WO2026027352A1 - Élimination de polyéthylèneglycols à partir d'éthoxylates - Google Patents

Élimination de polyéthylèneglycols à partir d'éthoxylates

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Publication number
WO2026027352A1
WO2026027352A1 PCT/EP2025/071067 EP2025071067W WO2026027352A1 WO 2026027352 A1 WO2026027352 A1 WO 2026027352A1 EP 2025071067 W EP2025071067 W EP 2025071067W WO 2026027352 A1 WO2026027352 A1 WO 2026027352A1
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WIPO (PCT)
Prior art keywords
particularly preferably
ethoxylated
oligo
alkanol
water
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Pending
Application number
PCT/EP2025/071067
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German (de)
English (en)
Inventor
Markus Hansch
Silvia BERG
Susan Carvalho
Petra Deckert
Christian Bittner
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from EP24192154.3A external-priority patent/EP4686718A1/fr
Application filed by BASF SE filed Critical BASF SE
Publication of WO2026027352A1 publication Critical patent/WO2026027352A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a process for separating oligo- and polyethylene glycols from ethoxylated alkanols.
  • alkanols The ethoxylation of alkanols is usually carried out industrially by reacting the alkanols with ethylene oxide under the catalysis of bases such as sodium or potassium hydroxide. Water is introduced into the reaction either through these bases or as an accompanying component of the alkanol, leading to the formation of oligoglycols and polyethylene glycols. These oligoglycols and polyethylene glycols exhibit higher hydrophilicity than the actual target products.
  • oligo- and polyethylene glycols are not detrimental, since the ethoxylated alkanols are already combined with polyethylene glycols in applications such as surfactants or cleaning and washing agents.
  • the diethylene glycol contained in oligoethylene glycols is a starting material for the formation of the toxicologically problematic dioxane; on the other hand, the hydrophilic higher ethylene glycols in the ethoxylated alkanols lead to turbidity. Furthermore, especially in the case of low-ethoxylated alkanols, where the hydrophobic character of the alkanol is pronounced, the properties of the ethoxylated alkanol are significantly impaired by the presence of the hydrophilic polyethylene glycols, as this affects the hydrophilicity-hydrophobicity balance of the product.
  • the object of the present invention was to provide a process for the removal of oligo- and polyethylene glycols from one- to three-fold ethoxylated Cs-Cu alkanols, especially those obtained from base-catalyzed ethoxylation.
  • DE 828839 describes the separation of polyglycols from reaction mixtures of the alkoxylation of alcohols, acids, phenols, alkylphenols, and naphthols with 20 to 400% water at elevated temperature.
  • the explicitly disclosed examples use 50 to 200 wt% water based on the alkoxylate, where the alkoxylates are structurally very different, but ethoxylated alcohols are not explicitly disclosed.
  • WO 2021/262439 A2 describes the extraction of polyethylene glycols from fatty alcohol ethoxylates, using at least 50 wt% water for the extraction. Such large quantities of water have the disadvantage that large quantities of the desired hydrophilic product also pass into the water phase and are thus lost.
  • WO 2021/262439 A2 also proposes extraction with electrolyte-containing solutions, for example aqueous sodium chloride solution, which facilitates phase separation.
  • EP 43963 A1 describes the ethoxylation of primary monoalcohols with Friedel-Crafts or acidic catalysts followed by basic washing. The washing serves to remove the acidic catalyst; polyethylene glycols are explicitly left in the reaction mixture.
  • EP 1015404 B1 describes the production of random polymers of fatty alcohols with ethylene oxide and propylene oxide. It notes that polyethylene glycols are formed as byproducts. These could, in principle, be removed by extraction with suitable solvents such as water, but this requires a further process step that is very time-consuming and not universally applicable.
  • n is a rational number of at least 2, preferably from 2 to 30, and particularly preferably from 2 to 20, from ethoxylated alkanols of the formula
  • R 1 straight-chain or branched, preferably straight-chain Cs-Cu-alkyl, preferably Cs-Cia-alkyl, particularly preferably C9-Ci3-alkyl, and most particularly preferably C9-C1i-alkyl and m is a rational number from 1 to 3, in which one (i) the mixture of oligo- and polyethylene glycols and ethoxylated alkanols mixed at a temperature of ambient temperature up to 90 °C with 0.05 to 10 times, for example 0.05 to 2.0 times, preferably 0.1 to 1.5 times, particularly preferably 0.15 to 1.0 times, most preferably 0.25 to 0.75 times the volume (v/v) of water per 1 volume of organic phase,
  • a preferred embodiment of the present invention consists in reducing the dissolved oxygen content in the ethoxylated alkanol and/or in the water before use in the extraction, particularly before heating to the temperature at which the extraction is carried out.
  • Another preferred embodiment of the present invention consists in reducing the dissolved oxygen content in the ethoxylated alkanol before use in the extraction to no more than 25% of the possible saturation at the storage temperature, preferably to no more than 20%, particularly preferably to no more than 15%, and most preferably to no more than 10%.
  • the storage temperature is the ambient temperature at which the ethoxylated alkanol is stored, preferably a temperature of 20 °C. Unless otherwise specified, the determination of dissolved oxygen is carried out as described below in the experimental section.
  • the present invention has the advantage that it keeps the losses of the ethoxylated alkanol as the value product low and at the same time allows both oligo- and polyethylene glycols as well as (earth)alkali metal ions to be removed from the catalyst used for the ethoxylation if the ethoxylation of the alkanol was carried out in the presence of at least one basic salt.
  • a further object of the present invention is a process for the production of ethoxylated
  • R 1 straight-chain or branched Cs-Cu alkyl, preferably Cs-C alkyl, particularly preferably Cg-C alkyl, and most preferably Cg-Cn alkyl and m a rational number of 1 to 3 with a reduced content of oligo- and polyethylene glycols of the formula
  • n is a rational number of at least 2, preferably from 2 to 30 and particularly preferably from 2 to 20, and a simultaneously reduced content of (earth)alkali metal ions, characterized in that one
  • (I) reacts an alkanol R 1 -OH with at least m equivalents of ethylene oxide in the presence of at least one basic salt of at least one (earth)alkali metal and in the presence of water at a temperature of 20 to 200 °C to obtain a mixture of oligo- and polyethylene glycols and ethoxylated alkanols and
  • Another object of the present invention is a method for separating oligo- and polyethylene glycols of the formula
  • n is a rational number of at least 2, preferably of 2 to 30 and particularly preferably of 2 to 20 from ethoxylated alkanols of the formula
  • R 1 straight-chain or branched, preferably straight-chain Cs-Cu alkyl, preferably Cs-C alkyl, particularly preferably Cg-C alkyl, and most preferably C9-C1 i-alkyl and m is a rational number from 1 to 3, wherein one
  • (iv) optionally reduces the water content of the organic phase, characterized in that, prior to extraction, the dissolved oxygen content in the ethoxylated alkanol is reduced to no more than 25% of the saturation at storage temperature, preferably to the saturation at 20 °C, preferably to no more than 20%, particularly preferably to no more than 15% and most particularly preferably to no more than 10%.
  • Another object of the present invention is a process for the preparation of ethoxylated alkanols of the formula
  • R 1 straight-chain or branched Cs-Cu alkyl, preferably Cs-Cn alkyl, particularly preferably Cg-Cn alkyl, and most preferably Cg-Cn alkyl and m a rational number of 1 to 3 with a reduced content of oligo- and polyethylene glycols of the formula HO-[-CH 2 -CH 2 -O] n -H wherein n is a rational number of at least 2, preferably from 2 to 30 and particularly preferably from 2 to 20, and a simultaneously reduced content of (earth)alkali metal ions, characterized in that one
  • (I) reacts an alkanol R 1 -OH with at least m equivalents of ethylene oxide in the presence of at least one basic salt of at least one (earth)alkali metal and in the presence of water at a temperature of 20 to 200 °C to obtain a mixture of oligo- and polyethylene glycols and ethoxylated alkanols and
  • (iv) optionally reduces the water content of the organic phase, characterized in that, prior to extraction, the dissolved oxygen content in the ethoxylated alkanol is reduced to no more than 25% of the saturation at storage temperature, preferably to the saturation at 20 °C, preferably to no more than 20%, particularly preferably to no more than 15% and most particularly preferably to no more than 10%.
  • the ethoxylated alkanols fulfill the formula
  • R 1 straight-chain or branched, preferably straight-chain Cs-Cu alkyl, preferably Cs-C alkyl, particularly preferably C9-Ci3 alkyl, and most particularly preferably C9-C1 i alkyl, and m is a rational number from 1 to 3.
  • Examples of the underlying alkanols R 1 OH are n-octanol (octyl alcohol, caprylic alcohol), 2-ethylhexanol, nonyl alcohol (pelargonyl alcohol), iso-nonanol, n-decanol, 2-propylheptanol, decyl alcohol (caprylic alcohol), undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol and tetradecyl alcohol (myristyl alcohol).
  • these are pure substances such as 2-ethylhexanol or 2-propyl heptanol.
  • the underlying alkanol R 1 OH can be a mixture of different alkanols, which on average have 8 to 14, preferably 9 to 11, carbon atoms. Since these are mixtures, the number of carbon atoms can also be non-integer values.
  • mixtures of fatty alcohols e.g., those obtained from coconut oil.
  • Such mixtures are predominantly composed of Cs to Cie alkanols with even numbers of carbon atoms, typically 4.6–10.0 wt% Cs alkanol, 5.0–8.0 wt% Cw alkanol, 45.1–53.2 wt% Ci2 alkanol, 16.8–21.0 wt% Cu alkanol, and 7.5–10.2 wt% C3 alkanol.
  • the alcohol R 1 -OH is a mixture of alcohols having about 13 carbon atoms, particularly preferably one that is obtainable by hydroformylation from a C12 olefin mixture which in turn is obtainable by oligomerization of an olefin mixture containing predominantly four carbon atoms hydrocarbons.
  • this olefin mixture has 11 to 16 carbon atoms, preferably 11.1 to 12.9, particularly preferably 11.2 to 12.8, most preferably 11.5 to 12.5 and particularly 11.8 to 12.2.
  • the alcohols obtained from it accordingly have one more carbon atom.
  • this alcohol R 1 -OH has a mean degree of branching, measured as ISO index, of 1.8 to 2.7.
  • Such mixtures are commercially available as tridecanols or iso-tridecanols.
  • the alkanol R 1 OH is a mixture of primary alcohols with the composition of 15-20 wt% C9, 40-45 wt% C10, and 35-40 wt% Cn alcohols, wherein the proportion of alcohols with 8 or fewer or with 12 or more carbon atoms is not more than 1 wt% in each case.
  • Particularly preferred are highly linear alkanols having a degree of branching, measured as an ISO index, of not more than 0.5, preferably not more than 0.3, particularly preferably not more than 0.2, and most preferably not more than 0.1.
  • the average molecular weight- The density of such an alcohol mixture ranges from 158 to 164 g/mol.
  • the OH number ranges from 342 to 355 mg KOH/g.
  • the degree of ethoxylation m of the ethoxylated alkanols is a rational number from 1 to 3, preferably 1.5 to 3, particularly preferably 1.75 to 3, very preferably 1.75 to 2.75 and particularly 2 to 2.75.
  • the degree of ethoxylation m is an arithmetic mean, therefore m can also take on non-integer values.
  • oligo- and polyethylene glycols of the formula HO-[-CH 2 -CH 2 -O] n -H are mostly formed as a by-product during the ethoxylation of alkanols.
  • the degree of polymerization n is also a rational number of at least 2, preferably from 2 to 30, and particularly preferably from 2 to 20. Here too, it is an arithmetic mean; therefore, m can also take on non-integer values.
  • the proportion of oligoglycols and polyethylene glycols in the ethoxylated alkanols varies and is mostly dependent on the water content during the ethoxylation and the reaction conditions. Due to the low molecular weight of water, even small amounts of water are sufficient to result in comparatively high concentrations of oligoglycols and polyethylene glycols.
  • Sources of water include, in particular, the alkanol used and the base used as a catalyst.
  • the base is usually used as an aqueous solution, and subsequent removal is either not entirely successful or uneconomical.
  • Other possible sources include atmospheric humidity or traces of moisture in any protective gas used, contamination in the equipment, and a small amount of water in the ethylene oxide.
  • the content of oligo- and polyethylene glycols in the ethoxylated alkanols can generally be up to 5 wt%, preferably up to 3, particularly preferably up to 2.5, most preferably up to 2, particularly up to 1.5 and especially up to 1 wt%.
  • the reaction of alkanols with ethylene oxide usually occurs under catalysis with bases, mostly basic (earth)alkali metal salts.
  • bases mostly basic (earth)alkali metal salts.
  • the (earth) alkali metal is usually sodium, potassium, magnesium or calcium, preferably sodium or potassium, especially preferably potassium.
  • the anion of these basic salts is selected from the group consisting of hydroxide, oxide, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, Ci-Cio alcoholate and Ci-Cio carboxylate, preferably hydroxide, oxide, carbonate or hydrogen carbonate, particularly preferably hydroxides.
  • Particularly preferred basic (earth)alkali metal salts are sodium hydroxide, sodium carbonate, sodium phosphate, sodium acetate, potassium hydroxide, potassium carbonate, potassium phosphate and potassium acetate; sodium hydroxide and potassium hydroxide are particularly preferred.
  • Ci-Cio alcoholates are preferred, preferably Ci-C4 alcoholates, particularly preferably methanolates or ethanolates of the (earth) alkali metals, especially sodium or potassium.
  • the underlying alkanol R 1 OH is converted to the corresponding (earth)alkali metal alkanolate prior to ethoxylation, for example by prior reaction with a methoxide or ethanolate or reaction with the metal in question, especially sodium or potassium.
  • Ethoxylation is generally carried out by reacting the alkanol R1OH and ethylene oxide in a molar ratio of at least 1 to m.
  • a molar ratio of 1 to m to 1 to (1.5 x m) is particularly advantageous, especially 1 to m to 1 to (1.25 x m), and particularly 1 to m to 1 to (1.1 x m).
  • the reaction with ethylene oxide can be carried out at 50 to 200 °C.
  • a temperature range of 100 to 180 °C is preferred, particularly 120 to 160 °C.
  • the process can be carried out at atmospheric pressure, under vacuum, and at elevated pressures, for example, at pressures from 0.8 to 50 bar (abs), particularly at pressures from 1 to 10 bar (abs). A slight overpressure up to 2 bar (abs) is especially advantageous.
  • the basic salt is used in amounts of 0.01 to 5 wt% based on the alkanol R 1 OH, preferably 0.05 to 2 wt% and particularly preferably 0.05 to 0.5 wt%.
  • the process does not require the use of solvents. However, it is possible, though less preferred, to carry out the process in the presence of organic solvents such as aliphatic, cycloaliphatic, or aromatic hydrocarbons, ethers, acetals, ketones, esters, or cyclic carbonates.
  • organic solvents such as aliphatic, cycloaliphatic, or aromatic hydrocarbons, ethers, acetals, ketones, esters, or cyclic carbonates.
  • a reaction carried out in suspension mode is advantageous, for example in one or more stirred reactors.
  • the basic salt can either remain in the reactor, for example it can be retained by a frit, filter or sieve, or it can be carried out with the reactor discharge and subsequently separated from the reaction mixture, for example by sedimentation, filtration, centrifugation or absorption, preferably by filtration, which may optionally be supported by a filtration aid such as Celite, aluminum oxide, silicates, silica gel or activated carbon.
  • the basic salt can be added to the alkanol in the form of an aqueous solution (usually around 50%), and then the water is removed under vacuum at elevated temperature until a certain water content (usually 1000 ppm) is reached. Ethylene oxide is then added to the resulting starter mixture at the appropriate reaction temperature.
  • the conversion can be carried out discontinuously, in the sense of a batch or semi-batch process, or continuously. It can be performed in a stirred reactor, tubular reactor, loop reactor, fixed-bed reactor, or fluidized-bed reactor.
  • the heat of reaction can be dissipated, for example, via a reactor jacket, welded-on half-pipe coils or pipe coils, cooling pipes in the reactor, downstream or upstream heat exchangers, a total condenser in boiling mode, or any combination of the aforementioned variants.
  • the reaction mixture is circulated in a closed loop. This is usually achieved by pumping the reaction mixture through an external circuit.
  • a heat exchanger may also be integrated into this external circuit.
  • the heat of reaction can be dissipated, for example, via a reactor jacket, welded-on half-pipe coils or pipe coils, cooling pipes in the reactor, downstream or upstream heat exchangers, a total condenser in boiling mode, or any combination of the aforementioned variants.
  • the finished ethoxylated alkanol is freed from residual ethylene oxide by applying a vacuum and, optionally, a stripping gas such as nitrogen, air, nitrogen-air mixtures, or steam.
  • a stripping gas such as nitrogen, air, nitrogen-air mixtures, or steam.
  • the ethoxylated alkanol is then purified and freed from volatile impurities, preferably by stripping in a vessel or column.
  • Ethoxylated alkanols especially those obtained by the process described above, contain oligo- and polyethylene glycols, depending on the water content of the starting materials, which can be up to 5 wt% or more.
  • the ethoxylated alkanol may also contain traces of this (earth)alkali metal, for example in amounts up to 0.5 wt%, preferably up to 0.3 wt%. Particularly preferably up to 0.2 wt% and especially up to 0.1 wt%.
  • the content of oligo- and polyethylene glycols and/or (earth)alkali metals may have a disruptive effect.
  • hydrophilic oligo- and polyethylene glycols when the hydrophobicity of the comparatively relatively hydrophobic ethoxylated alkanols is important in their application, for example in application in a hydrophobic medium, such as the distribution or dispersion of water in this hydrophobic medium in the sense of a w/o emulsion (water in oil).
  • diethylene glycol in the form of oligo- and polyethylene glycol, is a starting material for the formation of dioxane, which should be separated from the product for toxicological reasons.
  • Dioxane is formed from diethylene glycol particularly under acidic conditions, for example, during the production of polyether sulfates from ethoxylated alkanols. Therefore, the separation of the oligo- and polyethylene glycols according to the invention is preferred when the ethoxylated alkanol is exposed to acidic conditions in a subsequent use or derivatization, and is particularly preferred when the ethoxylated alkanol is later to be converted into the corresponding polyether sulfate.
  • (earth)alkali metals should also be kept as low as possible, especially in applications in a hydrophobic medium, as these cations tend to precipitate out of the hydrophobic medium and can thus lead to deposits.
  • the mixture of oligo- and polyethylene glycols and ethoxylated alkanols is subjected to a purification process in which one
  • the extraction is carried out in the presence of a gas atmosphere in which the proportion of oxygen is no more than 10 vol%, preferably no more than 8, particularly preferably no more than 6, most preferably no more than 5, in particular no more than 2 and specifically no more than 1 vol%.
  • the gas atmosphere can be oxygen-depleted air (lean air) or a gas inert under the extraction conditions, preferably nitrogen, argon or carbon dioxide, particularly preferably nitrogen.
  • steps (I), (II) or (ill) is carried out in the presence of an oxygen-deficient gas atmosphere, preferably at least one of steps (ii) or (ill), particularly preferably at least step (ii), most preferably at least steps (ii) and (ill) and in particular all three steps (i), (ii) and (ill).
  • such steps are carried out in the presence of an oxygen-deficient gas atmosphere in which the temperature of the ethoxylated alkanol reaches or exceeds at least 50 °C.
  • a preferred embodiment of the present invention consists in reducing the dissolved oxygen content in the ethoxylated alkanol and/or in the water before use in the extraction, preferably at least in the ethoxylated alkanol, and particularly preferably in both the ethoxylated alkanol and the water.
  • this reduction of the dissolved oxygen content takes place before heating to the temperature at which the extraction is carried out.
  • the reduction of the dissolved oxygen content can be achieved, for example, by applying a vacuum and/or passing a stripping gas through it, preferably a low-oxygen gas or water vapor, preferably lean air, nitrogen, argon, or water vapor, particularly preferably nitrogen or water vapor, and most preferably nitrogen.
  • a stripping gas is passed through the respective medium, optionally supported by applying a vacuum.
  • the stripping process should be carried out for at least 1 to 24 hours, preferably 1.5 to 20 hours, and most preferably 2 to 16 hours.
  • 0.1 to 20 times the volume of stripping gas relative to the volume of the ethoxylated alkanols is passed through the ethoxylated alkanol per hour, preferably 0.2 to 15 times, particularly preferably 0.5 to 10 times.
  • the stripping gas can be introduced, for example, through submerged inlet pipes, nozzles, frits, or pipes with openings for the stripping gas located in the liquid.
  • the reduction of the dissolved oxygen content can also be achieved by heating to a temperature of at least 50°C, preferably at least 60°C, particularly preferably at least 70°C, and most preferably at least 80°C.
  • a temperature of at least 50°C preferably at least 60°C, particularly preferably at least 70°C, and most preferably at least 80°C.
  • water under normal pressure has an oxygen content of less than 1 ppm (M. Ros, G. D. Zupancic, Acta Chim. Slov. 2002, 49, 931-943).
  • the water is heated to the temperature at which step (I) is carried out before contact with the ethoxylated alkanol.
  • the dissolved oxygen content in the mixture of ethoxylated alkanol and oligo- and polyethylene glycols is reduced by at least 20% compared to the saturated oxygen content of the mixture at 20 °C and normal pressure before use in the extraction process, preferably by at least 25%, particularly preferably by at least 30%, most preferably by at least 40%, particularly by at least 50%, and especially by at least 60%. It may be advantageous to reduce the oxygen content by at least 70%, at least 80%, or even at least 90%.
  • solubility of oxygen in the mixture of ethoxylated alkanol and oligo- and polyethylene glycols depends on the lipophilicity or hydrophilicity of the mixture, i.e., especially on the number of carbon atoms in the alkanol, the degree of ethoxylation, and the content of oligo- and polyethylene glycols, it is difficult to specify an absolute content of dissolved oxygen.
  • the dissolved oxygen content in the mixture of ethoxylated alkanol and oligo- and polyethylene glycols does not exceed 100 ppm by weight before use in the extraction process.
  • the concentration should not exceed 90 ppm, particularly preferably not more than 80 ppm, most preferably not more than 70 ppm, in particular not more than 60 ppm and specifically not more than 50 ppm by weight.
  • a further object of the present invention is a process for the preparation of ethoxylated alkanols of the formula
  • R 1 straight-chain or branched C9-C11 alkyl and m a rational number of 2 to 3, preferably of about 2.5, with a reduced content of oligo- and polyethylene glycols of the formula HO-[- CH2 - CH2 -O] n -H, wherein n is a rational number of at least 2, preferably of 2 to 30 and particularly preferably of 2 to 20, and a simultaneously reduced content of (earth)alkali metal ions, characterized in that one
  • (I) reacts an alkanol R 1 -OH with at least m equivalents of ethylene oxide in the presence of at least one basic salt of at least one (earth)alkali metal and in the presence of water at a temperature of 20 to 200 °C to obtain a mixture of oligo- and polyethylene glycols and ethoxylated alkanols and
  • step (i) the mixture of oligo- and polyethylene glycols and ethoxylated alkanols is mixed at a temperature of ambient temperature up to 90 °C with 0.05 to 10 times, for example 0.05 to 2.0 times the volume (v/v) of water per 1 volume of organic phase.
  • the temperature during mixing ranges from ambient temperature to 90 °C, preferably from 20 to 85 °C, particularly preferably from 35 to 80 °C, most preferably from 40 to 80 °C and particularly from 45 to 75 °C.
  • the temperature can remain the same or increase during mixing.
  • the duration of the mixing is less relevant; it can range from 1 minute to 8 hours, preferably from 5 minutes to 4 hours, particularly preferably from 10 minutes to 2 hours, and most preferably from 15 to 90 minutes.
  • the essential element in the mixing step (i) is the amount of water, which is 0.05 to 2.0 times, preferably 0.1 to 1.5 times, particularly preferably 0.15 to 1.0 times, most preferably 0.25 to 0.75 times the volume (v/v) of water per 1 volume of organic phase.
  • the water used according to the present invention should preferably be ion-free, i.e., water with a neutral pH value, which contains essentially no other ions than the hydroxide and hydronium ions from the autoprotolysis of water at the respective temperature.
  • the electrical conductivity (determined according to ASTM D 1125) at 25 °C of the ion-free water used should preferably not exceed 5 piS/cm, more preferably not exceed 3, more preferably not exceed 2 and in particular not exceed 1 piS/cm.
  • the ion-free water used can be pure distilled or double distilled water, or water that has been deionized, e.g., by ion exchange, preferably by ion exchange of at least the cations, and particularly preferably by ion exchange of both the cations and the anions.
  • the mixing of the organic phase with the water generally occurs through the input of energy via shear energy.
  • This can be achieved, for example, in dynamic mixing devices, i.e., by mixing using a stirrer or by pumping (natural or forced circulation) or pumping with static mixing devices such as static mixers or nozzles in the pumping circuit, by static mixing devices such as static mixers, nozzles, orifices, Y- or T-pieces in the inlet of the mixing tank, or by dynamic mixing devices such as mixing pumps or stirred tanks.
  • step (ii) the organic and aqueous phases are separated at elevated temperature, exploiting the fact that the systems according to the invention, consisting of oligo- and polyethylene glycols and ethoxylated alkanols, have an upper separation temperature (OET) or form an emulsion that separates upon increasing temperature.
  • OFET upper separation temperature
  • the emulsions are formed by the presence of ethoxylated alkanols with a value for m > 3, since such highly ethoxylated alkanols, which are present in small proportions in the ethoxylated alkanols due to production processes, can act as emulsifiers.
  • the temperature in step (ii) is generally selected from 30 to 90 °C, preferably from 35 to 85 °C, particularly preferably from 40 to 85 °C and most particularly preferably from 45 to 80 °C.
  • the duration of the separation process can range from 10 minutes to 8 hours, preferably from 15 minutes to 4 hours, particularly preferably from 30 minutes to 3 hours and most preferably from 45 minutes to 4 hours.
  • oligoglycols and polyethylene glycols can act as solubility enhancers between the organic and aqueous phases, which, through the formation of mixed phases, makes demixing more difficult and delays it.
  • an organic solvent can accelerate demixing, which, depending on the intended use, can later remain in the ethoxylated alkanol or be separated from it.
  • emulsion breakers or phase separation aids to improve or accelerate segregation or to stabilize the phase boundary is conceivable, although less preferred, since these usually remain in the product. Such aids are not preferably used in the process according to the invention.
  • step (ill) the organic phase is separated from the aqueous phase.
  • This separation is usually carried out at the same temperature as in step (ii), but it can exceptionally be down to 20, preferably down to 15 and particularly preferably down to 10 °C lower.
  • Steps (i) to (ill) can be carried out, for example, in a stirred vessel or in other conventional apparatus, e.g., in a column or mixer-settler apparatus.
  • stirred tanks or mixer-settler apparatuses as well as pulsed columns or those with rotating internals are used; stirred tanks and mixer-settler apparatuses are particularly preferred.
  • Steps (i) to (ill) in the method according to the invention can be carried out one or more times, preferably one to ten times, particularly preferably one to eight times and most preferably one to six times.
  • the water content of the organic phase can be reduced.
  • the product can be treated with water-binding compounds, such as zeolites or molecular sieves, to remove water, or it can be subjected to a membrane filtration process, in particular ultrafiltration, nanofiltration, and reverse osmosis.
  • water-binding compounds such as zeolites or molecular sieves
  • the membranes used have the inherent properties of Its function is to retain certain substances (such as organic compounds) and allow others (such as inorganic salts or water) to pass through.
  • step (iv) the water content of the organic phase is reduced by distillation, which can optionally be supported by passing a stripping gas, preferably the oxygen-poor gas, preferably lean air, nitrogen or argon, particularly preferably nitrogen.
  • a stripping gas preferably the oxygen-poor gas, preferably lean air, nitrogen or argon, particularly preferably nitrogen.
  • step (iv) is also carried out in the presence of a gas atmosphere in which the proportion of oxygen is not more than 10 vol%, preferably not more than 8, particularly preferably not more than 6, most particularly preferably not more than 5, in particular not more than 2 and especially not more than 1 vol%.
  • the distillation is carried out in less than 4 hours, particularly preferably in no more than 3h45min, most particularly preferably in no more than 3h30min.
  • the temperature during distillation should not exceed 100 °C, preferably not more than 98 °C and particularly preferably not more than 95 °C.
  • the distillation is carried out at reduced pressure, i.e., at ambient pressure, preferably at no more than 750 mbar, particularly preferably at no more than 500 mbar, most preferably at no more than 250 mbar, in particular at no more than 200 mbar and especially at no more than 150 mbar.
  • the combination of duration, temperature, and pressure is selected such that the water content in the organic phase is reduced to no more than 5 wt%, preferably no more than 4 wt%, particularly preferably no more than 3 wt%, most preferably no more than 2 wt%, and particularly no more than 1 wt%. Specifically, levels of no more than 0.75 wt%, and even no more than 0.5, 0.25, or 0.1 wt%, can be targeted.
  • Distillation can be carried out continuously or discontinuously in any manner.
  • the distillative separation of water takes place in a stirred tank with double-wall heating and/or internal heating coils under reduced pressure.
  • distillation can also be carried out by passing the mixture through a falling-film, thin-film, or wiper-blade evaporator one or more times.
  • the aqueous mixture is passed continuously or discontinuously,
  • the solution is passed through the apparatus under reduced pressure.
  • the effluent is preferably cooled after passing through the evaporator.
  • an inert gas preferably argon or a nitrogen-containing gas, particularly preferably argon, nitrogen or a mixture of air and nitrogen (lean air), most preferably nitrogen
  • a nitrogen-containing gas particularly preferably argon, nitrogen or a mixture of air and nitrogen (lean air), most preferably nitrogen
  • the distillation apparatus for example 0.1 - 1, preferably 0.2 - 0.8 and particularly preferably 0.3 - 0.7 m 3 /m 3 h, based on the volume of the liquid mixture.
  • a rectification column with up to 10 theoretical trays can be added to the distillation apparatus; however, this is usually not necessary for the simple separation of water and is therefore less preferred.
  • the process according to the invention it is possible to reduce the initial content of oligo- and polyethylene glycols in the ethoxylated alkanols generally by at least 10%, preferably by at least 15%, particularly preferably by at least 20%, and most preferably by at least 25%.
  • the process according to the invention makes it possible to remove the oligo- and polyethylene glycols almost completely and to reduce their formation during the process.
  • the initial content of (Earth)Al potassium imetal hones in the ethoxylated alkanols can generally be reduced by at least 20%, preferably by at least 30%, particularly preferably by at least 40% and most preferably by at least 50% and up to 95% or more.
  • ethoxylated alkanols obtained, preferably obtained, according to the inventive process which are depleted of oligo- and polyethylene glycols and/or (earth)alkali metal ions, can generally be used in all applications that are typically known for such ethoxylated alkanols that are not depleted.
  • ethoxylated alkanols are preferably used in applications where a reduced content of oligo- and polyethylene glycols and/or (earth) alkali metal ions is required.
  • These can be, for example, emulsifiers in w/o emulsions.
  • ethoxylated alkanols with a reduced content of oligo- and polyethylene glycols and/or (earth)alkali metal ions are particularly advantageously used as a surfactant for the distribution, especially dispersion, of water in fuels selected from the group consisting of gasoline, diesel, marine fuels and aviation fuels, preferably diesel or aviation fuels, especially preferably aviation fuels, particularly turbine fuels.
  • ethoxylated alkanols make it possible to distribute a water content of at least 50 ppm in liquid hydrocarbon fuels in stable microemulsions with a droplet size of no more than 0.25 pim. This is particularly useful for reducing or suppressing the formation of ice particles in the fuel when cooled to minus 50°C. Furthermore, it prevents the formation of a separated water phase at the bottom of aircraft fuel tanks, which can lead to undesirable corrosion due to biofilm formation.
  • the following quantities are preferably added to the fuel:
  • the at least one (C8-C24)alkyl amido (Ci-C6)alkyl betaine may preferably be Cocoamidopropyl betaine.
  • the fuel may also contain one or more of the following additional components: static dissipators, antioxidants, metal deactivators, leak detection additives, corrosion inhibitors, lubricants, alcohols, glycols and other standard products known to those skilled in the art, as well as impurities such as fatty acid methyl esters.
  • static dissipators antioxidants, metal deactivators, leak detection additives, corrosion inhibitors, lubricants, alcohols, glycols and other standard products known to those skilled in the art, as well as impurities such as fatty acid methyl esters.
  • the ethoxylated alkanols are mostly used in the form of liquid concentrates, essentially containing
  • glycol-based solubility enhancer preferably ethylene glycol
  • organic solvent preferably ethanol
  • Turbine fuels contain a primary component of liquid turbine fuel, such as a turbine fuel commonly used in civil or military aviation. Examples include fuels designated Jet Fuel A, Jet Fuel A-1, Jet Fuel B, Jet Fuel JP-4, JP-5, JP-7, JP-8, and JP-8+100. Jet A and Jet A-1 are commercially available, kerosene-based turbine fuel specifications. The relevant standards are ASTM D 1655 and DEF STAN 91-91. Jet B is a more highly refined fuel based on naphtha and kerosene fractions. JP-4 is equivalent to Jet B. JP-5, JP-7, JP-8, and JP-8+100 are military turbine fuels, such as those used by the Navy and Air Force. In some cases, these standards specify formulations that already contain further additives, such as corrosion inhibitors, icing inhibitors, static dissipators, etc.
  • SAF Sustainable Aviation Fuel
  • FT-SPK Fischer-Tropsch Synthetic Paraffinic Kerosene, Annex 1 of ASTM D7566
  • HEFA-SPK Hydroprocessed Esters and Fatty Acids
  • HFS-SIP Hynthesized Iso-paraffin from Hydro-processed Fermented Sugar, Annex 3 of ASTM D7566
  • FT-SKA Fischer Tropsch Synthetic Kerosene with Aromatics
  • ATJ-SPK Alcohol to Jet Synthetic Paraffinic Kerosene, from ethanol or iso-butanol, Annex 5 of ASTM D7566
  • CHJ Catalytic Hydrothermolysis Synthesized Kerosene, Annex 6 of ASTM
  • SAFs potential biomass feedstocks for SAFs include forestry waste, solid household waste, industrial exhaust gases, agricultural waste, used cooking oils (cooking oil, animal fat, tall oil), sugar, and algae.
  • the resulting SAFs can currently be blended with conventional fossil turbine fuels at concentrations of up to 50%, or up to 10% in the case of HFS-SIP and HC-HEFA-SPK.
  • SAFs can be produced, for example, using power-to-liquid (PtL) technology: Electricity is generated from renewable sources such as wind or solar power and used to split water into hydrogen and oxygen through electrolysis. The hydrogen obtained in this way is then combined with CO2, captured from the air or industrial processes, in several steps to produce an SAF, for example, through processes such as Fischer-Tropsch synthesis.
  • PtL power-to-liquid
  • Suitable additives that may be included in the turbine fuel composition typically include detergents, corrosion inhibitors, sulfur-free antioxidants such as sterically hindered tert-butylphenols, N-butylphenylenediamines or N,N'-diphenylamine and derivatives thereof, metal deactivators such as N,N'-disalicylidene-1,2-diaminopropane, solubilizers, antistatic agents such as Stadls 450, biocides, anti-icing agents such as diethylene glycol methyl ether or triethylene glycol methyl ether, and mixtures of the aforementioned additives.
  • detergents such as sterically hindered tert-butylphenols, N-butylphenylenediamines or N,N'-diphenylamine and derivatives thereof
  • metal deactivators such as N,N'-disalicylidene-1,2-diaminopropane
  • solubilizers solubilizers
  • microemulsions can be produced by mixing
  • emulsifier composition wherein the emulsifier composition comprises
  • oligo- and polyethylene glycols and/or (earth) alkali metal ions at least one ethoxylated alkanol, with a reduced content of oligo- and polyethylene glycols and/or (earth) alkali metal ions, wherein the proportions always refer to volume.
  • a further object of the present invention is a method for distributing water in fuels using ethoxylated alkanols of the formula
  • R 1 straight-chain or branched Cs-Cu alkyl, preferably Cs-C alkyl, particularly preferably Cg-C alkyl, and most preferably Cg-Cn alkyl and m a rational number from 1 to 3 with a reduced content of oligo- and polyethylene glycols of the formula
  • n is a rational number of at least 2, preferably from 2 to 30 and particularly preferably from 2 to 20, and a simultaneously reduced content of (earth)alkali metal ions, wherein one
  • (I) reacts an alkanol R 1 -OH with at least m equivalents of ethylene oxide in the presence of at least one basic salt of at least one (earth)alkali metal and in the presence of water at a temperature of 20 to 200 °C to obtain a mixture of oligo- and polyethylene glycols and ethoxylated alkanols and
  • (III) mixes the oligo- and polyethylene glycol-depleted, ethoxylated alkanol thus obtained into a fuel selected from the group consisting of gasoline, diesel, marine fuels and aviation fuels.
  • PEG concentrations were measured against a PEG standard using HPLC-MS.
  • the PEG standard used had a molar mass range determined in the sample by MS.
  • Water content was measured using volumetric Karl Fischer titration.
  • demineralized water is added in an amount sufficient to cover the frit and the syringe tip.
  • This is then connected to the measuring cell (electrochemical oxygen measuring cell ("heart cell” from Pro-Chem Analytik GmbH & Co. KG, Kamp-Lintfort, Germany (O2-Sensor 16T304), Range 2).
  • Nitrogen is then passed through the measuring cell and the water at ambient temperature as the stripping gas at a pressure of 150 kPa until the measuring device is oxygen-free, as indicated by the oxygen cell's signal. Optimal mixing of the two liquids is ensured by the bubbling stripping gas.
  • the measurement process ends when the oxygen cell's signal returns to the same level as before the sample was added.
  • the measurement signal from the oxygen cell is recorded and evaluated using a laboratory data system.
  • the O2 content is calculated via a calibration measurement, taking into account the current air pressure and ambient temperature.
  • a defined quantity of a calibration gas with a known oxygen content is dosed into the measuring cell with liquid reservoir using a gas-tight syringe, and the resulting measurement signal is evaluated using the laboratory data system.
  • Jet A-1 80 ml of an aviation fuel of specification Jet A-1 were shaken at ambient temperature with 20 ml of pH 7 buffer solution and the amount of additive and polyethylene glycol of mean molar weight 400 g/mol (PEG400) specified in the table, based on the fuel, and the phases and their separation were evaluated in a 100 ml graduated cylinder after periods of 5, 30 and 60 minutes.
  • PEG400 mean molar weight 400 g/mol
  • the additive is the composition according to Example 4 of WO 2011/045334 A1, wherein the ethoxylated alkanol is an on average 2.5-fold ethoxylated mixture of Cg-Cn alkanols. Table 1
  • the mixed phase is a cloudy phase between the aqueous and organic phases.
  • the aqueous phase was separated at 80°C. 250 ml of water were added and the mixture was stirred for 30 minutes at 80°C. The aqueous phase was then separated. The ethoxylate was extracted three more times in this manner, each time with 250 ml of desalinated water (a total of five extractions were performed, each with 250 ml of desalinated water).
  • the organic phase (549 g) contained 11.8% water.
  • the water was removed using a rotary evaporator at 100°C under vacuum.
  • the final product showed a water content of 0.2%, a potassium content of 4 ppm, and a PEG content of ⁇ 50 ppm.
  • the mass balance shows that the ethoxylated alkanol contained 109 mg of PEG at the beginning of the experiment, and the three phases together contained 302 mg of PEG at the end of the experiment. During the experiment, 193 mg of PEG were newly formed (177% of the original amount). The experiment further demonstrates that the PEG content cannot be reduced by extraction in the presence of oxygen.
  • a sample from the organic phase showed a water content of 18.2% and a PEG content of 50 ppm. Calculated based on the anhydrous ethoxylated alkanol, the PEG content was accordingly reduced to 61 ppm.
  • the mass balance shows that the two phases contained a total of 71 mg of PEG at the end of the experiment, while the ethoxylated alkanol contained 65 ppm PEG at the beginning of the experiment. During the course of the experiment, 6 mg of PEG were newly formed (9% of the original amount).
  • the ethoxylated alkanol (995 kg) was obtained with a PEG content of 41 ppm.
  • the samples were pretreated as follows:
  • Sample B Air (10 L/h) was passed through the sample (100 g) at room temperature for 3 hours.
  • the dissolved oxygen content in the ethoxylated alkanol can be reduced by passing an inert gas through it.
  • the saturation limit for oxygen in the ethoxylated alkanol used is approximately 23 mg of oxygen per kg of ethoxylated alkanol at room temperature. This is followed by a discussion of the ethoxylated alkanol and its concentration of dissolved oxygen.

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Abstract

L'invention concerne un procédé pour éliminer des oligoéthylèneglycols et des polyéthylèneglycols à partir d'alcanols éthoxylés.
PCT/EP2025/071067 2024-07-31 2025-07-22 Élimination de polyéthylèneglycols à partir d'éthoxylates Pending WO2026027352A1 (fr)

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EP24192154.3 2024-07-31
EP24192154.3A EP4686718A1 (fr) 2024-07-31 2024-07-31 Séparation de polyéthylène glycol d'éthoxylates
EP25166810 2025-03-27
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE828839C (de) 1949-02-09 1952-01-21 Anorgana Fa Verfahren zur Abtrennung von Polyglykolen aus Gemischen mit Anlagerungsprodukten von Alkylenoxyden an hydroxyl- oder carboxylhaltige organische Verbindungen
EP0043963A1 (fr) 1980-06-30 1982-01-20 Union Carbide Corporation Procédé d'éthoxylation d'alcools primaires de poids moléculaires très variés
EP1015404B1 (fr) 1997-09-01 2004-07-14 Cognis Deutschland GmbH & Co. KG Alcoxylats d'alcools gras stables au froid
WO2011045334A1 (fr) 2009-10-14 2011-04-21 Palox Offshore S.A.L. Protection de combustibles liquides
WO2021262439A2 (fr) 2020-06-22 2021-12-30 The Procter & Gamble Company Procédé de production d'éthoxylates d'alcool gras de glycol réduit, tensioactifs éthoxylés de sulfate de glycol réduit et produits

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE828839C (de) 1949-02-09 1952-01-21 Anorgana Fa Verfahren zur Abtrennung von Polyglykolen aus Gemischen mit Anlagerungsprodukten von Alkylenoxyden an hydroxyl- oder carboxylhaltige organische Verbindungen
EP0043963A1 (fr) 1980-06-30 1982-01-20 Union Carbide Corporation Procédé d'éthoxylation d'alcools primaires de poids moléculaires très variés
EP1015404B1 (fr) 1997-09-01 2004-07-14 Cognis Deutschland GmbH & Co. KG Alcoxylats d'alcools gras stables au froid
WO2011045334A1 (fr) 2009-10-14 2011-04-21 Palox Offshore S.A.L. Protection de combustibles liquides
WO2021262439A2 (fr) 2020-06-22 2021-12-30 The Procter & Gamble Company Procédé de production d'éthoxylates d'alcool gras de glycol réduit, tensioactifs éthoxylés de sulfate de glycol réduit et produits
US20230119920A1 (en) * 2020-06-22 2023-04-20 The Procter & Gamble Company Method for producing reduced glycol fatty alcohol ethoxylates, reduced glycol sulfate ethoxylated surfactants, and products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. LONESCU, CHEMISTRY AND TECHNOLOGY OF POLYOLS FOR POLYURETHANES, RAPRA TECHNOLOGY LIMITED, 2005, ISBN: 1-85957-491-2

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