Ethoxylates having a low polyethylene glycol content

Abstract

The invention relates to a process for preparing ethoxylated alkanols having a low oligo- and polyethylene glycol content.

Description

[0001] Ethoxylates with a low polyethylene glycol content

[0002] Description

[0003] The present invention relates to a process for the production of ethoxylated alkanols with a low content of oligo- and polyethylene glycols.

[0004] 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 a component of the alkanol itself, and reacts with the ethylene oxide to form oligoglycols and polyethylene glycols.

[0005] In many applications, the presence of oligo- and polyethylene glycols is not detrimental, since the ethoxylated alkanols are later combined with polyethylene glycols anyway, for example for applications in surfactants or cleaning and washing agents.

[0006] The diethylene glycol contained in oligoethylene glycols is a starting material for the formation of the toxicologically problematic dioxane, whereas the hydrophilic higher ethylene glycols in 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 strongly influenced by the presence of the hydrophilic polyethylene glycols.

[0007] This is particularly the case with 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).

[0008] Specifically, 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.

[0009] EP 3919596 A1 describes a process for the production of tridecanol ethoxylate in the presence of potassium methoxide in methanol at temperatures of 95 to below 100 °C. The aim of EP 3919596 A1 was to reduce the dioxane content after ethoxylation and subsequent sulfation, which is achieved by controlling the process conditions during these two reaction steps.

[0010] Measures to reduce polyalkylene glycols are not disclosed; on the contrary, polyalkylene glycols are recommended as solvents for the compositions.

[0011] EP 3601494 B1 describes the use of non-ionic alkoxylated surfactants, exemplified by C9.11 alcohol ethoxylates, as emulsifiers in fuel additive compositions.

[0012] The production of alkoxylated surfactants is not discussed, and the effect that oligo- and polyethylene glycols show in such additive compositions is not recognized.

[0013] The object of the present invention was to provide a process for the production of one- to three-fold ethoxylated Cs-Cu alkanols having a low content of oligo- and polyethylene glycols.

[0014] Two basic approaches can be pursued, which can also be combined:

[0015] The production of ethoxylated alkanols can be carried out under reaction conditions such that fewer oligo- and polyethylene glycols are formed than in the known catalysis in the presence of sodium or potassium hydroxide.

[0016] According to WO 2021 / 171209, the formation of polyethylene glycols is due to the presence of water in the alkaline catalyst, so WO 2021 / 171209 proposes ethoxylation in the presence of DMC (double metal cyanide) catalysts.

[0017] However, these DMC catalysts are complex to manufacture.

[0018] Alternatively or additionally, already formed oligo- and polyethylene glycols can be completely or partially removed from a mixture with ethoxylated alkanols.

[0019] The adsorption of polyethylene glycols onto sodium bentonite was described, for example, by F. Clegg et al., J. Phys. Chem. B, 2014, 118, 13268-13278. Sodium bentonite is a clay mineral containing predominantly montmorillonite, a sodium aluminum silicate with the general formula (Na,Ca)0.3(Al,Mg)2Si4O10(OH)2'nH2O. However, Clegg et al. only describe the adsorption of polyethylene glycols from aqueous solutions and not their removal from a reaction mixture containing similar compounds, such as ethoxylated alkanols. Therefore, when sodium bentonite is used in mixtures of ethoxylated alkanols and polyethylene glycols, it is to be expected that, in addition to the polyethylene glycol, the desired product will also be removed from the reaction mixture. This problem is solved by a process for the preparation of ethoxylated alkanols of the formula

[0020] R 1 -O-[-CH2-CH2-O-] m -H wherein

[0021] R 1straight-chain or branched, preferably straight-chain, Cs-Cu-alkyl and m a rational number of 1 to 3, with a low content of oligo- and polyethylene glycols of the formula

[0022] HO-[-CH2-CH2-O] n -H where n is a rational number of at least 2, preferably from 2 to 20, where one

[0023] (I) at least one alkanol R 1 OH with at least m equivalents of ethylene oxide in the presence of at least one (earth) alkali metal alcoholate of an alkanol R 2 OH converts, where R 2 a Ci- to C-cyl residue or R 1 may be, and / or one

[0024] (II) a mixture of at least one ethoxylated alkanol of the formula

[0025] R 1 -O-[-CH2-CH2-O-] m -H with oligo- and polyethylene glycols of the formula

[0026] HO-[-CH2-CH2-O]nH treated with at least one adsorbent selected from the group consisting of

[0027] (I) phenol-formaldehyde resins,

[0028] (II) Silica gel and

[0029] (ill) acidic ion exchangers in the potassium form.

[0030] The present invention has the advantage that, according to embodiment (I), it requires only a simple catalyst, and according to embodiment (II), any oligo- and polyethylene glycol formed can be removed from the reaction mixture. Furthermore, the materials used in step (II) can be easily regenerated, allowing them to be reused several times after desorption of the oligo- and polyethylene glycol. Moreover, these materials used according to the invention exhibit higher efficiency in separating the oligo- and polyethylene glycols than bentonite known from the prior art.

[0031] The formulas above are

[0032] R 1straight-chain or branched, preferably straight-chain Cs-Cu alkyl, preferably Cs-C alkyl, particularly preferably C9-Ci3 alkyl, and most preferably C9-C1 i alkyl, m a rational number from 1 to 3 and n a rational number of at least 2, preferably from 2 to 30 and particularly preferably from 2 to 20.

[0033] 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 (capric alcohol), undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol and tetradecyl alcohol (myristyl alcohol).

[0034] In a preferred embodiment, these are pure substances such as 2-ethylhexanol or 2-propyl heptanol.

[0035] In another embodiment, the underlying alkanol R can be 1OH refers to 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 take on non-integer values.

[0036] Examples of such mixtures are 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% C2 alkanol.

[0037] In another embodiment, the alcohol R 1-OH to a mixture of alcohols having about 13 carbon atoms, particularly preferably to one obtained by hydroformylation from a C12 olefin mixture which in turn is obtained by oligomerization of an olefin mixture containing predominantly four carbon atoms hydrocarbons.

[0038] On average, 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.

[0039] In a particularly preferred embodiment, this alcohol R 1 -OH exhibits a medium degree of branching, measured as an ISO index, of 1.8 to 2.7. Such mixtures are commercially available as tridecanols or iso-tridecanols.

[0040] Particularly preferred are mixtures of linear alcohols having 9, 10, and 11 carbon atoms. In a particularly preferred embodiment, the alkanol R is... 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%. Particularly preferably, these are highly linear alkanols exhibiting 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 of such an alcohol mixture is from 158 to 164 g / mol. The OH number is from 342 to 355 mg KOH / g.

[0041] 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.

[0042] The degree of ethoxylation m is an arithmetic mean, therefore m can also take on non-integer values.

[0043] The oligo- and polyethylene glycols of the formula HO-[-CH2-CH2-O] n -H are mostly formed as a byproduct during the ethoxylation of alkanols.

[0044] 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, n can also take on non-integer values.

[0045] 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.

[0046] Sources of water include the alkanol used and the base used as a catalyst. The base, especially sodium or potassium hydroxide, is usually used as an aqueous solution, making subsequent removal either incomplete or uneconomical. Other possible sources include atmospheric humidity or traces of moisture in any protective gas used, contamination of the apparatus, and a small amount of water in the ethylene oxide. When sodium or potassium hydroxide is used as a catalyst, the content of oligoglycols and polyethylene glycols in the ethoxylated alkanols can range from 1 to 5% by weight.

[0047] If the catalyst is used as an aqueous solution, higher levels of oligo- and polyethylene glycols are also achieved.

[0048] By carrying out the process according to the invention, steps (I) and / or (II), preferably step (II), it is possible to reduce the 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%. By the process according to the invention, with the selection of suitable experimental conditions in step (I) and / or (II), it is possible to reduce the content of oligo- and polyethylene glycols to no more than 2500 ppm.

[0049] The present invention relates to a process for the production of ethoxylated alkanols of the formula

[0050] R 1 -O-[-CH2-CH2-O-] m -H with a low content of oligo- and polyethylene glycols of the formula HO-[-CH2-CH2-O] n -H in which one either

[0051] (I) at least one alkanol R 1OH with at least m equivalents of ethylene oxide in the presence of at least one (earth) alkali metal alcoholate of an alkanol R 2 OH implements, or

[0052] (II) a mixture of at least one ethoxylated alkanol with oligo- and polyethylene glycols treated with at least one adsorbent (i), (ii) or (iii), or combining steps (I) and (II).

[0053] In a preferred embodiment, the method according to the invention comprises only step (I) in which at least one alkanol R 1 OH with at least m equivalents of ethylene oxide in the presence of at least one (earth) alkali metal alcoholate of an alkanol R 2 OH is implemented.

[0054] In a further preferred embodiment, the process according to the invention comprises only step (II) in which an arbitrarily prepared mixture of at least one ethoxylated alkanol with oligo- and polyethylene glycols is treated with at least one adsorbent (I), (II) or (iii). In a third embodiment, steps (I) and (II) can be combined, and first in step (I) at least one alkanol R 1 OH with at least m equivalents of ethylene oxide in the presence of at least one

[0055] (Earth) Alkali metal alcoholate of an alkanol R 2 react OH and treat the reaction mixture obtained in this way, preferably after removal of unreacted ethylene oxide, in a step (II) with at least one adsorbent (i), (ii) or (iii).

[0056] (I) Ethoxylation

[0057] According to one embodiment of the present invention, at least one alkanol R 1OH with at least m equivalents of ethylene oxide in the presence of at least one (earth)Al potassium imetallic kohlate of an alkanol R 2 OH implemented, where R 2 a Ci- to C-cyl residue or R 1 may be.

[0058] The (earth) alkali metal is preferably sodium, potassium, magnesium or calcium, particularly preferably sodium or potassium, most particularly preferably sodium.

[0059] Among the Ci-C icoholates of the alkanol R 2 OH, the methanolates or ethanolates of the (earth)alkali metals are particularly preferred, especially sodium or potassium.

[0060] In a preferred embodiment according to the invention, the (earth) alkali metal al kohlate of the alkanol R 1 OH is used as a catalyst.

[0061] This can, in principle, be produced in two ways:

[0062] One can add to the alkanol R 1 OH an (earth) alkali metal alcohol ate of the alkanol R2 Add OH so that the reaction mixture contains the alkanols R. 1 OH and R 2 OH are in equilibrium. From this equilibrium, the lower-boiling alkanol R can be released. 2 OH are removed, preferably distilled off and / or stripped, for example by stripping with argon, oxygen-depleted air or nitrogen, preferably with nitrogen, so that the equilibrium shifts towards the side of the desired alkanol R. 1 The OH is shifted. The distillation can preferably be carried out under reduced pressure, for example down to 500 mbar, preferably down to 300, particularly preferably down to 200, most preferably down to 100 and particularly down to 50 mbar.

[0063] The (earth) alkali metal alcoholate of the alkanol R is preferred. 1 OH, however, is produced by taking the alkanol R 1OH with metallic (earth) alkali metal, preferably metallic sodium or potassium, particularly preferably metallic sodium, to form the corresponding alcoholate of the alkanol R 1 OH implements.

[0064] This reaction takes place, for example, at a temperature of ambient temperature up to 120 °C, preferably up to 110 °C, most preferably up to 100 °C, and particularly up to 90 °C, for a reaction time of, for example, up to 4 hours, preferably up to 3 hours, and most preferably up to 2 hours. It is particularly advantageous if the materials used are largely freed of water before the reaction, i.e., the alkanols R 1 OH or R 2 OH, as well as any stripping gas that may be used.

[0065] This can be done using known drying agents, such as molecular sieves, sodium sulfate, calcium chloride or silica gel, but also by reverse osmosis, distillation or azeotropic distillation.

[0066] This drying process is completed by an excess of (earth)alkali metal alkoxide of the alkanol R. 2 OH or the (earth) alkali metal.

[0067] This makes it possible to reduce the water content of the feedstock materials to no more than 1000 ppm by weight, preferably no more than 750 ppm by weight, particularly preferably no more than 500 ppm by weight, most preferably no more than 350 ppm by weight, and particularly no more than 250 ppm by weight. The lower the water content in the feedstock materials, the fewer oligoglycols and polyethylene glycols are formed.

[0068] Ethoxylation is usually carried out by reacting the alkanol R 1 OH and ethylene oxide in the presence of at least one (earth) alkali metal alcoholate of an alkanol R 2 OH reacts in a molar ratio of 1 to at least m, preferably exactly 1 to m.

[0069] The reaction with ethylene oxide can be carried out in a temperature range of 100 to 180 °C, in particular from 120 to 160 °C.

[0070] Ethoxylation can be carried out at atmospheric pressure, under vacuum, and at elevated pressures, for example, at pressures of 0.8 to 50 bar (abs), particularly at pressures of 1 to 10 bar (abs). A slight overpressure up to 2 bar (abs) is especially advantageous.

[0071] The at least one (earth) alkali metal al kohl ate of the alkanol R 2 OH is added in amounts of 0.5 to 5 mol% based on the alkanol R 1 OH is used, preferably 0.75 to 4 mol% and particularly preferably 1 to 3 mol%.

[0072] Ethoxylation is preferably carried out under an inert gas cover, for example by nitrogen, argon, carbon dioxide or lean air, i.e. oxygen-depleted air, preferably nitrogen.

[0073] The inert gas may contain small amounts of molecular oxygen or nitrogen monoxide that are safe from a safety perspective, so that the explosion limit of the ethylene oxide is not exceeded, for example less than 5 vol%, preferably less than 2 vol%, particularly preferably less than 1 vol% and most preferably less than 0.5 vol%.

[0074] 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.

[0075] After completion of the ethoxylation, any unreacted ethylene oxide is removed, usually by a combination of stripping with an inert gas, preferably argon, oxygen-depleted air or nitrogen, preferably with nitrogen, and degassing under reduced pressure, for example up to 500 mbar, preferably up to 300, particularly preferably up to 200, very preferably up to 100 and particularly up to 50 mbar at elevated temperature, for example up to 120 °C, preferably up to 100 and particularly preferably up to 80 °C.

[0076] The basic salt is preferably subsequently separated from the reaction mixture, for example by sedimentation, filtration via frit, filter or sieve, 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.

[0077] Ethoxylation processes are generally described in M. lonescu: Chemistry and Technology of Polyols for Polyurethanes, Rapra Technology Limited, 2005, ISBN:1-85957-491-2.

[0078] 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.

[0079] It is also possible to connect several of the aforementioned reaction units in series. This allows the process to be operated in multiple stages. It is also possible to operate several reactors in parallel within a single process stage.

[0080] 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.

[0081] During continuous operation, 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.

[0082] 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 invention utilizes the (earth)alkali metal alcoholate of an alkanol R. 2 OH makes it possible to keep the content of oligo- and polyethylene glycols in the reaction mixture low.

[0083] As a rule, by this reaction procedure of step (I) according to the invention, when using starting materials whose water content has been reduced, the content of oligo- and polyethylene glycols in the ethoxylated alkanols can be reduced to less than 1 wt%, preferably to no more than 0.9, particularly preferably to no more than 0.75, most preferably to no more than 0.67, in particular to no more than 0.5 and especially to no more than 0.4 wt%.

[0084] To further reduce the content of oligo- and polyethylene glycols, it is possible to subject the mixture of oligo- and polyethylene glycols and ethoxylated alkanols obtained from step (I) to additional step (II).

[0085] Should the remaining content of (earth)alkali metal ions in the reaction mixture interfere with the planned application, it is possible to subject the reaction mixture to a washing process, preferably with water or a slightly acidic medium.

[0086] Alternatively or additionally, the content of (earth)Al potassium imetallic ions can also be removed by filtration using a filter aid, such as gel, aluminum oxide, silicates or silica gel.

[0087] (II) Treatment with adsorbent

[0088] According to step (II) of the invention, a mixture of at least one ethoxylated alkanol with oligo- and polyethylene glycols is treated with at least one adsorbent (I), (II) or (III), selected from the group consisting of

[0089] (I) phenol-formaldehyde resins,

[0090] (II) Silica gel and

[0091] (ill) acidic ion exchangers in the potassium form.

[0092] Phenol-formaldehyde resin

[0093] Phenol-formaldehyde resins (PFH) are used as adsorbents in a wide variety of applications due to their high specific surface area and porous structure. The selection of the appropriate PFH adsorbent depends on various factors, such as the intended application, the impurities to be adsorbed, and the required physical properties of the adsorbent. Phenol-formaldehyde resins are produced by the polymerization of phenol or substituted phenols and formaldehyde in the presence of catalysts such as acids or bases. Different starting materials can be used to influence the properties of the phenol-formaldehyde resin. For example, using phenol with various substituents can lead to phenol-formaldehyde resins with different chemical and physical properties.

[0094] Examples of phenols with different substituents are: ortho-cresol, meta-cresol and para-cresol

[0095] Xylenols: 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylphenol and their isomer mixtures

[0096] Alpha and beta naphthol

[0097] Pyrocatechol (1,2-dihydroxyphenol), resorcinol (1,3-dihydroxyphenol) and hydroquinone (1,4-dihydroxyphenol) 2-, 3- or 4-methoxyphenol

[0098] In addition to cresols and xylenols, mono- or di-C2- to Ci2-alkyl phenols can also be used, preferably mono-substituted, and particularly preferably predominantly para-substituted. This alkyl substitution allows the phenol-formaldehyde resin to be made more hydrophobic, thus enabling it to adsorb more hydrophobic impurities.

[0099] Phenol is the preferred substance.

[0100] These phenols with various substituents offer the possibility of varying the chemical and physical properties of the PFH adsorbent. By combining different phenols or using a single phenol, PFH adsorbents with different pore structures, specific surface areas, and adsorption capacities can be produced. The selection of the appropriate phenol with the corresponding substituents depends on the specific requirements of the application.

[0101] The porosity of phenol-formaldehyde resins is influenced by various factors:

[0102] Phenol-to-formaldehyde ratio: The ratio of phenol to formaldehyde during polymerization has a significant influence on the porosity of the resulting phenol-formaldehyde resin. A higher proportion of phenol generally leads to higher porosity, as this results in a greater number of polymer chains and thus a greater number of pores.

[0103] Catalysts: The type and amount of catalysts used can influence the porosity of phenol-formaldehyde resins. Catalysts such as acids or bases initiate the polymerization of phenol and formaldehyde, thus affecting the crosslinking and pore structure of the phenol-formaldehyde resin. Sufficient porosity ensures good accessibility of the active surface areas and efficient transport of the compound to be adsorbed into the interior of the adsorbent.

[0104] Polymerization conditions: The conditions during polymerization, such as temperature, reaction time, and pressure, can influence the porosity of phenol-formaldehyde resins. A higher polymerization temperature can lead to a larger pore size, while a longer reaction time can result in higher porosity.

[0105] Use of template molecules: The use of template molecules during polymerization can control the porosity of phenol-formaldehyde resins. Template molecules act as shapers and influence the pore size and structure of the phenol-formaldehyde resin. They are introduced during polymerization and removed after the reaction, thus preserving the pore structure of the phenol-formaldehyde resin.

[0106] Drying and curing conditions: The type and duration of drying and curing of phenol-formaldehyde resins can also influence porosity. Thorough drying and curing allow for optimal development of the pore structure and porosity.

[0107] These factors are closely interrelated and can be combined to achieve the desired porosity of phenol-formaldehyde resin. Precise control of these factors makes it possible to tailor the porosity of the PFH adsorbent to the specific requirements of the application.

[0108] For the synthesis of phenol-formaldehyde resins (PFH) as adsorbents, a specific ratio of phenol to formaldehyde is generally used. The exact ratio can vary depending on the desired properties of the PFH adsorbent, especially the porosity and pore structure (see above), but a molar ratio of 1:1 to 1:2 of phenol to formaldehyde is typically employed.

[0109] The ratio influences the cross-linking and structure of the PFH adsorbent, which in turn affects the porosity, specific surface area and adsorption capacity.

[0110] A higher molar ratio of phenol to formaldehyde (e.g., up to 1:2) can lead to a greater number of polymer chains and thus to higher porosity and specific surface area. This allows for more efficient adsorption of impurities. However, an excessively high molar ratio can also lead to increased cross-linking, which can reduce pore size and impair adsorption capacity.

[0111] A lower molar ratio of phenol to formaldehyde (e.g., down to 1:1) can lead to less crosslinking and thus to larger pores and a higher adsorption capacity. However, it is important to carefully control the ratio to ensure sufficient crosslinking and structural stability of the PFH adsorbent. The molecular weight of PFH adsorbents typically ranges from a few thousand to several hundred thousand Daltons. A higher molecular weight can lead to a larger pore size and a higher specific surface area, enabling increased adsorption capacity. The molecular weight is chosen so that the PFH adsorbent forms a solid polymer, making it thermally and mechanically stable and manageable.

[0112] The porosity of the PFH adsorbent ensures good accessibility of the active surface areas and efficient transport of contaminants into the interior of the adsorbent. Generally, a mesoporous to macroporous structure is preferred, as it offers a good balance between surface area and accessibility.

[0113] A high specific surface area of ​​the adsorbent indicates a large number of active sites where impurities can be adsorbed. A high specific surface area improves the adsorption capacity and enables effective removal of impurities.

[0114] Phenol-formaldehyde resins with a specific surface area (BET isotherm) of 100 to 400, preferably 125 to 300, and particularly preferably 150 to 250 m² are preferred. 2 exhibit / g.

[0115] The pore volume (determined by N2 isotherm) should be from 0.7 to 1.5, preferably 0.8 to 1.3 and particularly preferably 0.9 to 1.2 ml / g.

[0116] The average pore diameter (calculated from the N2 isotherms) is preferably from 400 to 800 angstroms, particularly preferably from 500 to 700 and most preferably from 550 to 650 angstroms.

[0117] The phenol-formaldehyde resin adsorbent is used as a polymeric solid which can have any geometric shape, for example, chips, granules, spheres, tablets or strands, preferably chips, granules or strands and particularly preferably chips or granules.

[0118] Such phenol-formaldehyde resin adsorbents are commercially available. A preferred example of such an adsorbent is AmberLite™ XAD™761, manufactured by DuPont.

[0119] The phenol-formaldehyde resins can be used dried or pre-wetted. Which state is advantageous for the desired adsorption can be determined through simple preliminary tests.

[0120] silica gel

[0121] Silica gel is a commonly used adsorbent, an amorphous silicate material with a large internal surface area due to its porous structure. It is typically amorphous silicon dioxide, though aluminum or titanium silicates are also possible, albeit less preferred. Specific surface area indicates the total surface area of ​​the material per unit mass or volume. A high specific surface area allows for a greater number of adsorption sites and thus a higher adsorption capacity. Silica gel with a high specific surface area is therefore advantageous for many adsorption processes.

[0122] For the application according to the invention, the inner (specific) surface area can be up to 600 m². 2 / g (N2 isotherm, sBET), preferably from 300 to 600, particularly preferably from 400 to 550 m 2 / G.

[0123] Preferably, the silica gel exhibits a mixture of macroporosity and microporosity, with the pore size determining which type of molecules can be adsorbed.

[0124] Preferably, the pore size (calculated from the N2 isotherm) is 4 to 9 nm, particularly preferably 4.5 to 8 nm, and most preferably 5 to 7.5 nm. The pore volume (N2 isotherm) is preferably 0.5 to 1.0 ml / g, particularly preferably 0.6 to 0.8 ml / g, and most preferably 0.7 to 0.85 ml / g.

[0125] The particle size of the silica gel can vary from 35 to 500 pim, preferably 40 to 200 and particularly preferably 60 to 200 pim.

[0126] For easier handling, these silica gel particles can also be formed into larger structures, for example, chips, granules, spheres, tablets or strands, preferably chips, granules or strands and especially preferably chips or granules.

[0127] Acid ion exchangers in potassium form

[0128] Acidic ion exchangers are mostly those containing carboxyl or sulfonic acid groups, preferably carboxylic acid groups, in a polymer matrix, often based on polystyrene, poly(meth)acrylates, or poly(meth)acrylic acid. Among acidic ion exchangers, strongly acidic ion exchangers are preferred, especially those whose acidity is determined by sulfonic acid groups. Particularly those based on polystyrene crosslinked with divinylbenzene are preferred.

[0129] The acid groups, preferably carboxyl or sulfonic acid groups, especially preferably sulfonic acid groups, are present in acidic ion exchangers in the delivery form mostly in acidic form or as a metal salt, especially with sodium ions as counterion.

[0130] The acidic ion exchangers usable according to the invention are in potassium form, which means that at least 10% of the acidic groups in the ion exchanger carry a potassium ion as a counterion, preferably at least 25%, particularly preferably at least 50%, most preferably at least 66%, and particularly preferably 75%. The degree of neutralization can be up to 100%, preferably up to 98%, and particularly preferably up to 95%. The acidic ion exchanger can have any geometric shape, for example, chips, granules, spheres, tablets, or strands, preferably spheres or granules, and particularly preferably spheres.

[0131] According to the invention, the diameter of the particles is less relevant and can, for example, range from 200 to 1500 pim, preferably from 250 to 1400, and particularly preferably from 300 to 1200 pim.

[0132] The capacity for acidic groups is typically from 1 to 5 eq / l, preferably from 1.2 to 4, and particularly preferably from 1.5 to 3 eq / l.

[0133] The specific surface area (N2 isotherm) can range from 500 to 1500 m² 2 / g, preferably from 550 to 1400 and particularly preferably from 600 to 1300 m 2 / G.

[0134] The ion exchangers also exhibit meso-, macro-, and / or transport pores, which can be determined from N2 adsorption. Their diameter can, for example, range from 50 to 500 angstroms, preferably from 60 to 450, and particularly preferably from 70 to 400 angstroms.

[0135] The pore diameter of the micropores (calculated from the N2 isotherms) is, for example, from 10 to 20 angstroms, preferably 12 to 18 and particularly preferably 13 to 17 angstroms.

[0136] The pore volume (N2 isotherm) can be from 0.1 to 2.5 ml / g, preferably from 0.2 to 2.2, particularly preferably from 0.3 to 2.0 ml / g.

[0137] Treatment in the presence of the adsorbent

[0138] According to the invention, the ethoxylated alkanols containing oligo- and polyethylene glycols are treated with at least one of the adsorbents mentioned above to reduce the oligo- and polyethylene glycol content. Alkanols ethoxylated by conventional methods, preferably in the presence of sodium or potassium hydroxide as a catalyst, typically contain 1 to 5% by weight of oligo- and polyethylene glycols (based on the amount of ethoxylated alkanols).

[0139] The mixture of ethoxylated alkanols and oligo- and polyethylene glycols may further contain at least one solvent, for example aliphatic, cycloaliphatic or aromatic hydrocarbons, ethers, acetals, ketones, esters, cyclic carbonates or alkanols, preferably Ci to C ikanols and particularly preferably ethanol.

[0140] In a preferred embodiment, this mixture of ethoxylated alkanols and oligo- and polyethylene glycols is used without solvents. The adsorbent is used in amounts of 0.5 to 50 wt%, preferably 1 to 33 wt%, particularly preferably 2.5 to 25 wt%, and most preferably 5 to 20 wt%, relative to the mixture of ethoxylated alkanols and oligo- and polyethylene glycols.

[0141] The treatment of the mixture of ethoxylated alkanols and oligo- and polyethylene glycols with the adsorbent can be carried out at a temperature of 0 to 100 °C, preferably from 5 to 80 °C, particularly preferably from 10 to 50 °C, most preferably from 15 to 40 °C and particularly at ambient temperature.

[0142] In particular, ion exchangers and phenol-formaldehyde resins, as organic polymers, are sensitive to high temperatures; preferably, the treatment remains at least 30 °C below their recommended maximum operating temperature, particularly preferably at least 40 °C and most preferably at least 50 °C.

[0143] In contrast, silica gel, as an inorganic product, is largely temperature-stable, so that the mixture of ethoxylated alkanols and oligo- and polyethylene glycols can exceptionally be treated at higher temperatures than those specified above.

[0144] The pressure at which the treatment according to the invention is carried out is less relevant. The treatment can be carried out under negative or positive pressure up to 20 bar; preferably, the treatment is carried out at ambient pressure or a slight positive pressure up to 1.5 bar.

[0145] The mixture of ethoxylated alkanols and oligo- and polyethylene glycols is exposed to the adsorbent for a duration of 5 min to 48 hours, preferably 10 min to 24 hours, particularly preferably 15 min to 12 hours and most preferably 20 min to 6 hours.

[0146] To ensure adsorption, the mixture of ethoxylated alkanols and oligo- and polyethylene glycols is brought into contact with the adsorbent, with the liquid phase of the mixture being agitated relative to the solid adsorbent. This can be achieved, for example, by stirring or shaking the mixture with the adsorbent. To reduce abrasion of the adsorbent, it is preferred to immobilize the adsorbent in packed beds and move the liquid phase through these beds. This can be done, for example, in one or more stirred reactors, in which the adsorbent is held, for instance, in cages, or preferably by packed beds in tubular reactors through which the liquid phase is passed in a straight line or in a recirculating circuit.

[0147] The adsorbent can be arranged in the reactor as a full-space reactor or a section reactor (unit reactor).

[0148] In a tray reactor, the adsorbent is divided into several successive packed beds (trays) within the same apparatus, each of which can be individually thermostated. It is therefore possible to set the adsorption temperature separately for each section; preferably, the temperature increases during the treatment. The treatment can be continuous or batchwise, preferably batchwise.

[0149] Since the movement of the liquid phase at the adsorbent can lead to abrasion, or the adsorbent may contain a proportion of small solid particles, it is preferred to filter the oligo- and polyethylene glycol-depleted ethoxylated alkanols after treatment. This is preferably done by filtration through a filter with a pore size of, for example, up to 1 pim, particularly preferably from 0.1 to 0.8, and most preferably from 0.25 to 0.6 pim.

[0150] The treatment of the mixture of ethoxylated alkanols and oligo- and polyethylene glycols with the adsorbent can be carried out one or more times, for example one to five times, preferably one to three times, in order to achieve low levels of oligo- and polyethylene glycols.

[0151] After separation of the adsorbent from the mixture, the adsorbent can be regenerated and reused.

[0152] This is done, for example, by washing with water, acids such as hydrochloric acid or sulfuric acid, or alkalis such as sodium hydroxide or potassium hydroxide, and / or alcohols such as monoethylene glycol or ethanol, preferably monoethylene glycol.

[0153] To remove the adsorbed oligo- and polyethylene glycols, at least 10 to 100 times the bed volume (BV) of the liquid in question is passed over the adsorbent. It can also be rinsed first with an acid or base and then with water. When using an acidic ion exchanger as the adsorbent, the desired counterion is then introduced by neutralization with the respective base until the desired degree of neutralization is reached. The adsorbent can then be dried under vacuum at elevated temperatures, for example, organic polymers at around 50 °C and inorganic substances at around 120 °C.

[0154] By carrying out the process step (II) 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%.

[0155] By the process according to the invention, it is possible, under suitable experimental conditions, to reduce the content of oligo- and polyethylene glycols to no more than 2500 ppm, preferably no more than 2000 ppm, particularly preferably no more than 1500 ppm, and most preferably no more than 1000 ppm. Concentrations of oligo- and polyethylene glycols in the ethoxylated alkanols of no more than 750 ppm and even no more than 500 ppm by weight can be achieved.

[0156] This is particularly the case when process steps (I) and (II) are combined and the reaction product obtained after process step (I) is subsequently subjected to process step (II). Uses

[0157] The ethoxylated alkanols obtained, preferably obtained, according to the inventive process, which are depleted of oligo- and polyethylene glycols, can generally be used in all applications that are typically known for such ethoxylated alkanols that are not depleted.

[0158] These could include, for example, use as

[0159] - wetting agent

[0160] - Detergent

[0161] - Dispersing agent

[0162] - Solution mediator

[0163] - for textile cleaning and textile dyeing

[0164] - Intermediate for the synthesis of anionic phosphates, sulfates or ethercarboxylates

[0165] - as an adjuvant in agrochemical formulations: aids for improving the

[0166] - - Liability

[0167] - - Retention (spray retention aid)

[0168] - - Distribution

[0169] - - Penetration

[0170] - - Wetting aid (spreading aid) for spray solutions.

[0171] However, ethoxylated alkanols are preferably used in applications where a reduced content of oligo- and polyethylene glycols is required.

[0172] These can be, for example, emulsifiers in w / o emulsions.

[0173] These ethoxylated alkanols with a reduced content of oligo- and polyethylene glycols are particularly advantageous when 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.

[0174] These 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 ethoxylated alkanols can be used alone or, preferably, in combination with a (C8-C24)alkylamido (Ci-cejalkyl betaine).

[0175] Such an application and corresponding mixtures are described in WO 2011 / 045334 A1 .

[0176] To reduce ice crystal formation, the following quantities are preferably added to the fuel:

[0177] - from 45 to 4575 ppm, preferably 45 to 500 ppm of at least one ethoxylated alkanol and / or

[0178] - from 0 to 425 ppm, e.g. 1 to 425 ppm, preferably 1 to 5 ppm of at least one (C8-C24)alkylamido (Ci-C6)alkyl betaine.

[0179] The at least one (C8-C24)alkyl amido (Ci-C6)alkyl betaine may preferably be Cocoamidopropyl betaine.

[0180] In addition to this surface-active agent or emulsifier, 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.

[0181] The ethoxylated alkanols are mostly used in the form of liquid concentrates, essentially containing

[0182] 0.1 to 10 wt% of at least one (C8-C24)alkylamido (Ci-Cejalkyl betaine, preferably Cocoamidopropyl betaine)

[0183] 30 to 95 wt% of at least one ethoxylated alkanol, with a reduced content of oligo- and polyethylene glycols

[0184] 0 to 20 wt% of at least one glycol-based solubility enhancer, preferably ethylene glycol, and 0 to 65 wt% of at least one organic solvent, preferably ethanol.

[0185] Analogous to WO 2011 / 045334 A1 is a preferred composition of the liquid concentrate

[0186] 2 parts cocoamidopropyl betaine

[0187] 60 parts of at least one ethoxylated alkanol, with a reduced content of oligo- and polyethylene glycols

[0188] 4 parts ethylene glycol, and

[0189] 34 parts ethanol.

[0190] Turbine fuels contain a major proportion 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.

[0191] Furthermore, turbine fuels made from renewable biomass are conceivable; these are referred to as Sustainable Aviation Fuel (SAF). The requirements for these SAFs are specified in ASTM D7566, currently in revision 24d. Preferred SAFs are FT-SPK (Fischer-Tropsch Synthetic Paraffinic Kerosene, Annex 1 of ASTM D7566), HEFA-SPK (Hydroprocessed Esters and Fatty Acids, Annex 2 of ASTM D7566), HFS-SIP (Synthesized Iso-paraffin from Hydro-processed Fermented Sugar, Annex 3 of ASTM D7566), FT-SKA (Fischer Tropsch Synthetic Kerosene with Aromatics, Annex 4 of ASTM D7566), 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 D7566) and HC-HEFA-SPK (Hydroprocessed Hydrocarbons, Annex 7 of ASTM D7566).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.

[0192] 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.

[0193] In the related Solar to Liquid (StL) process, energy is provided directly via solar thermal energy. Electrolysis is eliminated; water and CO2 are directly converted into a synthesis gas using solar energy. The subsequent steps correspond to Power to Liquid technology.

[0194] Further additives, known per se, may be added to the turbine fuel. 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.

[0195] Specifications for turbine fuel and approved additives with their respective dosages are listed in ASTM D 1655-24. The microemulsions can be prepared by mixing

[0196] - 99,995 to 99,999 parts, e.g. 99,998 parts, of a fuel, e.g. a turbine fuel and

[0197] - approximately 0.0001 to approximately 0.01 parts, e.g. 0.025 parts, emulsifier composition, wherein the emulsifier composition comprises

[0198] - - at least one (C8-C24)alkylamido (Ci-C6)alkyl betaine, preferably Cocoamidopropyl betaine and

[0199] - - at least one ethoxylated alkanol, with a reduced content of oligo- and polyethylene glycols, wherein the proportions always refer to volume.

[0200] Accordingly, a further object of the present invention is a method for distributing water in fuels using ethoxylated alkanols of the formula

[0201] R 1 -O-[-CH2-CH2-O-] m -H wherein

[0202] R 1 straight-chain or branched Cs-Cu alkyl, preferably Cs-Cia alkyl, particularly preferably Cg-C alkyl, and most preferably C9-C1 i alkyl and m a rational number of 1 to 3 with a reduced content of oligo- and polyethylene glycols of the formula

[0203] HO-[-CH2-CH2-O]nH wherein n is a rational number of at least 2, preferably from 2 to 30 and particularly preferably from 2 to 20, wherein one

[0204] (I) at least one alkanol R 1 OH with at least m equivalents of ethylene oxide in the presence of at least one (earth) alkali metal alcoholate of an alkanol R 2 OH converts, where R 2 a Ci- to C-cyl residue or R 1 may be, and / or one

[0205] (II) a mixture of at least one ethoxylated alkanol of the formula

[0206] R 1 -O-[-CH2-CH2-O-] m-H with oligo- and polyethylene glycols of the formula

[0207] HO-[-CH2-CH2-O]nH treated with at least one adsorbent selected from the group consisting of

[0208] (I) phenol-formaldehyde resins,

[0209] (ii) Silica gel and

[0210] (iii) acidic ion exchangers in potassium form,

[0211] (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.

[0212] Examples

[0213] Materials and methods

[0214] Mixture of primary Cg-Cn alkanols, molecular weight 158 ​​- 164 g / mol, OH number 342 - 355 mg KOH / g (Neodol® 91 from Shell, GAS No. 66455-17-2).

[0215] On average, a 2.5-fold ethoxylated mixture of Cg-Cn alkanols (Synperonic™ 91 / 2.5 from Croda, GAS 68439-46-3).

[0216] 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.

[0217] The hydroxyl numbers (OH numbers) were determined according to DIN 53240-2 - 2007-11

[0218] Comparative example 1: 09-011 - Alcohol, ethoxylated with 2.5 mol ethylene oxide per mol, catalyzed with aqueous potassium hydroxide

[0219] In a 5-liter autoclave, 1601.0 g of O9-O11 alcohols and 8.1 g of potassium hydroxide (50 wt% in water) were stored at room temperature. A vacuum of < 50 mbar was applied and the mixture was heated to 95 °C. At this temperature and pressure, the mixture was dehydrated for 15 minutes.

[0220] The vessel was purged with nitrogen three times and heated to 175°C. Over 6 hours, 1108.2 g of ethylene oxide were added. To complete the reaction, the mixture was allowed to react for an additional 3 hours at 175°C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C.

[0221] After filtration, 2715.0 g of a light yellow oil were obtained (hydroxyl value: 210.8 mg KOH / g). The polyethylene glycol (PEG) content was determined by HPLC: 1.67 wt.% (MS determination). Example 1: C9-C11 alcohol, ethoxylated with 2.5 mol ethylene oxide per mol, catalyzed with sodium C9-C11 alkoxide, reaction temperature 120 °C

[0222] In a 1.0 L four-necked flask equipped with a reflux condenser and nitrogen inlet, 636.4 g of C9-C11 alcohol were added at 60 °C. Over 10 minutes, 1.8 g of sodium metal were added in portions. The temperature was increased to 90 °C and the mixture was stirred for 0.5 hours until the sodium was completely dissolved.

[0223] In a 2-liter pressure vessel, 636.4 g of the obtained solution of sodium C9-C11 alkoxide in C9-C11 alcohol were placed at room temperature. The vessel was purged three times with nitrogen and heated to 120 °C. Within 4 hours, 440.5 g of ethylene oxide were added. To complete the reaction, the mixture was reacted for a further 6 hours at 120 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80 °C.

[0224] After filtration, 1084.0 g of a light yellow oil were obtained (hydroxyl value: 210.7 mg KOH / g). The PEG content was determined by HPLC: 0.06 wt%.

[0225] Example 2: C9-C11 alcohol, ethoxylated with 2.5 mol of ethylene oxide per mol, catalyzed with sodium C9-C11 alkoxide, reaction temperature 175°C

[0226] In a 1.0 L four-necked flask equipped with a reflux condenser and nitrogen inlet, 850.0 g of C9-C11 alcohol were added at 60°C. Over 10 minutes, 2.2 g of sodium were added in portions. The temperature was increased to 90°C and the mixture was stirred for 0.75 hours until the sodium was completely dissolved.

[0227] In a 2-liter autoclave, 795.5 g of the obtained solution of sodium C9-C11 alkoxide in C9-C11 alcohol were added at room temperature. The vessel was purged three times with nitrogen and heated to 175°C. Within 3 hours, 550.7 g of ethylene oxide were added. For complete reaction, the mixture was allowed to react for a further 3 hours at 175°C. The reaction mixture was degassed with nitrogen, and volatile compounds were removed at 80°C under vacuum.

[0228] After filtration, 1342.0 g of a light yellow oil were obtained (hydroxyl value: 210.0 mg KOH / g). The PEG content was determined by HPLC: 0.39 wt.% (MS determination).

[0229] Example 3: C9-C11 alcohol, ethoxylated with 2.5 mol of ethylene oxide per mol, catalyzed with sodium C9-C11 alkoxide, reaction temperature 175 °C, pre-drying of the C9-C11 alcohol

[0230] In a glass flask, 850.0 g of C9-C11 alcohol and 8.5 g of sodium sulfate were placed and stirred overnight at room temperature. The upper phase was separated, and 820.0 g of this pre-dried C9-C11 alcohol were transferred at 60 °C to a 1.0-1-4-neck flask equipped with a reflux condenser and nitrogen inlet. Over 10 minutes, 2.1 g of sodium metal were added in portions. The temperature was increased to 90 °C, and the mixture was stirred for 0.75 hours until the sodium was completely dissolved.

[0231] In a 2-liter autoclave, 797.5 g of the obtained solution of sodium C9-C11 alkoxide in C9-C11 alcohol were placed at room temperature. The vessel was purged three times with nitrogen and heated to 175 °C. Within 3 hours, 550.7 g of ethylene oxide were added. For complete reaction, the mixture was allowed to react for an additional 3 hours at 175 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80 °C.

[0232] After filtration, 1334.0 g of a light yellow oil were obtained (hydroxyl value: 207.3 mg KOH / g). The PEG content was determined by HPLC: 0.47 wt.% (MS determination).

[0233] Example 4: C9-C11 alcohol, ethoxylated with 2.5 mol of ethylene oxide per mol, catalyzed with sodium methoxide, reaction temperature 175 °C

[0234] In a 5-liter autoclave, 2683.8 g of C9-C11 alcohol and 27.0 g of sodium methoxide (25 wt% in methanol) were placed at room temperature. A vacuum of < 50 mbar was applied, and the mixture was heated to 110 °C. The mixture was dehydrated for 2 hours at 110 °C under a vacuum of less than 50 mbar. The vessel was purged three times with nitrogen and heated to 175 °C. Within 12 hours, 1857.8 g of ethylene oxide were added. To complete the reaction, the mixture was allowed to react further for 3 hours at 175 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed at 80 °C under vacuum.

[0235] After filtration, 2690.0 g of a slightly yellowish liquid were obtained (hydroxyl value: 210.8 mg KOH / g). The PEG content was determined by HPLC: 0.13 wt% (MS determination).

[0236] Example A - Separation of PEG from 2.5-fold ethoxylated Cg-Cn alkanols using adsorbents

[0237] 100 g of a mixture of ethoxylated linear C9 / C11 alcohols with an average degree of ethoxylation of 2.5 were shaken with 2 g of adsorbent in glass bottles for 24 hours at room temperature. The adsorbent was then separated using a 0.45 pm membrane filter and the PEG content was measured. The PEG content of the alcohol used was 0.82%.

[0238] The adsorbents were prepared as follows:

[0239] Sodium bentonite and silica gel were dried at 120 °C under vacuum.

[0240] Phenol-formaldehyde resin: Wash with water and remove the water on filter paper. Then dry at 50 °C under vacuum.

[0241] Loading the acidic ion exchanger with potassium:

[0242] A glass tube (approx. 35 ml) was filled with Purolite C150S and rinsed with 105 ml demineralized water, 350 ml of 10% potassium chloride in demineralized water, and finally 105 ml demineralized water. Excess water was removed on filter paper, and the adsorbent was dried under vacuum at 50°C. Loading of the acidic ion exchanger with barium:

[0243] A glass tube (approx. 35 ml) was filled with Purolite C150S and rinsed with 105 ml demineralized water, 350 ml of 10% barium chloride in demineralized water, and finally 105 ml demineralized water. Excess water was removed on filter paper, and the adsorbent was dried under vacuum at 50°C.

[0244] Table A: Depletion of PEG content in ethoxylated alcohol after treatment with adsorbent

[0245] Example B - Separation of PEG from 2.5-fold ethoxylated Cg-Cn alkanols using adsorbents, variation of the amount of adsorbent

[0246] 50 g of a mixture of ethoxylated linear C9 / C11 alcohols with an average degree of ethoxylation of 2.5 were treated with additional PEG and shaken for 24 hours at room temperature in glass bottles containing 0.5–10 g of adsorbent (see table). The adsorbent was then separated using a membrane filter, and the PEG content was measured. The PEG content of the alcohol used was 2.55%.

[0247] Table B

[0248] Example C

[0249] 88 g of a mixture of ethoxylated linear C9 / C11 alcohols with an average degree of ethoxylation of 2.5 and a low PEG content of 600 ppm (achieved through optimized synthesis) was shaken with 10 g of dry Amberlite XAD761 for 24 hours. The adsorbent was filtered off, and the PEG content was determined to be 60 ppm.

[0250] Example D

[0251] A glass column (inner diameter 2 cm, length 50 cm) was filled with a bed volume (BV) of 157 ml of AmberLite XAD761, and the process steps listed in the table were performed. The liquids were pumped upwards through the column at room temperature, samples were taken, and analyzed.

[0252] The ethoxylate used had an APHA color number of 18 and a PEG content of 1376 ppm, which could be reduced to an average of 142 ppm in the first two fractions (= 2 BV) and to 194 ppm in the last two fractions. The last two fractions had an APHA color number of 74.

[0253] In regeneration step 1, the first two fractions of the eluate had a PEG content of 865 ppm, the last two 1241 ppm.

[0254] The eluate had a PEG content of < 50 ppm at the end of regeneration step 3.

[0255] The increase in the color number is due to a color bleeding of the resin, which cannot be completely suppressed or removed by pretreatment with monoethylene glycol.

[0256] Example E

[0257] A glass column (inner diameter 2 cm, length 50 cm) was filled with a bed volume (BV) of 157 ml of AmberLite XAD761, and the process steps listed in the table were performed. The liquids were pumped upwards through the column at room temperature, samples were taken, and analyzed.

[0258] The ethoxylate used had an APHA color number of 18 and a PEG content of 1376 ppm, which could be reduced to an average of 50 ppm in the first two fractions (2 BV) and to 281 ppm in the last two fractions. The last two fractions had an APHA color number of 10.

[0259] In regeneration step 1, the first two fractions of the eluate had a PEG content of 369 ppm, the last two 489 ppm.

[0260] The eluate had a PEG content of < 50 ppm at the end of regeneration step 3.

[0261] Therefore, ethanol is better suited for decolorizing the resin than monoethylene glycol, whereas monoethylene glycol is better able to displace the adsorbed PEG from the resin.

[0262] Example F

[0263] A glass column (inner diameter 2 cm, length 50 cm) was filled with a bed volume (BV) of 157 ml of AmberLite XAD761, and the process steps listed in the table were performed. The liquids were pumped upwards through the column at room temperature, samples were taken, and analyzed.

[0264] The ethoxylate used had an APHA color number of 18 and a PEG content of 1376 ppm, which could be reduced to an average of < 50 ppm in the first two fractions (2 BV) and to 50 ppm in the last two fractions.

[0265] During the regeneration step, the first two fractions of the eluate had a PEG content of 185 ppm, the last two < 50 ppm.

Claims

Patent claims 1. Method for the preparation of ethoxylated alkanols of the formula R 1 -O-[-CH2-CH2-O-] m -H wherein R 1 straight-chain or branched, preferably straight-chain, Cs-Cu-alkyl and m a rational number of 1 to 3, with a low content of oligo- and polyethylene glycols of the formula HO-[-CH2-CH2-O] n -H where n is a rational number of at least 2, preferably from 2 to 20, characterized in that one (I) at least one alkanol R 1 OH with at least m equivalents of ethylene oxide in a temperature range of 100 to 180 °C, in particular from 120 to 160 °C in the presence of at least one (Earth)Al potassium imetallic alcoholate of an alkanol R 2 OH converts, where R 2 a Ci- to C-cyl residue or R 1 may be, and / or one (II) a mixture of at least one ethoxylated alkanol of the formula R 1-O-[-CH2-CH2-O-] m -H with oligo- and polyethylene glycols of the formula HO-[-CH2-CH2-O] n -H treated with at least one adsorbent selected from the group consisting of (i) phenol-formaldehyde resins, (ii) Silica gel and (iii) acidic ion exchangers in potassium form.

2. Method according to claim 1, characterized in that in step (I) the water content in the alkanol R 1 OH, the (earth)alkali metal alcoholate and the alkanol R 2 OH does not exceed 1000 ppm by weight.

3. A method according to claim 1 or 2, characterized in that the (earth) alkali metal is selected from the group consisting of sodium, potassium, magnesium and calcium.

4. Method according to one of the preceding claims, characterized in that for case R 2 = R 1 the (Earth) Alkali metal alcoholate of alkanol R 2 OH through the reaction of the alkanol R1 OH is obtained with metallic (earth) alkali metal.

5. Method according to one of claims 1 to 3, characterized in that the alkanol R is added 1 OH a (Earth) Alkali metal alcoholate of alkanol R 2 OH is added and the alkanol R 2 OH removed from equilibrium.

6. Method according to one of the preceding claims, characterized in that the adsorbent in step (II) is at least a phenol-formaldehyde resin having a pore diameter calculated from the N2 isotherms of 400 to 800 angstroms.

7. Method according to one of claims 1 to 5, characterized in that the adsorbent is in Step (II) involves at least one silica gel with a pore size calculated from the N2 isotherms of 4 to 9 nm.

8. Method according to any one of claims 1 to 5, characterized in that the adsorbent is in Step (II) involves at least one acidic ion exchanger with sulfonic acid groups having an acid group capacity of 1 to 5 eq / l, whose acidic groups carry at least 10% of a potassium ion as a counterion.

9. Use of oligo- and polyethylene glycol-depleted ethoxylated alkanols obtained by one of the above methods as - wetting agent - Detergent - Dispersing agent - Solution mediator - for textile cleaning and textile dyeing - Intermediate for the synthesis of anionic phosphates, sulfates or ethercarboxylates - as an adjuvant in agrochemical formulations: aids for improving the - - Liability - - Retention (spray retention aid) - - Distribution - - Penetration - - Wetting aid (spreading aid) for spray solutions.

10. Use of oligo- and polyethylene glycol-depleted ethoxylated alkanols obtained according to a Methods according to any one of claims 1 to 8 as emulsifiers in w / o emulsions.

11. Use of oligo- and polyethylene glycol-depleted ethoxylated alkanols obtained according to a Method according to any one of claims 1 to 8 for distributing water in fuels, especially gasoline, diesel, marine fuels and aviation fuels.

12. Method for distributing water in fuels using ethoxylated alkanols of the formula R 1 -O-[-CH2-CH2-O-] m -H wherein R 1 straight-chain or branched Cs-Cu-alkyl and m a rational number of 1 to 3 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 from 2 to 20, wherein one considers an ethoxylated alkanol of the formula R 1 -O-[-CH2-CH2-O-] m -H according to one of the preceding claims and mixes the oligo- and polyethylene glycol-poor, ethoxylated alkanol thus obtained into a fuel selected from the group consisting of gasoline, diesel, marine fuels and aviation fuels.

13. Fuel, especially gasoline, diesel, marine fuel and aviation fuel, in particular aviation fuel, containing an oligo- and polyethylene glycol-depleted, ethoxylated alkanol with an oligo- and polyethylene glycol content of not more than 2500 ppm.

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