined according to EN 13468:2001.

3. The pipe section according to claim 1 or claim 2, which is a thermal and / or sound insulation product.

4. A pipe section as claimed in any preceding claim, wherein the pipe section is a thermal and / or acoustic insulation material for a pipe, tank, boiler, container or column, and / or The pipe section has a thickness in the range of 20 mm to 500 mm, preferably 30 mm to 300 mm, for example 50 mm to 150 mm.

5. The pipe section according to any of the preceding claims, wherein the mineral fibers are hydrophobically treated mineral fibers, preferably hydrophobically treated asbestos, wherein the hydrophobic treatment is preferably performed by treating the mineral fibers with at least one hydrophobizing agent selected from mineral oils, siloxanes or silicone resins.

6. The pipe section according to any one of the preceding claims, wherein the uncured cement composition is an aqueous cement composition, wherein preferably at least a portion of the water or all of the water contained in the aqueous cement composition is non-purified water, wherein the non-purified water is preferably selected from tap water, rain water, production water or a combination thereof.

7. The pipe segment of any one of the preceding claims, wherein the uncured cement composition comprises: - component (i) in the form of one or more oxidized lignins; - component (ii) in the form of one or more crosslinking agents; - Optionally, component (iii) in the form of one or more plasticizers.

8. The pipe section of any of the preceding claims, wherein the one or more oxidized lignins are oxidation products of lignin selected from the group consisting of kraft lignin, alkali lignin, lignosulfonate lignin, organosolv lignin, lignin from a biorefining process of a lignocellulosic feedstock, or any mixture thereof.

9. The pipe section of any one of the preceding claims, wherein the one or more oxidized lignins are in the form of one or more ammonia oxidized lignins (AOL).

10. The pipe section of any one of the preceding claims, wherein the one or more oxidized lignins have a carboxylic acid group content of 0.05 to 10 mmol / g, such as 0.1 to 5 mmol / g, such as 0.20 to 1.5 mmol / g, such as 0.40 to 1.2 mmol / g, such as 0.45 to 1.0 mmol / g, based on the dry weight of the one or more oxidized lignins.

11. The pipe section of any one of claims 7 to 10, wherein the component (ii) is in the form of one or more cross-linking agents selected from the group consisting of: a) a β-hydroxyalkylamide crosslinking agent and / or an oxazoline crosslinking agent, and / or b) polyfunctional organic amines, for example alkanolamines, diamines such as 1,6-hexanediamine, triamines, and / or c) epoxidized oils based on fatty acid triglycerides or one or more flexible oligomers or polymers, such as low T g Acrylic-based polymers, such as low T g Vinyl polymers, such as low T g Polyethers containing reactive functional groups such as carbodiimide groups, such as anhydride groups, such as oxazoline groups, such as amino groups, such as epoxy groups, and / or d) molecules having three or more epoxy groups, and / or e) one or more cross-linking agents selected from the group consisting of polyethyleneimine, polyvinylamine, fatty amine; and / or f) one or more cross-linking agents in the form of fatty amides; and / or g) one or more cross-linking agents selected from the group consisting of dimethoxyacetaldehyde, glycolaldehyde, glyoxylic acid; and / or h) one or more crosslinking agents selected from polyester polyols such as polycaprolactone; and / or i) one or more cross-linking agents selected from the group consisting of starch, modified starch, CMC; and / or j) one or more crosslinking agents in the form of aliphatic polyfunctional carbodiimides; and / or k) one or more crosslinking agents selected from melamine-based crosslinking agents such as hexa(methylmethoxy)melamine (HMMM)-based crosslinking agents, The one or more crosslinking agents are preferably selected from β-hydroxyalkylamide crosslinking agents and / or oxazoline crosslinking agents.

12. The pipe section of any one of claims 7 to 11, wherein component (iii) is contained in the uncured cement composition in the form of one or more plasticizers, the one or more plasticizers being selected from the group consisting of polyethylene glycols, polyethylene glycol ethers, polyethers, hydrogenated sugars, phthalates and / or acids, such as adipic acid, vanillic acid, lactic acid and / or ferulic acid, acrylic polymers, polyvinyl alcohol, polyurethane dispersions, ethylene carbonate, propylene carbonate, lactones, lactams, lactides, acrylic polymers with free carboxyl groups, and / or polyurethane dispersions with free carboxyl groups, and / or - one or more plasticizers selected from the group consisting of fatty alcohols, monohydric alcohols such as amyl alcohol, stearyl alcohol; and / or - one or more plasticizers selected from the group consisting of alkoxylates such as ethoxylates, for example butanol ethoxylates such as butoxytriglycol; and / or - one or more plasticizers in the form of propylene glycol; and / or - one or more plasticizers in the form of glycol esters; and / or - one or more plasticizers selected from the group consisting of adipates, acetates, benzoates, cyclobenzoates, citrates, stearates, sorbates, sebacates, azelates, butyrates, valerates; and / or - one or more plasticizers selected from the group consisting of phenol derivatives, such as alkyl or aryl substituted phenols; and / or - one or more plasticizers selected from the group consisting of silanols, siloxanes; and / or - one or more plasticizers selected from the group consisting of sulfates such as alkyl sulfates, sulfonates such as alkyl arylsulfonates, for example alkyl; and / or - sulfonates, phosphates such as tripolyphosphates; and / or - one or more plasticizers in the form of hydroxy acids; and / or - one or more plasticizers selected from the group consisting of monomeric amides, such as acetamide, benzamide, fatty acid amides such as tall oil amide; and / or - one or more plasticizers selected from the group consisting of quaternary ammonium compounds such as trimethylglycine, distearyldimethylammonium chloride; and / or - one or more plasticizers selected from the group consisting of vegetable oils, such as castor oil, palm oil, linseed oil, soybean oil; and / or - tall oil, and / or - one or more plasticizers selected from the group consisting of hydrogenated oils, acetylated oils; and / or - one or more plasticizers selected from acid methyl esters; and / or - one or more plasticizers selected from the group consisting of alkyl polyglucosides, glucamides, aminoglucamides, sucrose esters, sorbitan esters; and / or - One or more plasticizers selected from the group consisting of polyethylene glycol, polyethylene glycol ethers.

13. Use of a preformed pipe section as thermal and / or acoustic insulation material, in particular a non-corrosive thermal and / or acoustic insulation material, the preformed pipe section being a mineral fiber product comprising mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the pipe section optionally has a water-leachable chloride content of less than 10 mg / kg, determined according to EN 13468:2001.

14. The use according to claim 13, wherein the pipe section is used as thermal and / or acoustic insulation material, in particular non-corrosive thermal and / or acoustic insulation material, for an object, preferably a pipe, selected from the group consisting of a pipe, a tank, a boiler, a container or a column.

15. Use according to claim 13 or claim 14, at a temperature in the range of -20°C to 320°C, preferably 0°C to 200°C, for example 50°C to 175°C.

16. The use according to any one of claims 13 to 15, wherein the pipe section is used as thermal and / or acoustic insulation material, in particular non-corrosive thermal and / or acoustic insulation material, for articles made of metal, wherein the metal is preferably selected from copper or steel, in particular carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low-alloy steel.

17. The use according to any one of claims 13 to 16, wherein the pipe section is as defined in any one of claims 1 to 12.

18. A method of making a preformed pipe section, the preformed pipe section being a mineral fibre product comprising mineral fibres bonded by a cured binder composition, the uncured binder composition comprising one or more oxidised lignins, wherein the pipe section optionally has a water leachable chloride content of less than 10 mg / kg, measured according to EN 13468:2001, The method comprises the following steps: a) providing an uncured aqueous binder composition comprising one or more oxidized lignins and water, b) contacting mineral fibers with said uncured aqueous binder composition, and c) curing the binder composition in contact with the mineral fibers, At least a portion of the water or all of the water contained in the uncured aqueous binder composition is added non-purified water, wherein the non-purified water is preferably selected from tap water, rainwater, production water or a combination thereof.

19. The method of claim 18, wherein The proportion of the non-purified water added is in the range of 30 to 100 wt %, preferably in the range of 50 to 100 wt %, based on the total weight of water contained in the uncured cement composition, and / or The water content in the uncured aqueous binder composition is in the range of 40 to 90 wt %, preferably in the range of 60 to 85 wt %, based on the total weight of the uncured aqueous binder composition.

20. A method as claimed in claim 18 or claim 19, wherein the pipe section is as defined in any one of claims 1 to 12.

21. A hollow article covered with a preformed pipe segment as thermal and / or acoustic insulation material, wherein the preformed pipe segment is a mineral fiber product and comprises mineral fibers bonded by a cured binder composition, the uncured binder composition comprising one or more oxidized lignins, wherein the pipe segment optionally has a water leachable chloride content of less than 10 mg / kg, determined according to EN 13468:2001.

22. The hollow article according to claim 21, wherein the hollow object is selected from a tube, a tank, a boiler, a container or a column, preferably a tube, and / or The hollow article is made of metal, wherein the metal is preferably selected from copper or steel, in particular carbon steel, stainless steel, austenitic stainless steel, non-alloy steel or low-alloy steel.

23. A hollow article as claimed in claim 21 or claim 22, wherein the tube section is as defined in any one of claims 1 to 12.

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