Novel coolant composition

Abstract

The present invention relates to a novel coolant composition for cooling systems, which is based on renewable raw materials.

Description

[Technical Field]

[0001] This invention describes a novel coolant composition for cooling systems based on renewable raw materials. [Background technology]

[0002] Coolants used not only in mobile or stationary internal combustion engines but also in the cooling circuits of electric vehicles or vehicles that combine electric motors and internal combustion engines are generally liquid mixtures of water, glycol, corrosion inhibitors, and further components.

[0003] The glycol component that lowers the freezing point is usually monoethylene glycol and / or monopropylene glycol, and is primarily monoethylene glycol.

[0004] Monoethylene glycol is typically produced industrially by ring-opening ethylene oxide with water, which is produced from ethene, which in turn is obtained by cracking fossil naphtha in a steam cracker.

[0005] This manufacturing method has at least the following drawbacks: - Fossil fuels are a finite resource. - The use of fossil fuels increases the carbon footprint, resulting in a worse life cycle assessment of the resulting products. - Ethylene oxide (oxirane) is a carcinogen, and due to its high toxicity and safety characteristics (flash point, ignition temperature, explosion limits), its manufacture and handling cannot be carried out without strict safety measures. - When ethylene oxide is reacted with water, not only is the desired monoethylene glycol obtained, but higher molecular weight low polymers with various properties, particularly diethylene glycol and triethylene glycol, are also produced.

[0006] These higher molecular weight low polymers must usually be carefully separated from monoethylene glycol by distillation, but small amounts inevitably remain in the monoethylene glycol. The presence of higher molecular weight low polymers results in, firstly, a non-uniform boiling point of the product; and secondly, because higher molecular weight alkylene glycols often act as emulsifiers or foaming agents, when mixed with water in high proportions, they can cause foaming when used by the end user.

[0007] Because monoethylene glycol has a high boiling point of approximately 197°C under standard pressure, a lot of energy is required to supply heat and generate a reduced pressure to remove the higher molecular weight low polymer by distillation, and even then, the higher molecular weight low polymer is not completely separated.

[0008] Although not very common in practice, monopropylene glycol (1,2-propylene glycol) is sometimes used as a glycol component to lower the freezing point, instead of monoethylene glycol. However, 1,2-propylene glycol is produced in the same way from propylene oxide, and propylene oxide is obtained from propene, which is similarly obtained from naphtha, so the problem is essentially the same. [Overview of the project] [Problems that the invention aims to solve]

[0009] The object of the present invention was to provide a coolant that reduces the aforementioned drawbacks, particularly its high carbon footprint. [Means for solving the problem]

[0010] This objective was achieved by using a coolant containing monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials, as a glycol component that lowers the freezing point. [Modes for carrying out the invention]

[0011] The production of glycols, especially monoethylene glycol, from renewable raw materials is basically known. Monoethylene glycol as a C2 species can be obtained, broadly speaking, by the various routes exemplified below: - From C1 compounds, by formation of C2 and formation of C-C bonds - From C2 compounds, usually by oxidation or reduction - From compounds having at least three carbon atoms, by decomposition and / or cleavage of the carbon skeleton.

[0012] These production variants are briefly described below:

[0013] From C1 compounds Preferably, ethylene glycol can be prepared from C1 compounds derived from a gas or gas mixture containing CO2 and / or CO, in the presence of reduction equivalents, such as hydrogen, more preferably by a biological method.

[0014] A preferred process is described in WO 2019 / 126400 A1. This involves converting a gas mixture containing hydrogen (H2) and carbon dioxide (CO2) and / or carbon monoxide (CO) into monoethylene glycol or a possible precursor of monoethylene glycol (see section on C2 compounds below) by a genetically modified microorganism.

[0015] Genetic modification can relate to the production of exogenous dissimilar heterologous enzymes for the conversion of oxaloacetic acid to citric acid, glycine to glyoxylic acid, isocitric acid to glyoxylic acid and glycolic acid to glycolaldehyde.

[0016] These can be the following enzymes: Conversion of oxaloacetate to citrate: citrate[si] synthase [2.3.3.1], ATP citrate synthase [2.3.3.8]; or citrate(re) synthase [2.3.3.3]. Conversion of glycine to glyoxylic acid: alanine-glyoxylate aminotransferase [2.6.1.44], serine-glyoxylate aminotransferase [2.6.1.45], serine-pyruvate aminotransferase [2.6.1.51], glycine-oxaloacetate aminotransferase [2.6.1.35], glycine aminotransferase [2.6.1.4], glycine dehydrogenase [1.4.1.10], alanine dehydrogenase [1.4.1.1] or glycine dehydrogenase [1.4.2.1]. Conversion of isocitrate to glyoxylic acid: isocitrate lyase [4.1.3.1]. Conversion of glycolic acid to glycolaldehyde: glycolaldehyde dehydrogenase [1.2.1.21], lactaldehyde dehydrogenase [1.2.1.22], succinic acid semialdehyde dehydrogenase [1.2.1.24], 2,5-dioxovalerate dehydrogenase [1.2.1.26], aldehyde dehydrogenase [1.2.1.3 / 4 / 5], betaine aldehyde dehydrogenase [1.2.1.8] or aldehyde ferredoxin oxidoreductase [1.2.7.5].

[0017] Such enzymes can be obtained from microorganisms selected from the group consisting of the genera Bacillus, Clostridium, Escherichia, Gluconobacter, Hypomicrobium, Lysinibacillus, Paenibacillus, Pseudomonas, Sedimenticola, Sporosarcina, Streptomyces, Thermithiobacillus, Thermotoga, and Zea.

[0018] Similarly, microorganisms containing enzymes selected from the group consisting of isocitrate dehydrogenase, glycerate dehydrogenase, glycolate dehydrogenase, glycerate dehydrogenase, glycolate dehydrogenase, aldehyde ferredoxin oxidoreductase, and aldehyde dehydrogenase are also possible.

[0019] In a preferred embodiment, the microorganism is selected from the group consisting of the genera Acetobacterium, Alkalibaculum, Blautia, Butyribacterium, Clostridium, Eubacterium, Moorella, Oxobacter, Sporomusa, and Thermoanaerobacter. More preferably, these include Acetobacterium woodii, Alkalibaculum bacchii, Blautia producta, Butyribacterium methylotrophicum, Clostridium aceticum, Clostridium autoethanogenum, Clostridium carboxidivorans, Clostridium coskatii, Clostridium drakei, Clostridium formicoaceticum, and Clostridium jungdalii. (ljungdahlii), Clostridium magnum, Clostridium ragsdalei, Clostridium scatologenes, Eubacterium limosum, Moorella thermautotrophica, Moorella thermoacetica, Oxobacter phoenigiiThe group is selected from the species consisting of *Sporomusa pfennigii*, *Sporomusa ovata*, *Sporomusa silvacetica*, *Sporomusa sphaeroides*, and *Thermoanaerobacter kiuvi*, and in particular from the group consisting of *Clostridium autoethanogenum*, *Clostridium ljungdahlii*, and *Clostridium ragsdalei*.

[0020] The enzymes or nucleic acids encoding the above-mentioned species are preferably from the genera Bacillus, Clostridium, Escherichia, Gluconobacter, Hyphomicrobium, Lysinibacillus, Paenibacillus, Pseudomonas, Sedimenticola, and Sporosarcina. Genus Arcina, Streptomyces, Thermithiobacillus, Thermotoga, Zea, Klebsiella, Mycobacterium, Salmonella, Mycobacteroides, Staphylococcus, Burkholderia, Listeria ria, Acinetobacter, Shigella, Neisseria, Bordetella, Streptococcus, Enterobacter, Vibrio, Legionella, Xanthomonas, Serratia, Cronobacter, Cupriavidus, Heli Helicobacter, Yersinia, Cutibacterium, Francisella, Pectobacterium, Arcobacter, Lactobacillus, Shewanella, Erwinia, Sulfurospirillum, Peptococcaceae,Genera: Thermococcus, Saccharomyces, Pyrococcus, Glycine, Homo, Ralstonia, Brevibacterium, Methylobacterium, Geobacillus, Bos, Gallus, Anaerococcus, Xenopus , genera Amblyrhynchus, rattus, mus, sus, Rhodococcus, Rhizobium, Afegasphaera, Mesorhizobium, Peptococcus, Agrobacterium, Campylobacter, Acetobacterium, Al The genera include Alkalibaculum, Blautia, Butyribacterium, Eubacterium, Moorella, Oxobacter, Sporomusa, Thermoanaerobacter, Schizosaccharomyces, Paenibacillus, and Fictibacillus. genus acillus, Lysinibacillus, Ornithinibacillus, Halobacillus, Kurthia, Lentibacillus, Anoxybacillus, Solibacillus, Virgibacillus, Alicyclobacillus, Sporosarcina,It is expressed in microorganisms selected from the group consisting of the genera Salimicrobium, Sporosarcina, Planococcus, Corynebacterium, Thermaerobacter, Sulfobacillus, and Symbiobacterium.

[0021] Regarding at least one of the enzymes mentioned above, Clostridium acetobutylicum, Clostridium beijerinckii, Escherichia coli, Saccharomyces cerevisiae, Acetobacterium woodii, Alkalibaculum bacchii, Blautia product, Butyribacterium methylotrophicum, Clostridium aceticum, Clostridium autoethanogenum, Clostridium carboxydivorce carboxidivorans), Clostridium coskatii, Clostridium drakei, Clostridium formicoaceticum, Clostridium ljungdahlii, Clostridium magnum, Clostridium ragsdalei, Clostridium scatologenes, Eubacterium limosum, Moorella thermautotrophica, Moorella thermoacetica, Oxobacter phoenix Sporomusa pfennigii), Sporomusa ovata, Sporomusa silvacetica, Sporomusa spheroidesA genetically modified microorganism selected from the group consisting of sphaeroides and Thermoanaerobacter kiuvi, more preferably selected from the group consisting of Clostridium autoethanogenum, Clostridium ljungdahlii and Clostridium ragsdalei, in particular, Clostridium autoethanogenum LZ1561 described in International Publication No. 2012 / 015317 is preferred.

[0022] The carbon dioxide (CO2) and / or carbon monoxide (CO) used may be derived from any source, such as exhaust gases, combustion gases, fermentation gases, synthesis gases, or from separation from air (also known as carbon capture (CC) or carbon capture and utilization (CCU)).

[0023] If the carbon dioxide (CO2) and / or carbon monoxide (CO) used in this process are not specially produced from fossil resources for this process, there is an advantage in terms of carbon footprint. On the other hand, it is also advantageous to use carbon dioxide (CO2) and / or carbon monoxide (CO) derived from exhaust gases or combustion gases that would otherwise be released into the atmosphere if not used in this process.

[0024] Preferably, the carbon dioxide (CO2) and / or carbon monoxide (CO) used in this process are derived from renewable raw materials, for example, from a combustion process or fermentation.

[0025] The use of carbon dioxide (CO2) separated from the air is also advantageous when used in this process (carbon capture and utilization (CCU)). In this case, the monoethylene glycol obtained from this process constitutes a carbon sink.

[0026] The product mixture obtained by this process may include, in addition to monoethylene glycol, its biosynthetic precursors, such as glycolic acid, glyoxylic acid, and / or glycolaldehyde. Therefore, to convert these into the desired monoethylene glycol product, the reaction mixture may preferably be subjected to hydrogenation.

[0027] Typically, the reaction mixture is obtained as an aqueous solution, from which monoethylene glycol can be separated, preferably by distillation, rectification, or stripping (collectively referred to as distillation in this specification for simplicity). Since the by-products of the reaction have relatively low boiling points, the energy consumption in distillation is less than when separating monoethylene glycol from a lower molecular weight polymer in the reaction of ethylene oxide with water.

[0028] Furthermore, monoethylene glycol can also be separated by methods other than distillation, such as membrane filtration or reverse osmosis. A combination of distillation and other methods is also possible.

[0029] One example of a process for producing monoethylene glycol precursors starting from a C1 source other than CO or CO2 is the production of oxalic acid or its salts from formic acid or its salts. This is usually done by reacting an alkali metal formate, such as sodium formate or potassium formate, with a strong base, such as a metal hydride or alkali metal hydroxide, especially sodium hydroxide. However, this process is not very desirable.

[0030] Similarly, glycolaldehyde can be produced by reacting formaldehyde with carbon monoxide and hydrogen through hydroformylation. The glycolaldehyde thus obtained can then be hydrogenated to monoethylene glycol, as described in U.S. Patent No. 4,496,781,B1.

[0031] In other embodiments, CO2 and / or CO can be hydrogenated to methanol, which is then converted to ethene in a methanol-to-olefin (MTO) process, where the ethene is oxidized to ethylene oxide, which is then converted to monoethylene glycol using water.

[0032] The production of methanol by hydrogenation of carbon oxides, particularly carbon dioxide, is well known.

[0033] A general overview of suitable catalyst systems is described in Kristian Stangeland, Hailong Li, and Zhixin Yu, Energy, Ecology and Environment, volume 5, pages 272-285 (2020). This process requires a multi-component catalyst system. Interactions between components are crucial for enhancing the activity and selectivity of the catalytic reaction from CO2 to methanol. This has been demonstrated in many catalyst systems consisting of various metals (e.g., Cu, Pd, Ni) and metal oxides (e.g., ZnO, ZrO2, In2O3). These complex systems may include mixtures of metallic phases, alloy phases, and metal oxide phases. Currently, the most promising catalyst systems for industrial-scale processes are Cu and In-based catalysts, which exhibit excellent catalytic performance.

[0034] The process for synthesizing methanol from CO2 can be carried out, for example, by the method known from German Patent Application Publication No. A-4220865, in which methanol is produced under the influence of silent discharge.

[0035] Alternatively, and preferably, methanol synthesis can be carried out in a thermal reactor under pressure and high temperature in the presence of a copper-based catalyst (German Patent Application Publication No. 4332789A1; German Patent Application Publication No. 19739773A1).

[0036] Typical catalysts are described, for example, in the publication N. Kanoun et al., “Catalytic properties of Cu-based Catalysts containing Zr and / or V for methanol synthesis from a carbon dioxide and hydrogen mixture”, Catalysis Letters 15(1992)231-235. Possible catalysts, such as CuO / ZnO and Cu-ZnO-Al2O3, are also described in R. Navarro et al.: “Methanol Synthesis from CO2: A Review of the Latest Developments in Heterogeneous Catalysis” Materials (2019),12,3902 and “Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies”, Chemical Engineering Research and Design 92(2014)2557-2567.

[0037] Recently, highly selective In2O3 / ZrO2 catalysts for use under industrially applicable conditions have been described. Typical industrially applicable conditions for hydrogenating CO2 to methanol include T=200-300°C, p=10-50 MPa, and gas space velocity (GHSV) of 16,000-48,000 h. -1 (Angew. Chem. Int. Ed. 2016, 55, 6261-6265).

[0038] This process can be carried out in the presence of a copper-zinc-alumina catalyst. When using a copper-zinc-alumina catalyst, the preferred temperature is in the range of 150 to 300°C, preferably 175 to 300°C, and the preferred pressure is in the range of 10 to 150 bar (abs).

[0039] The conversion of methanol to ethylene oxide via ethene is described, for example, in U.S. Patent Application Publication No. 2002 / 132864A1; the subsequent conversion of ethylene oxide to monoethylene glycol using water is industrially standard.

[0040] In a preferred embodiment, the hydrogen used in this hydrogenation is not obtained from fossil resources but from the electrolysis of water, and the power for the electrolysis is more preferably obtained from a renewable energy source. Hydrogen obtained from the electrolysis of water is known to have a deuterium content lower than natural levels, preferably less than 90 ppm. This low deuterium content is then reflected in the corresponding conversion product. Such a process for producing methanol from CO2 is described in International Publication Brochure 2023 / 213583; the production of monoethylene glycol is described in the unpublished European Patent Application No. (reference) 23206933.6, filed on 31 October 2023. According to this latter application, particularly preferred monoethylene glycol has a deuterium content of 117 ppm or less, preferably 115 ppm or less, more preferably 113 ppm or less, and most preferably 110 ppm or less.

[0041] From C2 compounds In this modified form of manufacturing, the existing C2 carbon skeleton is typically modified by oxidation or reduction, and at least a portion of the parent C2 species is preferably entirely derived from natural sources or obtained from renewable raw materials.

[0042] For example, monoethylene glycol can be produced by reducing the following substances, which are derived from natural sources or obtained from renewable raw materials: glycolic acid (HO-CH2-COOH), glyoxylic acid (OHC-COOH), oxalic acid (HOOC-COOH), glyoxal (OHC-CHO), and / or glycolaldehyde (HO-CH2-CHO), or mixtures thereof. In this specification, these compounds, individually or as mixtures thereof, are referred to as “precursors” of monoethylene glycol.

[0043] Reduction can be carried out biochemically or by hydrogenation using conventional chemical methods. Electrochemical reduction to monoethylene glycol is also a possibility.

[0044] Alternatively, ethanol, acetaldehyde, or acetic acid, or mixtures thereof, derived from natural sources or renewable raw materials, may be used. These are first oxidized to one of the aforementioned components and then reduced. Oxidation can be carried out biochemically or by conventional chemical methods.

[0045] In certain embodiments, some or all of ethene or propene can be produced from renewable raw materials. This can be done, for example, by replacing or adding some or all of naphtha with renewable raw materials in a steam cracker or other cracking operation, and then converting the thus obtained ethene or propene to ethylene oxide or propylene oxide by known methods, and then to monoethylene glycol or monopropylene glycol.

[0046] In one embodiment, the renewable raw material is biogas, i.e., a mixture of gases formed by the fermentation of biomass, which mainly contains methane as a hydrocarbon. Further components of biogas are generally carbon dioxide (CO2) and usually, in addition to this, nitrogen (N2), oxygen (O2), hydrogen sulfide (H2S), hydrogen (H2) and / or ammonia (NH3). However, these further components are preferably separated before reuse.

[0047] For example, the following can be used as biomass for fermentation: - Fermentable biomass-containing residues such as sludge, plant waste, or food residues - Industrial fertilizers (liquid compost, manure), - Plants or parts of plants that have no other use (intercropping crops or plant residues) and - Specially cultivated energy crops.

[0048] Examples include corn, pasture grass, rye and sugar beets, feed beets, plant waste, sugarcane-derived silage, and manure or liquid compost derived from the raising of chickens, pigs and cattle.

[0049] In a further preferred embodiment, the preferred renewable raw material in this case is a fat or oil, more preferably a triglyceride comprising stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and / or linolenic acid.

[0050] Industrially common oils and fats, such as beef tallow, coconut oil, fish oil, coconut kernel oil, rapeseed oil, soybean oil, colza oil, peanut oil, macauba oil, and palm oil containing oleic acid and palmitic acid as main components, are particularly preferred.

[0051] Other possible substrates include fatty acids obtained by the hydrolysis of oils and fats, such as stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and / or linolenic acid. Industrially common fatty acid mixtures are preferably beef tallow fatty acids, coconut oil fatty acids, fish oil fatty acids, coconut kernel oil fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, peanut oil fatty acids, or palm oil fatty acids mainly composed of oleic acid and palmitic acid.

[0052] In certain embodiments, when oil obtained from palm palm is used, the oil is extracted from palm palm, preferably from palm palms of the genus Acrocomia, more preferably from macau palm, particularly from Acrocomia aculeata, the oil is extracted from palm palm pulp and / or palm palm kernel, the plant is preferably macau palm, the oil is extracted from macau palm kernel, particularly from Acrocomia aculeata, the plant is Acrocomia aculeata, and the oil is extracted from Acrocomia aculeata kernel.

[0053] As used herein, the term “macauva palm” refers to a species of palm tree. Representative species include “Acrocomia aculeata” (also known as “macaiba,” “boicaiuva,” “macauva,” “coco-de-catarro,” “coco-baboso,” and “coco-de-espinho”), “Acrocomia hassleri,” and “Acrocomia totei.” For example, the macauva palm can grow to a height of approximately 15m. The fruit of the macauva consists of pulp and a seed. As used herein, the term “pulp” refers to the inner pulp of the fruit. As used herein, the term "kernel" is interchangeable with "seed" or "almond."

[0054] Makau palm has a high oil yield per ton / hectare / year. The term “oil yield per ton / hectare / year” as used herein refers to oil obtained, for example, through extraction, from the fruit, including the pulp and kernel of the plant. This represents the oil production per hectare. It will be clear that this value refers to the oil yield obtained from a monoculture of the plant, grown under standard conditions known to those skilled in the art, which vary depending on the specific plant. Therefore, if the plant is not grown in a monoculture (e.g., cattle pasture), the respective values ​​for this particular cultivation may decrease. Typically, the oil yield per ton / hectare / year for oil palm is approximately 3.8 t / ha / year, for rapeseed it is approximately 0.8 t / ha / year, for sunflower it is approximately 0.7 t / ha / year, and for soybeans it is approximately 0.6 t / ha / year.

[0055] As used herein, the term "monoculture" refers to cultivating only one type of plant, such as macau palm, on farmland at a time. Taking macau palm as an example, it is possible to plant approximately 500 to 600 palm trees per hectare. In this specification, the distance between trees is preferably at least 3.5 to 4.5 meters. This value may vary, for example, depending on the soil.

[0056] While this process does not mitigate the drawbacks associated with handling ethylene oxide and / or ethylene glycol, it does reduce the carbon footprint by replacing some or all of the fossil-derived raw materials with those derived from renewable resources. One advantage of this modified form of production is that it does not require any modification to existing ethylene oxide or ethylene glycol production facilities, and as a result, established and optimized processes can continue to operate without significant changes, even when renewable-source-based ethene is available.

[0057] C ≧3 From the compound In preferred embodiments, monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, is obtained from an optionally repeating organic compound of a renewable raw material having at least three carbon atoms. Preferably, these compounds have 3 to 20, preferably 4 to 18, more preferably 5 to 16, even more preferably 6 to 14, and especially 6 carbon atoms. These compounds may, for example, be in monomeric form or in biopolymer form.

[0058] The compound may be derived from plants or animals, and is preferably derived from plants.

[0059] Carbohydrate substrates are preferred; in particular, monomeric sugars and biopolymer forms of starch, fiber, lignin, cellulose, and hemicellulose are preferred. Sugars are preferably selected from the group consisting of arabinose, fructose, galactose, glucose, lactose, mannose, maltose, sucrose, and xylose. Carbohydrates may preferably be biopolymers based on one or more of these sugars.

[0060] Although not particularly desirable, another substrate that can be considered is oils and fats, such as triglycerides containing stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and / or linolenic acid.

[0061] Commonly used oils and fats in industry include beef tallow, coconut oil, fish oil, coconut kernel oil, rapeseed oil, soybean oil, colza oil, peanut oil, and palm oil, which is mainly composed of oleic acid and palmitic acid.

[0062] Other possible substrates include fatty acids obtained by the hydrolysis of oils and fats, such as stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and / or linolenic acid. Industrially common fatty acid mixtures are preferably beef tallow fatty acids, coconut oil fatty acids, fish oil fatty acids, coconut kernel oil fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, peanut oil fatty acids, or palm oil fatty acids mainly composed of oleic acid and palmitic acid.

[0063] In a preferred embodiment, monoethylene glycol is obtained from a carbohydrate substrate. In this case, monoethylene glycol can be obtained from the main product derived from the conversion of the carbohydrate substrate, either as a by-product or in a precursor form, from which monoethylene glycol can then be prepared, preferably by hydrogenation.

[0064] The conversion of hydrocarbon substrates can preferably be carried out by the following reaction: - Hydrolysis - Fermentation - pyrolysis - Hydrocracking.

[0065] Hydrolysis For this purpose, the carbohydrate substrate is reacted with water in one or more steps, and optionally further reacted with at least one acid and / or at least one enzyme (see the "Fermentation" section below).

[0066] In other words, in many cases, biomacromolecules such as cellulose, hemicellulose, or lignin are cleaved into low polymers or monomers of sugars by using water and optionally at least one acid at high temperatures. These are then cleaved into monoethylene glycol and / or its precursors by using water and optionally at least one acid or at least one enzyme.

[0067] The precursors used herein may be glycolic acid (HO-CH2-COOH), glyoxylic acid (OHC-COOH), oxalic acid (HOOC-COOH), glyoxal (OHC-CHO), and / or glycolaldehyde (HO-CH2-CHO), or mixtures thereof.

[0068] fermentation During the fermentation process, the carbohydrate substrate is incubated in the presence of at least one microorganism or at least one enzyme to obtain monoethylene glycol and / or its precursor (see above).

[0069] For this purpose, it may be necessary to pre-treat the carbohydrate substrate by, for example, acid and / or alkali cleavage or hydrolysis at high temperatures. This is particularly suitable when the carbohydrate substrate is a high molecular weight, as it is needed to cleave it into oligomeric or monomeric carbohydrates.

[0070] When acid cleavage is performed, the carbohydrate substrate is treated with at least one acid, preferably hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, carbonic acid, formic acid, acetic acid, citric acid, tartaric acid, glucuronic acid, galacturonic acid, or succinic acid. Equally possible are its precursors, such as hydrogen chloride, phosphorus(V) oxide, disulfuric acid, sulfur dioxide, sulfur trioxide, or carbon dioxide.

[0071] The temperature for the acid treatment is 100 to 270°C, preferably 120 to 230°C, more preferably 130 to 200°C, and the duration is 1 to 300 minutes, preferably 30 to 250 minutes, more preferably 60 to 150 minutes.

[0072] In the case of alkaline cleavage, the carbohydrate substrate is treated with at least one base, preferably calcium hydroxide (Ca(OH)2), calcium oxide (CaO), ammonia, sodium hydroxide (NaOH), sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3), potassium hydroxide (KOH), potassium carbonate (K2CO3), potassium bicarbonate (KHCO3), or a mixture thereof.

[0073] The alkaline treatment temperature is 50 to 150°C, preferably 70 to 120°C, more preferably 80 to 100°C, and the duration is 1 to 300 minutes, preferably 30 to 250 minutes, more preferably 60 to 150 minutes.

[0074] It is preferable to use carbohydrate substrates; in particular, monomeric forms of sugars and biopolymer forms of starch, fiber, lignin, cellulose, and hemicellulose are preferred. Sugars are preferably selected from the group consisting of arabinose, fructose, galactose, glucose, lactose, mannose, maltose, sucrose, and xylose. Carbohydrates may preferably be biopolymers based on one or more of these sugars, preferably starch, lignin, cellulose, and hemicellulose.

[0075] The microorganisms may be genetically modified microorganisms, fungi, or yeasts.

[0076] Preferred microorganisms are those belonging to the genera Thermoanaerobacterium, Thermoanaerobacter, Clostridium, Geobacillus, Saccharococcus, Paenibacillus, Bacillus, or Anoxybacillus, and more preferably Thermoanaerobacterium thermosulfurigenes, Thermoanaerobacterium aotearoense, and Thermoanaerobacterium polysaccharoliticum. Thermoanaerobacterium polysaccharolyticum, Thermoanaerobacterium zeae, Thermoanaerobacterium xylanolyticum, Thermoanaerobacterium saccharolyticum, Thermoanaerobacterium brockii, Thermoanaerobacterium thermosaccharolyticum, Thermoanaerobacter thermohydrosulfuricus, Thermoanaerobacter ethanolicus, Thermoanaerobacter brockii brocki), Clostridium thermocellum, Geobacillus thermoglucosidasiusThe group is selected from the following species: thermoglucosidasius, Geobacillus stearothermophilus, Saccharococcus caldoxylosilyticus, Saccharococcus thermophilics, Paenibacillus campinasensis, Bacillus flavothermus, Anoxybacillus kamchatkensis, and Anoxybacillus gonensis.

[0077] The fungi are preferably selected from the group consisting of the phyla Chytridiomycota, Blastocoladiomycota, Neocallimastigomycota, Zygomycota, Glomeromycota, Ascomycota, Basidiomycota, and Trichoderma reesei Rut 30.

[0078] Preferred yeasts are selected from the group consisting of Ascomycota, Basidiomycota, and Saccharomycetales.

[0079] Enzymes useful for hydrolyzing carbohydrate substrates, preferably those that have been previously subjected to acid and / or base cleavage, are preferably cellulose-degrading enzymes or cellulases, more preferably endoglucanases, cellobiohydrolases or β-glucosidases, polypeptides that enhance cellulose-degrading enzymes, more preferably GH61 polypeptides, hemicellulose-degrading enzymes or hemicellulases, xylanases, β-xylosidases, acetylxylanesterases, feruloylesterases, α-glucuronidases or α-L-arabinofuranosidases. These enzymes and fermentation conditions are known, for example, from International Publication No. 2012 / 075963 or International Publication No. 2015 / 17869.

[0080] Fermentation is preferably carried out at a temperature of 20-60°C, more preferably 25-50°C, and most preferably 32-50°C. The pH during fermentation is preferably 3-7, more preferably 4-6, and most preferably 4-5.

[0081] For example, monoethylene glycol and / or its precursors are often obtained as by-products, such as in the fermentation of ethanol from carbohydrate substrates, and these can be separated from there by distillation or other methods.

[0082] Traditionally, glucose has been fermented to produce ethanol, and ethene has been obtained from the ethanol by dehydration. This ethene can then be used as a bio-based ethene in the conventional production process of monoethylene glycol via ethylene oxide. However, fermenting glucose to produce ethanol generates 2 moles of CO2 per mole of glucose, and therefore this method has the disadvantage of having an atom economy of only 67%.

[0083] pyrolysis In the thermal decomposition process, the sugar is heated to a high temperature and thermally cleaved, preferably as a monosaccharide or disaccharide, more preferably as a monosaccharide, and more preferably as a monomer (hexose). The reaction mixture obtained by thermal decomposition mainly consists of C1, C3 and / or C4 species as precursors and by-products of monoethylene glycol.

[0084] Preferred monosaccharides are arabinose, fructose, galactose, glucose, lactose, mannose, maltose, sucrose, and xylose, more preferably glucose.

[0085] The thermal decomposition of sugars can be carried out in an aqueous solution or an alcoholic solution, preferably an aqueous alcoholic solution, and particularly preferably an aqueous solution. As the alcohol, methanol, ethanol, ethylene glycol, or propylene glycol, or mixtures thereof can be used.

[0086] For example, a method for thermal decomposition is described in International Publication No. 2002 / 40436A1. This involves thermal decomposition of an aqueous solution of sugar, preferably glucose, in a fine mist form, at 500-600°C, preferably 520-560°C, for a residence time of 0.1-5 seconds, preferably 0.5-2 seconds. The resulting reaction mixture is condensed and contains glycolaldehyde as the main product. The by-products formed are C1, C2, C3 and / or C4 species, which are mainly so-called oxygenates, i.e., C1, C2, C3 and / or C4 species with different oxidation states of their respective carbon atoms. These C1, C2, C3 and / or C4 species generally have hydroxyl groups, aldehyde groups, keto groups and / or carboxylic acid groups. Common by-products include formaldehyde, glyoxal, acetol, and pyrubaldehyde.

[0087] From the standpoint of the stability of glycolaldehyde, it may be useful to first oxidize glycolaldehyde to glycolic acid in the presence of oxygen and a metal, preferably a noble metal, more preferably palladium or platinum, and then hydrogenate the reaction mixture thus obtained.

[0088] The resulting reaction mixture is then hydrogenated to obtain a mixture of products containing monoethylene glycol, which is purified by distillation or other means.

[0089] Hydrogenation can be carried out in the presence of hydrogen, with a hydrogen pressure of 30 to 150 bar, preferably 40 to 140 bar, more preferably 50 to 120 bar, and at a temperature of 40 to 160°C, preferably 50 to 150°C, more preferably 60 to 130°C, and most preferably 80 to 120°C.

[0090] The hydrogenation catalysts used are generally supported copper, cobalt, ruthenium, palladium, platinum, or nickel. Suitable supports are carbon, aluminum oxide, silicates, titanium dioxide, zinc oxide, zircon, or mixtures thereof; activated carbon is a preferred support. Copper, cobalt, and nickel can also be used in the form of Raney copper, Raney cobalt, and Raney nickel.

[0091] Hydrogenation can be carried out in the gas phase or the liquid phase, preferably in the liquid phase.

[0092] Although not ideal, it is also possible to first purify the product and then hydrogenate the reaction mixture obtained from thermal decomposition.

[0093] Hydrocracking In one embodiment of hydrocracking, glucose is reduced to sorbitol and then converted to ethylene glycol by hydrocracking. An exemplary procedure is described in U.S. Patent No. 6,297,409,B1 or U.S. Patent Publication No. 2008 / 0228014,A1. The by-products formed here are typically propylene glycol and butanediol, which, since both have freezing point depressant properties (see below), are acceptable in monoethylene glycol for coolants within certain limits.

[0094] In further embodiments, the carbohydrate substrate is converted in a reactor using hydrogen, a tungsten compound, and a hydrogenocrackable metal from Group 8, 9, or 10 of the periodic table. Such a method is preferably carried out as described in International Publication No. 2016 / 114661A1.

[0095] The carbohydrate substrates available here are also polysaccharides, oligosaccharides, disaccharides, and / or monosaccharides such as arabinose, fructose, galactose, glucose, lactose, mannose, maltose, sucrose, and / or xylose. Examples of useful sources include starch, fiber, lignin, cellulose, hemicellulose, and sugars.

[0096] The tungsten compound is preferably in an oxidation state of at least +2, more preferably +5 or +6. In this case, the tungsten compound is appropriately selected from the group consisting of tungstic acid (H2WO4), ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds containing at least one group 1 or 2 element, metatungstic acid compounds containing at least one group 1 or 2 element, paratungsten compounds containing at least one group 1 or 2 element, tungsten oxide (WO3), tungsten heteropoly compounds, and combinations thereof.

[0097] The hydrogenocracable metals of Group 8, 9, or 10 of the periodic table are preferably selected from the group consisting of Cu, Fe, Ni, Co, Pt, Pd, Ru, Rh, Ir, Os, and combinations thereof.

[0098] The metal for hydrocracking is preferably selected from the noble metals Pd, Pt, Ru, Rh, Ir, and combinations thereof. These metals have been shown to yield good yields. The metal is preferably in its metallic form or in its hydride or oxide form. Metal oxides are thought to be reduced when the reaction is carried out in the presence of hydrogen.

[0099] This metal is generally supported on a carrier; suitable carriers include carbon, aluminum oxide, silicates, titanium dioxide, zinc oxide, zircon, or mixtures thereof.

[0100] The reaction is carried out, for example, at a temperature of 120-280°C, preferably 140-270°C, more preferably 150-250°C, and most preferably 160-200°C, with a hydrogen pressure of 1-16 MPa, preferably 2-12 MPa, and more preferably 3-10 MPa. The residence time is generally 5 minutes to 6 hours, preferably 5 minutes to 2 hours.

[0101] Bio-based monoethylene glycol Monoethylene glycol obtained from renewable raw materials, preferably monoethylene glycol obtained by one of the methods described above, 14 C / 12 The 14C isotope ratio can be characterized by determining it, preferably according to ASTM D 6866 ("Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis").

[0102] This test method allows the sample 14 C / 12The C isotope ratio is measured and compared with the C isotope ratio of the reference 100% bio-based material. The result obtained is the bio-based content of the sample. 14 C / 12 The use of ASTM-D6866 to derive "bio-based content" is based on the same concept as radiocarbon dating, but does not use the age equation. This analysis is performed by comparing the amount of radiocarbon (

[0103] C) in the unknown sample with a modern reference standard to determine the ratio. This metric is expressed as a percentage in units of "pMC" (percent modern carbon). If the material to be analyzed is a mixture of modern radiocarbon and fossil-derived carbon (which has a very low radiocarbon content), the resulting pMC value will be directly correlated with the amount of biomass material present in the sample. 14 A "bio-based material" is an organic material obtained from carbon in atmospheric CO2 that has been recently (on a human time scale) fixed by solar energy (photosynthesis). On land, this CO2 is absorbed or fixed by plants (e.g., crops or forest plantations). In the ocean, this CO2 is bound or fixed within them by photosynthesis by bacteria or phytoplankton. Thus, the C / C isotope ratio of bio-based materials is greater than 0. In contrast, the C / C isotope ratio of fossil-derived materials is approximately 0.

[0104] Of the carbon dioxide in the atmosphere, a small amount of carbon atoms are the radioactive isotope 14 C / 12 C. This is formed by neutrons generated by cosmic radiation colliding with nitrogen in the atmosphere, causing this nitrogen to lose a proton and become carbon with an atomic mass of 14 ( 14 C / 12 C), which is then immediately oxidized to carbon dioxide. Although a small but measurable proportion of atmospheric carbon is

[0105] 14 14 C. This is formed when neutrons generated by cosmic radiation collide with nitrogen in the atmosphere, causing this nitrogen to lose a proton and become carbon with an atomic mass of 14 ( 14 C), which then immediately oxidizes to carbon dioxide. A small but measurable proportion of atmospheric carbon is 14It exists in the form of CO2. Atmospheric carbon dioxide assimilated by green plants to produce organic molecules in a process known as photosynthesis. Almost all living organisms on Earth depend on the production of organic molecules by green plants for the chemical energy that enables their growth and reproduction. Therefore, it is formed in the atmosphere. 14 C ultimately includes all living organisms and some of their biological products that increase biomass, as well as 14 It becomes part of organisms that feed on carbon-containing biomass. In contrast, carbon derived from fossil resources, especially fuels, characterizes renewable organic molecules obtained from atmospheric carbon dioxide. 14 C: 12 It does not have a C ratio.

[0106] The monoethylene glycol used in the coolant of the present invention is according to ASTM-D6866. 14 C: 12 The biobased fraction, measured as the C ratio, is greater than 0%, preferably at least 1%, more preferably at least 5%, even more preferably at least 10%, particularly at least 20%, and especially at least 25%.

[0107] Advantageously, this bio-based percentage can be at least 30%, preferably at least 40%, more preferably at least 50%, even more preferably at least 66%, particularly at least 75%, and especially at least 85%.

[0108] If this proportion is at least 90%, preferably at least 95%, more preferably at least 98%, and even more than 100%, it can be referred to as a very predominantly or completely bio-based monoethylene glycol.

[0109] The C-14 content of a material can be determined by measuring the decay of C-14 in the material using liquid scintillation. Preferably, if the C-14 contained in such a raw material exhibits radioactive decay of 1.5 dpm / gC (decay rate per gram of carbon per minute) or more, preferably 2 dpm / gC or more, more preferably 2.5 dpm / gC or more, and even more preferably 5 dpm / gC or more, then this raw material is considered to have been obtained from renewable raw materials.

[0110] The monoethylene glycol used in the coolant can be obtained from entirely renewable sources, or it can consist of a blend of monoethylene glycol derived from renewable and fossil resources.

[0111] In particular, when forming monoethylene glycol from a C1 source (see above), the monoethylene glycol 14 C: 12 The C ratio is determined by the C1 source, i.e., CO and / or CO2, especially in CO2. 14 C: 12 It should be emphasized that this is determined by the carbon ratio. Therefore, if part of the carbon source is fossil-derived and part is renewable resource-derived, the proportion of bio-based material in the product will still be less than 100%. In extreme cases, if the CO2 used is entirely derived from fossil raw materials, even if it is collected and utilized for monoethylene glycol production, i.e., even if it comes from a carbon capture and utilization process (CCU), the proportion of fossil-derived carbon may be 100% and the proportion of bio-based carbon may be 0%. Nevertheless, even monoethylene glycol obtained in this way still conforms to the present invention in that it fixes CO2 and reduces the carbon footprint of monoethylene glycol. This is because the product constitutes a carbon sink in that it removes CO2 formed from fossils from the atmosphere or prevents it from being released into the atmosphere by converting it.

[0112] range of by-products Monoethylene glycol or monopropylene glycol obtained from renewable raw materials has an advantage over those obtained from the hydrolysis of ethylene oxide or propylene oxide in that it contains less of these lower molecular weight polymers.

[0113] Generally, the proportion (total) of the higher molecular weight low polymers in the monoethylene glycol or monopropylene glycol thus obtained, i.e., preferably di-, tri-, and tetraethylene and propylene glycol, is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight, and particularly less than 0.5% by weight.

[0114] The proportion of these higher molecular weight low polymers, particularly diethylene glycol, is preferably 0.4% by weight or less, more preferably 0.2% by weight or less, even more preferably 0.15% by weight or less, especially 0.1% by weight or less, and especially 0.05% by weight or less.

[0115] As mentioned above, these low polymers have surfactant properties, so using monoethylene glycol or monopropylene glycol derived from renewable raw materials results in a lower tendency to foam.

[0116] Depending on the manufacturing process described above, the monoethylene glycol or monopropylene glycol thus obtained from renewable raw materials may also contain other by-products.

[0117] For example, the monoethylene glycol obtained in this way contains at least one of the following specific components: - Diethylene glycol in an amount of 0.01 to 0.25% by weight, preferably 0.02 to 0.2% by weight, more preferably 0.03 to 0.15% by weight, and most preferably 0.03 to 0.1% by weight. - 1,2-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,3-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,2-butylene glycol and / or in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 2,3-butylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. It may include.

[0118] A lower diethylene glycol content results in less foaming of the coolant.

[0119] Therefore, the monopropylene glycol thus obtained contains, for example, at least one of the specific components: - 1,2-ethylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,3-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,2-butylene glycol and / or in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 2,3-butylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. It may include.

[0120] These glycols, which may be present as by-products, are also effective as freezing point depressants and do not significantly impair the freezing point depressant effect; therefore, a certain amount may remain in the monoethylene glycol or monopropylene glycol. These glycols may even have higher thermal stability, heat capacity, or thermal conductivity than monoethylene glycol or monopropylene glycol, which is advantageous under the conditions of a cooling circuit.

[0121] Furthermore, glycols containing secondary hydroxyl groups, namely 1,2-propylene glycol, 1,2-butylene glycol, and 2,3-butylene glycol, are more stable to oxidation than 1,2-ethylene glycol. 1,2-ethylene glycol forms glycolic acid upon oxidation, which is corrosive in cooling systems. Similar acid formation is less likely to occur with 1,2-propylene glycol and 1,2-butylene glycol, and in the case of 2,3-butylene glycol, it is not a problem under the conditions of a cooling circuit.

[0122] Furthermore, these may also contain alkanols such as ethanol, 1-propanolol, 2-propanolol, 1-propanol, 2-butanol and / or isobutanol in amounts of 1% by weight or less, preferably 0.75% by weight or less, more preferably 0.5% by weight or less, even more preferably 0.25% by weight or less, and particularly 0.15% by weight or less.

[0123] Furthermore, these may also contain oxidation products, namely, in the case of monoethylene glycol, glycolic acid (HO-CH2-COOH), glyoxylic acid (OHC-COOH), oxalic acid (HOOC-COOH), glyoxal (OHC-CHO), and / or glycolaldehyde (HO-CH2-CHO), or in the case of monopropylene glycol, similar products, in an amount of 2% by weight or less, preferably 1.5% by weight or less, more preferably 1% by weight or less, even more preferably 0.75% by weight or less, and particularly 0.5% by weight or less.

[0124] The advantage of using renewable raw materials in the above-described manufacturing process is that the boiling point of the by-products is lower than that of the low polymer, thus reducing the energy requirements of this manufacturing process.

[0125] coolant Therefore, the present invention provides a coolant comprising monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials, as a glycol component that lowers the freezing point.

[0126] This is especially true - Water (A) at least 40% by weight, - Alkylene glycol, alkylene glycol monoalkyl ether and glycerol (B) in an amount of at least 30% by weight, As an inhibitor (C): - (C1) At least one inorganic compound selected from the group consisting of silicates, borates, nitrates, molybdates, and phosphates, - (C2a) Optionally, benzoic acid as an aromatic monocarboxylic acid, - (C2b) at least one aliphatic monocarboxylic acid, - (C3) At least one organic dicarboxylic acid having 4 to 20 carbon atoms, - (C4) at least one azole compound, preferably at least one triazole compound, - (D) Optionally, at least one inorganic base, - (E) At least one other component selected from the group consisting of hard water stabilizers, defoamers, dyes, and bittering substances. Includes, Component (B) is a coolant containing at least some monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

[0127] component (A) Water The water used in connection with the present invention should be neutral with a pH of 7; this may be demineralized water or distilled water, although this is not strictly necessary. To allow the use of hard water, the compositions of the present invention generally include at least one hard water stabilizer (see below).

[0128] (B) Alkylene glycol, alkylene glycol monoalkyl ether and glycerol In the coolant, component (B) primarily exhibits a freezing point depression effect.

[0129] According to the present invention, component (B) includes, at least to some extent, monoethylene glycol and / or monopropylene glycol obtained at least partially from renewable raw materials, preferably monoethylene glycol.

[0130] In addition to this monoethylene glycol and / or monopropylene glycol obtained from renewable sources, component (B) may also contain other alkylene glycols, alkylene glycol monoalkyl ethers, or glycerols, which are monoethylene glycol and / or monopropylene glycols not obtained from renewable sources.

[0131] However, in a preferred embodiment of the present invention, component (B) consists solely of monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol.

[0132] In a particularly preferred embodiment, the monoethylene glycol and / or monopropylene glycol used, preferably at least 10%, preferably at least 20%, more preferably at least 30%, most preferably at least 40%, particularly at least 50%, and especially at least 66% of the monoethylene glycol, is derived from renewable raw materials.

[0133] Advantageously, this percentage can be at least 75%, preferably at least 85%, more preferably at least 90%, even more preferably at least 95%, particularly at least 98%, and especially even 100%.

[0134] Other types of component (B) other than monoethylene glycol and / or monopropylene glycol obtained from renewable raw materials are monomer-to-tetrameric 1,2-ethylene glycol, 1,2-propylene glycol, or, less commonly, 1,3-propylene glycol, preferably monomer-to-trimeric 1,2-ethylene glycol or 1,2-propylene glycol, more preferably monomer-to-dimeric 1,2-ethylene glycol, even more preferably monomeric 1,2-ethylene glycol, and mixtures thereof in each case.

[0135] The alkylene glycol monoalkyl ether is a mono-C1 to C4 alkyl ether of the alkylene glycol described above, preferably monomethyl, monoethyl, or mono-n-butyl ether, more preferably monomethyl or mono-n-butyl ether, and most preferably monomethyl ether.

[0136] Furthermore, glycerol or a low polymer of glycerol can also be used as component (B).

[0137] Preferred alkylene glycol components or derivatives include, in particular, monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and mixtures thereof, but in addition to these, monopropylene glycol, dipropylene glycol and mixtures thereof, polyglycols, glycol ethers, such as monoethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, monoethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether, or glycerol, can also be used individually or as mixtures thereof.

[0138] Particularly preferred are monoethylene glycol alone or a mixture mainly composed of monoethylene glycol, that is, a mixture in which the content of monoethylene glycol in a mixture with other alkylene glycols or alkylene glycol derivatives is more than 50% by weight, especially more than 80% by weight, and especially more than 95% by weight.

[0139] Inhibitor (C) The inhibitor (C) acts as a corrosion inhibitor against metal corrosion of materials containing iron, aluminum, non-ferrous metals, or solder, for example.

[0140] The composition of the present invention, - (C1) At least one inorganic compound selected from the group consisting of silicates, borates, nitrates, molybdates, phosphates, and organosilicates, - (C2a) Optionally, benzoic acid as an aromatic monocarboxylic acid, - (C2b) at least one aliphatic monocarboxylic acid, - (C3) At least one organic dicarboxylic acid having 4 to 20 carbon atoms, - (C4) at least one azole, preferably at least one triazole compound Includes.

[0141] Inorganic inhibitor (C1) The inorganic inhibitor (C1) is a silicate, borate, nitrate, molybdate, or phosphate, or a mixture thereof, in the form of a free acid or its salt, particularly an alkali metal salt thereof, more preferably a sodium or potassium salt thereof. The form in which these are used in a composition, superconcentrate, concentrate, or coolant (protonated form or salt form) is determined by the amount of base (D) in the compound and composition, respectively. a Furthermore, it depends on the pH of each medium.

[0142] Inorganic silicates primarily act as corrosion inhibitors for aluminum and are usually used in the form of alkali metal salts, or less commonly, magnesium, calcium, or aluminum salts, preferably in the form of sodium or potassium salts.

[0143] The silicate is preferably orthosilicate (SiO4 4- ), metasilicate (SiO3 2- ) and pyrosilicate (Si2O7 6- Selected from the group consisting of ), more preferably metasilicate (SiO3 2- ), more preferably sodium metasilicate (Na2SiO3) or potassium metasilicate (K2SiO3), particularly sodium metasilicate (Na2SiO3).

[0144] If the solid composition of the present invention contains at least one inorganic silicate or organic silicate ester, in preferred embodiments, at least one silicophosphonate is added in addition to the silicate, as described in European Patent No. 4015596, or in the case of silicate esters, in International Publication No. 2022 / 043303.

[0145] Silicophosphonates are preferably of the general formula: [ka] (In the formula, R 5 This is a divalent organic group, preferably a 1,ω-alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene or 1,4-butylene, even more preferably 1,2-ethylene or 1,3-propylene, particularly 1,2-ethylene. R 6 These are independently hydrogen, C1-C4-alkyl or hydroxy-C2-C4-alkyl, preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, 2-hydroxyethyl or 2-hydroxypropyl, more preferably hydrogen, methyl, ethyl or propyl. R 7 The compound is a C1-C4 alkyl group, preferably methyl, ethyl, n-propyl, or n-butyl, more preferably methyl, ethyl, or n-butyl, even more preferably methyl or ethyl, particularly methyl.

[0146] Silicophosphonates can be used in free acid form or as alkali metal salts, preferably as sodium or potassium salts, and more preferably as sodium salts.

[0147] The borate is preferably used in the form of sodium tetraborate (borax) or potassium tetraborate, more preferably sodium tetraborate.

[0148] Nitrates are used in the form of alkali metal or alkaline earth metal nitrates, preferably sodium nitrate, potassium nitrate, or magnesium nitrate, preferably sodium nitrate or potassium nitrate, and more preferably sodium nitrate.

[0149] The phosphate is used as a free acid (H3PO4), a hydrogen phosphate, a dihydrogen phosphate, or a phosphate, preferably as a sodium or potassium salt.

[0150] While the use of corresponding diphosphate, triphosphate, or oligophosphate salts is also conceivable, these are preferably used in monomeric phosphates.

[0151] It is preferable to use free acid (H3PO4), disodium hydrogen phosphate, or trisodium phosphate.

[0152] Orthosilicate esters are given by formula: Si(OR 1 )4 (In the formula, R 1 This is a compound of an organic substituent having 1 to 6 carbon atoms, for example, a linear or branched substituent having 1 to 6 carbon atoms, preferably a linear alkyl substituent or an aromatic substituent having 6 carbon atoms, more preferably an alkyl substituent having 1 to 4 carbon atoms, and most preferably an alkyl substituent having 1 or 2 carbon atoms.

[0153] Alkoxyalkylsilanes are less preferred, and both the alkoxy substituent and the alkyl group include linear or branched alkyl substituents having 1 to 6 carbon atoms, preferably linear alkyl substituents, more preferably alkyl substituents having 1 to 4 carbon atoms, and most preferably alkyl substituents having 1 or 2 carbon atoms.

[0154] Typical examples of compound (D) are tetraalkoxysilanes, preferably tetramethoxysilane and tetraethoxysilane, and alkoxyalkylsilanes, preferably triethoxymethylsilane, dithoxydim-thylsilane, ethoxytrimethylsilane, trimethoxymethylsilane, dimethoxydimethylsilane, and methoxytrimethylsilane. Tetraalkoxysilanes are preferred, tetramethoxysilane and tetraethoxysilanes are particularly preferred, and tetraethoxysilanes are especially very preferred.

[0155] Component (C1) is preferably at least one compound selected from the group consisting of silicates, borates, nitrates, or phosphates, and more preferably at least one compound selected from the group consisting of silicates, nitrates, or phosphates.

[0156] (C2a) Aromatic monocarboxylic acid Optionally, the aromatic monocarboxylic acid is preferably benzoic acid, which can be used as a free acid or more preferably in the form of its alkali metal salt, most preferably as sodium benzoate.

[0157] In preferred embodiments of the present invention, aromatic monocarboxylic acids are absent.

[0158] (C2b) Aliphatic monocarboxylic acid Aliphatic monocarboxylic acids are organoaliphatic alkane carboxylic acids or alkene carboxylic acids. Those with sufficient water solubility are frequently used in coolants as corrosion inhibitors to combat the corrosion of iron-containing materials. Preferably, these are aliphatic monocarboxylic acids having 5 to 12, more preferably 6 to 10, and most preferably 8, 9, or 10 carbon atoms.

[0159] Typical monocarboxylic acids of this type include pentanoic acid, 2,2-dimethylpropanoic acid, hexanoic acid, 2,2-dimethylbutanoic acid, octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, isononanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid, as well as mixtures of their isomers, particularly mixtures of isomers of 2-ethylhexanoic acid, n-nonanoic acid, and isononanoic acid.

[0160] However, one possible embodiment is to use the aliphatic monocarboxylic acid not as a free acid, but in the form of its alkali metal salt, preferably in the form of its lithium, sodium, or potassium salt, more preferably in the form of its sodium or potassium salt.

[0161] (C3) Organic dicarboxylic acids having 4 to 20 carbon atoms The organic dicarboxylic acid having 4 to 20 carbon atoms is a linear or branched alkanedicarboxylic acid, preferably a linear alkane- or alkenedicarboxylic acid, more preferably a linear alkanedicarboxylic acid, more preferably having 5 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms.

[0162] The dicarboxylic acid (C3) is preferably succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid (heptanediic acid), azelaic acid (nonanediic acid), sebacic acid (decanediic acid), undecanediic acid, dodecanediic acid, and alkyl- and alkenyl succinic acid and -glutaric acid, for example, 2-methylbutanediic acid, 2-ethyl-3-methylbutanediic acid, 2-ethylpentanediic acid, 2-dodecylbutanediic acid, 2- The following are selected from the group consisting of dodecenylbutanediic acid, 2-phenylbutanediic acid, 2-(p-methylphenyl)butanediic acid, 2,2-dimethylbutanediic acid, 2,3,4-trimethylpentanediic acid, 2,2,3-trimethylpentanediic acid, glutaconic acid (pento-2-enedioic acid), itaconic acid, hexa-2-enedioic acid, hexa-3-enedioic acid, 5-methylhexa-2-enedioic acid, and 2,3-dimethylpenta-2-enedioic acid.

[0163] Among these, dicarboxylic acids having 6 to 12 carbon atoms are preferred, and among these, alkanedicarboxylic acids having 6 to 12 carbon atoms are particularly preferred, and linear alkanedicarboxylic acids having 6 to 12 carbon atoms are especially very preferred.

[0164] Particularly preferred dicarboxylic acids (D3) are adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid.

[0165] (C4) Azole compounds As used herein, azole derivatives (C4) are understood to mean five-membered heterocyclic compounds having two or three heteroatoms from the group consisting of nitrogen and sulfur, wherein the ring either does not contain a sulfur atom or incorporates up to one sulfur atom, and may optionally have an aromatic or saturated six-membered fused ring.

[0166] Such five-membered heterocyclic compounds (azole derivatives) typically contain two nitrogen atoms and no sulfur atoms, or three nitrogen atoms and no sulfur atoms, or one nitrogen atom and one sulfur atom.

[0167] The preferred group of the above-mentioned azole derivative is the general formula: [ka] (In the formula, The variable element R is hydrogen or C1~C 10 - Alkyl alkyl groups, particularly methyl or ethyl, The variable element X is a condensed imidazole or condensed 1,2,3-triazole (which is a nitrogen atom or a CH moiety).

[0168] Typical preferred examples of azole derivatives of general formula (III) are benzimidazole (X=CH, R=H), benzotriazole (X=N, R=H), and tolyltriazole (X=N, R=CH3). A typical example of an azole derivative of general formula (IV) is hydrogenated 1,2,3-tolyltriazole (X=N, R=CH3).

[0169] A further preferred group of the above-mentioned azole derivative is general formula (V): [ka] (In the formula, The variable element R is equivalent to the above, The variable element R' is hydrogen, C1~C 10 -A benzothiazole with an alkyl group, particularly methyl or ethyl, or particularly a mercapto group (-SH). Although not very preferred, a possible alternative is to use R' as in formula -(C m H 2m )-COOR''(where m is a number from 1 to 4, and R'' is hydrogen or C1 to C 10 -Alkyl, especially methyl or ethyl or C6-C 12 It can also be a carboxyalkyl group (which is aryl). Examples of these include (2-benzothiadylthio)acetic acid, (2-benzothiadylthio)acetic acid ester, 3-(2-benzothiadylthio)propionic acid, or 3-(2-benzothiadylthio)propionic acid ester. When these compounds are used in acid form, they are not included in the carboxylic acids excluded according to the present invention. A typical example of an azole derivative of general formula (V) is 2-mercaptobenzothiazole.

[0170] General formula (VI): [ka] (In the formula, both variable elements X and Y are two nitrogen atoms, or Non-condensed azole derivatives of nitrogen atoms and CH moieties, For example, 1H-1,2,4-triazole (X=Y=N) or preferably imidazole (X=N, Y=CH) can also be mentioned.

[0171] Particularly preferred azole derivatives of the present invention are benzimidazole, benzotriazole, toltriazole, hydrogenated toltriazole, or mixtures thereof, especially benzotriazole or toltriazole, and especially toltriazole.

[0172] The azole derivatives mentioned above are commercially available or can be manufactured by common methods. Similarly, hydrogenated benzotriazoles, such as hydrogenated toltriazole, can be produced in accordance with German Patent Application Publication A-1948794 and are also commercially available.

[0173] The azole is preferably selected from the group consisting of benzotriazole, toltriazole, (2-benzothiadylthio)acetic acid, 3-(2-benzothiadylthio)propionic acid, and 2-mercaptobenzothiazole.

[0174] (D) Inorganic bases The pH of antifreeze prepared by the end user is typically in the range of 4 to 11.5, preferably 5 to 10, and particularly 6 to 9.

[0175] To achieve this pH, at least one inorganic base (D) is added at any stage in a method for producing a coolant from a concentrate precursor. At least one inorganic base can be present in the composition of the present invention, in the superconcentrate, or in the concentrate, or it can be added by mixing it with components (A) and / or (B) in the process of producing a superconcentrate from the composition of the present invention, by mixing it with components (A) and / or (B) when producing a concentrate from the superconcentrate, or by mixing it with components (A) and / or (B) when producing a coolant from the concentrate.

[0176] Therefore, the compositions of the present invention optionally contain an amount of inorganic base that, when properly diluted, allows the coolant to achieve the desired pH. For this purpose, the compositions of the present invention preferably contain an alkali metal hydroxide, more preferably solid lithium hydroxide, sodium hydroxide, or potassium hydroxide, which may optionally be in the form of an aqueous solution of lithium hydroxide, sodium hydroxide, or potassium hydroxide.

[0177] Lithium, sodium, or potassium carbonates or bicarbonates are not very desirable.

[0178] Preferred alkali metals are sodium and potassium.

[0179] In a preferred embodiment, at least a portion, preferably all, of the inorganic bases required are already present in the composition of the present invention. This has the advantage, firstly, that there is no need to add bases in any of the later manufacturing stages, and therefore there is no risk of dosage errors; and secondly, therefore the added acid is in the form of an alkali metal salt that is more easily crystallized than usual, making it easier to formulate the solid composition of the present invention in solid form.

[0180] (E) Other components selected from the group consisting of hard water stabilizers, defoamers, dyes, and bittering substances As further conventional auxiliary agents, the compositions of the present invention may also contain, in conventional amounts, an antifoaming agent (generally in an amount of 0.003 to 0.008% by weight in the ready-diluted coolant), and, considering hygiene and safety in case of ingestion, a bittering substance (e.g., denatonium benzoate) and a dye.

[0181] Furthermore, the composition may contain one or more hard water stabilizers, primarily composed of polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, polyvinylpyrrolidone, polyvinylimidazole, vinylpyrrolidone-vinylimidazole copolymer, and / or copolymers of unsaturated carboxylic acids and olefins. The proportion in the composition is selected so that, after appropriate dilution, the amount in the ready-diluted coolant is a maximum of 1% by weight.

[0182] concentrate, super concentrate To reduce transport volume, concentrated coolants with reduced or no water content are sold instead of the original coolant with a high water content. The end user prepares the coolant from this concentrate by adding water.

[0183] To further reduce transport volume, so-called ultra-concentrates are often produced intensively, with not only water but also glycol removed or significantly reduced in quantity. These ultra-concentrates are then used by regional compounders to produce concentrates by adding glycol.

[0184] According to the present invention, it is essential that these glycols used in the formulation satisfy the requirement of the present invention that they are at least partially derived from renewable raw materials.

[0185] Furthermore, the present invention, - Water (A) in an amount of 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, - At least one alkylene glycol, alkylene glycol monoalkyl ether or glycerol (B), As an inhibitor (C): - (C1) At least one inorganic compound selected from the group consisting of silicates, borates, nitrates, molybdates, and phosphates, - (C2a) Optionally, benzoic acid as an aromatic monocarboxylic acid, - (C2b) at least one aliphatic monocarboxylic acid, - (C3) At least one organic dicarboxylic acid having 4 to 20 carbon atoms, - (C4) at least one azole compound, preferably at least one triazole compound, - (D) Optionally, at least one inorganic base, - (E) At least one other component selected from the group consisting of hard water stabilizers, defoamers, dyes, and bittering substances. Includes, Component (B) provides a coolant concentrate containing at least some monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

[0186] Furthermore, the present invention, - Water (A) in an amount of 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, - At least one alkylene glycol, alkylene glycol monoalkyl ether or glycerol (B), As an inhibitor (C): - (C1) At least one inorganic compound selected from the group consisting of silicates, borates, nitrates, molybdates, and phosphates, - (C2a) Optionally, benzoic acid as an aromatic monocarboxylic acid, - (C2b) at least one aliphatic monocarboxylic acid, - (C3) At least one organic dicarboxylic acid having 4 to 20 carbon atoms, - (C4) at least one azole, preferably at least one triazole compound, - (D) Optionally, at least one inorganic base, - (E) At least one other component selected from the group consisting of hard water stabilizers, defoamers, dyes, and bittering substances. Includes, Component (B) provides a coolant superconcentrate containing at least some monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

[0187] Furthermore, the present invention provides a process for producing a coolant concentrate from the coolant superconcentrate, comprising mixing the coolant superconcentrate with an appropriate amount of at least one alkylene glycol, alkylene glycol monoalkyl ether, or glycerol (B), wherein at least a portion of the component (B) used comprises monoethylene glycol and / or monopropylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

[0188] Sustainability Index Furthermore, the present invention provides a method for reducing emissions in the production of alkylene glycol-containing coolants, for example, emissions of nitrogen oxides and sulfur oxides, particularly carbon dioxide emissions, preferably as a carbon footprint, by life cycle assessment or in accordance with DIN EN ISO 14021, DIN EN ISO 14067, particularly 2019-02 edition as specified herein, DIN EN ISO 14044, particularly 2006+A1:2018 edition as specified herein, and / or DIN EN ISO 14040, particularly 2009-11 edition as specified herein, wherein in the production of the coolant, at least in part, at least partially, monoethylene glycol and / or monopropylene glycol obtained from renewable raw materials, preferably monoethylene glycol, is used.

[0189] The criteria for determining the life cycle assessment are preferably DIN EN ISO 14040, in particular the 2009-11 edition as specified herein, and / or DIN EN ISO 14044, in particular the 2006+A1:2018 edition as specified herein.

[0190] The standard used to determine the carbon footprint in this specification is preferably DIN EN ISO 14067, in particular the 2019-02 edition.

[0191] By producing monoethylene glycol and / or monopropylene glycol from renewable raw materials, the drawbacks detailed above are avoided, resulting in a more favorable life cycle assessment and / or a reduced carbon footprint for the monoethylene glycol and / or monopropylene glycol thus obtained.

[0192] If the CO2 used is entirely derived from fossil fuels, even if it is collected and utilized for the production of monoethylene glycol, i.e., derived from a carbon capture and utilization process (CCU), it is possible that 100% of the carbon is fossil-derived and 0% is bio-based carbon. Nevertheless, even monoethylene glycol obtained in this way still conforms to the present invention in that it fixes CO2 and reduces the carbon footprint of monoethylene glycol. This is because the product constitutes a carbon sink in that it removes CO2 formed from fossils from the atmosphere or prevents it from being released into the atmosphere by converting it.

[0193] As stated above, for example, with respect to the dehydration of glucose-derived ethanol, when all or part of the monoethylene glycol is produced from ethylene oxide or ethene derived from renewable raw materials, the advantage of the present invention lies not in avoiding the handling of ethylene oxide, but rather in the fact that even in this method, renewable raw materials are used in at least part of the production of monoethylene glycol, and this production is similarly more favorable in terms of life cycle assessment and / or has a smaller carbon footprint than production from entirely petroleum-derived raw materials.

Claims

1. It is a coolant, - Water (A) at least 40% by weight, - At least 30% by weight of alkylene glycol, alkylene glycol monoalkyl ether, and glycerol (B), As an inhibitor (C): - (C1) At least one inorganic compound selected from the group consisting of silicates, borates, nitrates, molybdates, and phosphates, - (C2a) Optionally, benzoic acid as an aromatic monocarboxylic acid, - (C2b) Optionally, at least one aliphatic monocarboxylic acid, - (C3) at least one organic dicarboxylic acid having 4 to 20 carbon atoms, - (C4) at least one azole compound, preferably at least one triazole compound, - (D) Optionally, at least one inorganic base, - (E) At least one other component selected from the group consisting of hard water stabilizers, defoamers, dyes, and bittering substances. Includes, Component (B) comprises at least partially monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials, and the monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol used is in accordance with ASTM D 6866. １４ C / １２ A coolant having a biobase, measured as a C isotope ratio, greater than 0%, preferably at least 1%, more preferably at least 5%, even more preferably at least 10%, particularly at least 20%, and especially at least 25%.

2. The component (B) used comprises monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, which is at least partially converted by genetically modified microorganisms and / or enzymes to carbon dioxide (CO2). ２ The coolant according to claim 1, which is obtained by converting ) and / or carbon monoxide (CO).

3. The component (B) used comprises monoethylene glycol, which is at least in part derived from natural sources or obtained from renewable raw materials, including the following substance: glycolic acid (HO-CH ２ (-COOH), glyoxylic acid (OHC-COOH), oxalic acid (HOOC-COOH), glyoxal (OHC-CHO) and / or glycolaldehyde (HO-CH) ２ The coolant according to claim 1, obtained by reducing -CHO) or a mixture thereof.

4. The coolant according to claim 1, wherein the component (B) used comprises monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, which is obtained at least in part by converting ethene or propene derived from cracking of renewable raw materials to ethylene oxide or propylene oxide, and subsequently to monoethylene glycol or 1,2-propylene glycol.

5. The coolant according to claim 1, wherein the component (B) used comprises monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, which is obtained by cracking an optionally repeating organic compound of a renewable raw material having at least three carbon atoms.

6. The coolant according to claim 5, wherein the organic compound of the renewable raw material is selected from the group consisting of sugar, starch, fiber, lignin, cellulose, and hemicellulose.

7. The coolant according to claim 5, wherein the organic compound of the renewable raw material comprises monomers or biopolymers based on arabinose, fructose, galactose, glucose, lactose, mannose, maltose, sucrose, and / or xylose.

8. The carbohydrate substrate is subjected to hydrolysis, fermentation, thermal decomposition, or hydrolysis to obtain monoethylene glycol and / or glycolic acid (HO-CH ２ (-COOH), glyoxylic acid (OHC-COOH), oxalic acid (HOOC-COOH), glyoxal (OHC-CHO) and / or glycolaldehyde (HO-CH) ２ The coolant according to claim 5, which is converted to a precursor selected from the group consisting of -CHO) or mixtures thereof, and any of the precursors is converted to monoethylene glycol by reduction.

9. In accordance with ASTM D 6866 １４ C / １２ The bio-based content of the monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, measured as the C / C isotope ratio, used in the coolant according to any one of claims 1 to 8 is at least 30%, preferably at least 40%, more preferably at least 50%, still more preferably at least 66%, particularly at least 75%, especially at least 85%.

10. The component (B) obtained from renewable raw materials is a specific component: - Diethylene glycol in an amount of 0.01 to 0.25% by weight, preferably 0.02 to 0.2% by weight, more preferably 0.03 to 0.15% by weight, and most preferably 0.03 to 0.1% by weight. - 1,2-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight, - 1,3-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,2-butylene glycol and / or in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 2,3-butylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. The coolant according to any one of claims 1 to 9, which is a monoethylene glycol containing at least one of the following.

11. The component (B) obtained from renewable raw materials is a specific component: - 1,2-ethylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,3-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,2-butylene glycol and / or in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 2,3-butylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. The coolant according to any one of claims 1 to 9, which is 1,2-propylene glycol containing at least one of the following.

12. Use in coolants of monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

13. Use of monoethylene glycol according to claim 12, wherein the diethylene glycol content is 0.01 to 0.25% by weight, for reducing foaming of a coolant.

14. - Diethylene glycol in an amount of 0.01 to 0.25% by weight, preferably 0.02 to 0.2% by weight, more preferably 0.03 to 0.15% by weight, and most preferably 0.03 to 0.1% by weight. - 1,2-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight, - 1,3-propylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 1,2-butylene glycol and / or in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. - 2,3-butylene glycol in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.25 to 1% by weight. Use of the monoethylene glycol according to claim 12, including, to improve the thermal stability, heat capacity, thermal conductivity and / or oxidative stability of the freezing point depression component in a coolant.

15. A method for reducing emissions in the production of an alkylene glycol-containing coolant, for example, emissions of nitrogen oxides and sulfur oxides, particularly emissions of carbon dioxide, preferably as a carbon footprint, determined by a life cycle assessment or in accordance with DIN EN ISO 14021, DIN EN ISO 14067, particularly 2019-02 edition as specified herein, DIN EN ISO 14044, particularly 2006+A1:2018 edition as specified herein, and / or DIN EN ISO 14040, particularly 2009-11 edition as specified herein, wherein the coolant is produced using at least a portion of monoethylene glycol and / or 1,2-propylene glycol, preferably monoethylene glycol, obtained at least partially from renewable raw materials.

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