Method for removing aromatic sulphonic acids and their salts from aqueous phases

Abstract

The invention relates to a simple and environmentally friendly method for removing aromatic sulphonic acids or the salts thereof from alkaline aqueous phases.

Description

[0001] Process for the separation of aromatic sulfonic acids and their salts from aqueous phases

[0002] The invention relates to a simple and environmentally friendly process for the separation of aromatic sulfonic acids or their salts from aqueous phases.

[0003] Aromatic sulfonic acids based on the benzene or naphthalene and anthraquinone skeleton are important intermediates in the production of dyes, wetting and dispersing agents as well as pharmaceuticals.

[0004] Certain aromatic sulfonic acids are also frequently undesirable byproducts of chemical reactions. Sulfonic acids are formed, for example, during the conversion of aromatic hydrocarbons in the presence of sulfuric acid or sulfur trioxides, for example, in the sulfonation of aromatics. For example, tetrahydroquinoline derivatives can be rearranged under acid catalysis, for example, in the presence of sulfuric acid, to aminoindane derivatives. These aminoindane derivatives are important intermediates in the production of fungicides, for example, N-indanylcarboxamide derivatives. However, sulfonic acid derivatives of the aminoindanes are formed as secondary components. These are water-soluble and therefore enter wastewater during the processing of reaction mixtures.

[0005] Some of these substances are soluble in water, especially in the form of their salts. Therefore, chemical processes in which these substances are used or produced, or the application of such substances, often result in wastewater contaminated with these substances.

[0006] Due to the environmentally hazardous properties and chemical stability of these substances, disposal of this wastewater in wastewater treatment plants is generally not an option. One technical solution for disposing of this wastewater is incineration at high temperatures, which completely evaporates the water and thermally decomposes the organic components. However, this requires large amounts of energy.

[0007] Various processes are already known for the separation of aromatic sulfonic acids or their salts from aqueous systems. These include precipitation processes, in which water-insoluble salts, such as calcium salts, are produced and then separated from the wastewater to be treated by filtration. These processes have the disadvantage that they usually produce large quantities of solids, such as calcium carbonate or calcium sulfate, which require complex disposal. Extraction processes, usually involving two or more liquid phases, are also known. These generally use water-insoluble organic solvents. Often, the solubility of the sulfonic acids to be separated in the organic solvent is insufficient to completely remove them from the aqueous phase.Therefore, the solubility of the substance to be separated in the aqueous phase often has to be reduced by a process known as "salting out." However, this method has the disadvantage that phase separation is often insufficient and saline wastewater is produced, which in turn requires complex disposal.

[0008] US Patent No. 3,719,703 describes how certain sulfonic acids can be extracted into an organic phase in an acidic medium by treating the organic phase with a higher tertiary aliphatic amine, such as tricaprylamine, and a water-insoluble organic solvent, such as chloroform, ethyl acetate, nitrobenzene, toluene, or cyclohexane. The organic phase, which then contains the amine and the sulfonic acid or its salt, is separated from the aqueous phase. The sulfonic acid can then be isolated from the organic solution by treating the organic phase with sodium hydroxide solution and separating the aqueous alkaline phase together with the sodium salt of the sulfonic acid. This process is less suitable for industrial scale production, primarily because it produces large quantities of solvent, which are also contaminated with the sulfonic acids and must also be disposed of at great expense.

[0009] EP 41134 A2 describes a process for separating water-soluble salts of aromatic sulfonic acids, for example, m-nitrobenzenesulfonic acid, 2-nitro-5-chloro-p-toluenesulfonic acid, and α-naphthalenesulfonic acid, from sulfonation mixtures. These sulfonation mixtures contain, in addition to water and the products, sulfuric acid, which are diluted with water in the first step to a sulfuric acid content of 2 to 75 wt.% in the mixture. Subsequently, the mixture is admixed with an equivalent amount of a non-emulsifying, solvent-free, water-insoluble amine containing a total of 12 to 40 carbon atoms, which forms a salt with the sulfonic acid, causing phase separation. The phase containing the ammonium salt of the sulfonic acid is separated and treated with an excess of aqueous base, whereby the sulfonic acid is released from the ammonium salt and separates from the aqueous phase as an organic phase, which can then be isolated.Examples of such water-insoluble amines include tri-n-octylamine, tri-2-ethylhexylamine, tribenzylamine, methyldioctylamine, methyldidecylamine, tridodecylamine, tributylamine, di-2-ethylhexylamine, didecylamine, or N,N-dibutylaniline. Most primary amines with 12 to 40 carbon atoms are less suitable due to their emulsifying properties. The process according to EP 41134 A2 has the advantage of being solvent-free. However, if small amounts of neutral substances, e.g., diarylsulfone compounds, are present in the reaction mixture, these also pass into the organic phase. They must then be removed using conventional methods (e.g., filtration, distillation).

[0010] In H. Gai et al.: Journal of Cleaner Production 201 (2018) 774-782, the extraction of 1-amino-2-naphthol-4-sulfonic acid from wastewater using trioctylamine (TOA) with methyl isobutyl ketone (MIBK) or kerosene was investigated. The effects of the organic solvent, the concentration of trioctylamine, temperature, and pH on the partition coefficient of 1-amino-2-naphthol-4-sulfonic acid (ANS) were investigated. It was found that methyl isobutyl ketone is a better organic solvent than kerosene, that lower temperatures are more suitable for extraction than high temperatures (optimum: 25 °C), that a higher amount of trioctylamine is better than a lower amount (optimum: 50% TOA: 50% MIBK), and that a lower pH is more suitable than a higher pH (optimum: pH 1.1). Under optimal conditions, a maximum distribution coefficient D of 76 could be achieved.D is defined as the quotient C(orgANS) / C(aq ANS), where C(orgANS) is the ANS concentration (in mol / L) in the organic phase after extraction and C(aq ANS) is the ANS concentration (in mol / L) in the aqueous phase after extraction. It is not known whether this process is suitable for removing traces of 1-amino-2-naphthol-4-sulfonic acid from the aqueous phase in wastewater. However, this process requires an organic solvent (here, MIBK) in addition to the amine TOA, which then has to be recycled or incinerated, which is energy-intensive.

[0011] The task therefore remains to provide an improved process for the removal of aromatic sulfonic acids that avoids the disadvantages of the prior art.

[0012] Surprisingly, a process has now been found for separating sulfonic acids or their salts from aqueous phases, comprising the steps of a) adjusting the pH of the aqueous phase in which the at least one sulfonic acid or its salt is present to pH 13 to 15, and b) bringing the aqueous phase from step a) into contact with and mixing the aqueous phase from step a) with at least one amine selected from the group of alicyclic and aromatic amines having a number of carbon atoms in the molecule of 5 to 12 and a number of nitrogen atoms in the molecule of 1 to 2, whereby a mixture comprising at least one aqueous phase and an aminic phase is formed, wherein the aminic phase contains the at least one sulfonic acid or its salt to be separated, and c) separating the aqueous phase and the aminic phase.

[0013] The process according to the invention is directed to the separation of sulfonic acids or their salts from aqueous phases. In this aqueous phase, the sulfonic acids are present in protonated form, i.e., in the form of sulfonic acid, depending on the pH of the aqueous phase, or at higher pH values, in the form of sulfonic acid salts, also called sulfonates. The corresponding countercation then originates from the aqueous phase. These are usually alkali metal ions, alkaline earth metal ions, or organic cations, for example, ammonium ions. The content of sulfonic acids or their salts in the various phases is generally detected by liquid chromatography, preferably HPLC. In the first step of the process according to the invention, i.e., step a), the aqueous phase is brought to a pH in the range of 13 to 15. The pH is usually measured using pH meters or glass electrodes.Since the measurement is performed in a predominantly aqueous medium, the measurement accuracy is usually sufficiently high. Alternatively, the pH value of a solution can also be calculated.

[0014] Preferably, in step a), the pH of the aqueous phase is adjusted by adding a base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, preferably sodium hydroxide and potassium hydroxide.

[0015] The base can preferably be added in pure form or dissolved in water. Since experience has shown that pH changes are exothermic reactions, the base is preferably added by mechanically or hydraulically mixing the aqueous phase, metering the base into the mixed aqueous phase, and, if necessary, cooling the entire mixture. The base is usually added in pure form to keep the total volume of the mixture as low as possible.

[0016] Due to the high pH value, the sulfonic acid is present in the aqueous phase in the form of its dissolved and thus dissociated salt, whose countercation is predominantly defined by the cation of the base.

[0017] A pH value lower than 13 leads to significantly poorer phase separation of the mixture after addition of the amine in step b). A larger proportion of the amine remains in the aqueous phase, which is undesirable. In contrast, pH values ​​greater than 15 are not mathematically possible in aqueous solutions containing sodium hydroxide as a base. This does not improve the phase separation in step c). pH values ​​higher than 14 can generally no longer be measured but can only be calculated.In a preferred embodiment of the process according to the invention, in step a) the pH of the aqueous phase is increased with so much base, particularly preferably selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, very particularly preferably sodium hydroxide and potassium hydroxide, that ultimately after the addition of the base in the aqueous phase, i.e. at the beginning of step b), there is an excess of hydroxide ions of 1 to 3 mol of hydroxide ions per liter of aqueous phase, preferably of 1.0 to 2.0 mol of hydroxide ions per liter of aqueous phase, particularly preferably of 1.2 to 1.8 mol of hydroxide ions per liter of aqueous phase.

[0018] Step a) is preferably carried out at a temperature of 0 to 70 °C, preferably 15 to 60 °C, particularly preferably 20 to 50 °C.

[0019] In the subsequent step b), the aqueous phase from step a) is brought into contact with an amine selected from the group of alicyclic and aromatic amines having a number of carbon atoms in the molecule of 5 to 12 and a number of nitrogen atoms in the molecule of 1 to 2. Preferably, the amine is selected from the group of cyclohexylamine, isophoronediamine and aniline.

[0020] Step b) is also exothermic. Therefore, the amine is preferably added with mechanical or hydraulic mixing of the aqueous phase, metered addition of the amine to the mixed aqueous phase from step a), and optionally with cooling of the entire mixture. The amine is usually added in pure form to keep the total volume of the mixture as low as possible.

[0021] Step b) is preferably carried out at a temperature of 0 to 70 °C, preferably 15 to 60 °C, particularly preferably 20 to 50 °C.

[0022] During the addition and / or after the addition of the amine in step b), the resulting mixture is mixed, forming two phases at rest: an aqueous phase and an aminic phase. According to the invention, the "aminic phase" can also be referred to synonymously as the "organic phase." This mixing is usually carried out mechanically, for example, with a stirring device, or hydraulically, for example, by pumping. It is important to avoid the formation of two phases during mixing, which the mixture would form without sufficient mixing.

[0023] During the mixing of the two-phase mixture from step b), a transfer of the sulfonic acid or its salts from the aqueous phase into the aminic phase surprisingly occurs.

[0024] The extraction number E is a suitable parameter for the quantitative description of extractive separation. According to the invention, this is defined as the quotient of the absolute substance masses of the sulfonic acid m(org) in the organic phase and m(aq) in the aqueous phase with the volumes V(org) of the organic phase and V(aq) of the aqueous phase. Here, c(org) is the concentration [mol / liter] of the sulfonic acid in the organic phase and c(aq) is the concentration of the sulfonic acid in the aqueous phase:

[0025] E = m(org) / m(aq) = c(org) x V(org) / c(aq) x V(aq)

[0026] According to the invention, the substance mass or the concentration of the sulfonic acid in the respective phase is calculated as the sum of the ionized and non-ionized compound, i.e. the acid in its neutral form and in the form of its salt.

[0027] In the process according to the invention, unusually high extraction numbers of greater than 100, preferably greater than 500, are achieved. In non-inventive comparative experiments with other amines, for example triethylamine or tributylamine, the extraction numbers are at most 10.

[0028] For the process according to the invention, it is irrelevant whether the aqueous phase used in step a) contains other inorganic acids, such as sulfuric acid. If the aqueous phase used in step a) contains other inorganic acids, more base must be used in step a) to neutralize the inorganic acid as well. This produces salts in the aqueous phase, but these do not affect the extraction of the sulfonic acid into the organic phase.

[0029] The mixing time in step b) is, for example, from 5 minutes to 8 hours, preferably from 1 to 6 hours. The optimal mixing time can be easily determined by in-process control of the sulfonic acid content in the aqueous and amine phases.

[0030] Preferably, the mass ratio between aqueous phase and aminic phase in step b) is from 1:1 to 25:1, particularly preferably from 3:1 to 15:1. Due to the high extraction number of the sulfonic acid between aminic and aqueous phase, lower mass ratios, i.e. a higher mass of amine relative to the aqueous phase, are not necessary but make the process less economical.

[0031] After mixing in step b) of the process according to the invention, the aqueous phase formed from the mixture is separated from the amine phase in step c). The amine phase contains the sulfonic acid or its salt to be separated, and the sulfonic acid is present in only small amounts in the aqueous phase due to the high extraction number of the sulfonic acid between the amine and aqueous phases. The separated aqueous phase can be safely used for further use in other process steps, for example, discharge to a wastewater treatment plant or isolation of desired reaction products.

[0032] The aminic phase from step c) can preferably be reused in a new step b) without further treatment, without the extraction number changing significantly. Typically, an aminic phase can be reused in a new separation process up to twenty times or more without further treatment. By monitoring the sulfonic acid concentrations in both phases, the skilled person can easily determine the number of possible repetitions based on the individual circumstances and requirements. After the last use of the aminic phase in steps b) and c) of the process according to the invention, it can be disposed of as waste, for example by thermal decomposition.

[0033] The method according to the invention can preferably be applied for the following embodiments with the parameters and conditions described above.

[0034] For example, the sulfonic acid is a compound of formula (I),

[0035] in which at least one of the residues R 1 , R 2 , R 3 or R 4 stands for SO3X, and in which the radicals R 1 , R 2 , R 3 and R 4 which do not represent SO3X, each independently represent hydrogen, amino, nitro, fluorine, chlorine, bromine or alkyl and in which R 5 and R 6 together with the carbon atoms to which they are connected, form a fused alicyclic 5-membered to 7-membered ring or a 6-membered aromatic or heteroaromatic ring which itself may be substituted one or more times with the radicals R 7 , R 8 , R 9 and R 10 can be substituted, whereby

[0036] R 7 , R 8 , R 9 and R 10each independently represents COOX, SO3X, hydroxy, amino, nitro, fluorine, chlorine, bromine or alkyl and in which X represents hydrogen, an alkali metal ion, an alkaline earth metal ion or an ammonium ion.

[0037] Particularly preferred compounds of formula (I) are benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, p-toluenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid and tetradecylbenzenesulfonic acid, as well as their alkali metal salts, alkaline earth metal salts or ammonium salts.

[0038] Preferably, the compound of formula (I) is a compound of formula (II), in which the residues R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10have the meaning given for formula (I). Particularly preferred compounds of formula (II) are naphtha-2-sulfonic acid, naphtha-1,5-disulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 4-amino-5-hydroxynaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-

[0039] 1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 5-hydroxynaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 7-hydroxynaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 7-hydroxynaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,5-disulfonic acid, 4-Aminonaphthalene-1,6-disulfonic acid, 4-Hydroxynaphthalene-1,6-disulfonic acid, 8-Aminonaphthalene-1,6-disulfonic acid, 8-Hydroxynaphthalene-1,6-disulfonic acid, 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid, 4-Amino-5-hydroxynaphthalene-1,7-disulfonic acid, 4-Aminonaphthalene-1,7-disulfonic acid, 1-Hydroxynaphthalenesulfonic acid, 4-Aminonaphthalene-2-sulfonic acid, 5-Aminonaphthalene-2-sulfonic acid, 6-Amino-4-hydroxynaphthalene-2-sulfonic acid,6-Aminonaphthalene-2-sulfonic acid, 6-Hydroxynaphthalene-2-sulfonic acid, 7-Amino-4-hydroxynaphthalene-2-sulfonic acid, 7-Aminonaphthalene-2-sulfonic acid, 7-Hydroxynaphthalene-2-sulfonic acid, 8-Amino-4-hydroxynaphthalene-2-sulfonic acid, 8-Aminonaphthalene-,

[0040] 2-sulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 1-aminonaphthalene-2,7-disulfonic acid, 3,5-

[0041] Dihydroxynaphthalene-2,7-disulfonic acid, 3-Amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-Aminonaphthalene-2,7-disulfonic acid, 3-Hydroxynaphthalene-2,7-disulfonic acid, 4,5-

[0042] Dihydroxynaphthalene-2,7-disulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 4-hydroxynaphthalene-2,7-disulfonic acid, 8-aminonaphthalene-1,3,5-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid or 8-aminonaphthalene-1,3,6-trisulfonic acid, as well as their alkali metal salts, alkaline earth metal salts or ammonium salts.

[0043] Also preferably, the compound of formula (I) is a compound of formula (III),

[0044] (III) in which the radicals R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 have the meaning given for formula (I).

[0045] Particularly preferred compounds of formula (III) are tetrahydronaphthalene-1-sulfonic acid and tetrahydronaphthalene-2-sulfonic acid, as well as their alkali metal salts, alkaline earth metal salts or ammonium salts.

[0046] Also preferably, the compound of formula (I) is a compound of formula (IV),

[0047] in which at least one of the residues R 1 , R 2 , R 3 or R 4 stands for SO3X, and in which the radicals R 1 , R 2 , R 3 and R 4 which do not stand for SO3X, and the residues R 7 , R 8 and R 9have the meaning given for formula (I). The sulfonic acid of formula (I) is particularly preferably a compound of formula (IV),

[0048] (IV) in which at least one of the radicals R 1 , R 2 or R 3 stands for SO3X, and in which the radicals R 1 , R 2 and R 3 which do not stand for SO3X, and the residues R 7 , R 8 and R 9 each independently represents hydrogen, COOX, SO3X, amino, nitro, fluorine, chlorine, bromine or alkyl, and in which R 4 stands for amino, and in which X stands for hydrogen, an AI potassium metal ion or an alkaline earth metal ion or an ammonium ion.

[0049] Also particularly preferably, the sulfonic acid of formula (I) is a compound of formula (V),

[0050] (V), or a compound of formula (VI), or their alkali metal salts, alkaline earth metal salts or ammonium salts.

[0051] Alkyl in the formulas (I), (II), (III) or (IV) preferably represents linear or branched C1-C8-alkyl, which may be unsubstituted, mono- or polysubstituted, or alkyl in the formulas (I), (II), (III) or (IV) preferably represents C3-C8-cycloalkyl, which may be unsubstituted, mono- or polysubstituted, or alkyl in the formulas (I), (II), (III) or (IV) preferably represents aralkyl, which may be unsubstituted, mono- or polysubstituted.

[0052] Linear or branched C1-C6 alkyl is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, sec-pentyl, 3-pentyl, 2-methylbutyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-

[0053] 2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl or 3-ethyl-1-butyl, where the linear or branched C1-C6-alkyl may be polysubstituted, for example 2-methoxy-1-ethyl, 2-ethoxy-1-ethyl, 3-methoxy-1-propyl, 3-ethoxy-1-propyl or 1-cyclopropylmethyl.

[0054] Likewise particularly preferably, C3-C8-cycloalkyl represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 2-methylcyclopentyl,

[0055] 3-methylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2-methylcycloheptyl, 3-methylcycloheptyl, 4-methylcycloheptyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 2-ethylcyclopentyl, 3- Ethyl-cyclopentyl, 2-ethyl-cyclohexyl, 3-ethyl-cyclohexyl, 4-ethyl-cyclohexyl, 2-propyl-cyclobutyl, 3-propyl-cyclobutyl, 2-propyl-cyclopentyl, 3-propyl-cyclopentyl, 2-butyl-cyclobutyl, 3-butyl-cyclobutyl, 2-hydroxycyclopropyl or 2-fluorocyclopropyl, where the C3-C8-cycloalkyl is unsubstituted, simple or can be substituted multiple times

[0056] Aralkyl can also particularly preferably represent benzyl, phenethyl, 2-furylmethyl, 3-furylmethyl, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, 1-naphthylmethyl or 2-naphthylmethyl, which can be unsubstituted, mono- or polysubstituted.

[0057] For all preferred and particularly preferred embodiments, the process according to the invention is carried out as generally described above for sulfonic acids. Surprisingly, a large group of aromatic sulfonic acids can be separated economically and efficiently from aqueous phases using the process according to the invention.

[0058] In the examples, the capitalized terms ACID, BASE, and AMINE represent the specific substances used in Table 1. The capitalized terms PHASE A, PHASE B, and PHASE C represent the phases used or obtained listed in Table 1.

[0059] Variant A: The aqueous phase, which contains the ACID to be removed and any other components (volume of the aqueous phase, concentration of the ACID in the aqueous PHASE A: see Table 1), was adjusted to the desired pH value (pH value: see Table 1) with BASE (base and amount of base: see Table 1) and then layered with AMIN (amine and volume of amine: see Table 1). The resulting two-phase mixture was mixed intensively by stirring or shaking for a period of 15 minutes at ambient temperature. After mixing was complete, two phases formed, with the upper PHASE B containing the AMIN and the majority of the ACID and the lower PHASE C representing the aqueous phase, which contains only a small amount of the ACID or no ACID and AMIN at all.

[0060] Variant B: The amine (amine and volume of amine: see Table 1) was initially introduced, and the aqueous phase containing the acid to be removed and any other components (acid and its concentration in the aqueous phase A: see Table 1) was added, and the resulting mixture was mixed thoroughly, if necessary by stirring or shaking. This usually results in a single-phase mixture. The mixture was then adjusted to the desired pH value with base (base and amount of base: see Table 1) (pH value: see Table 1), and the resulting mixture was mixed thoroughly by stirring or shaking for a period of 15 minutes at ambient temperature. After mixing was complete, two phases formed: the upper phase B containing the amine and the majority of the acid, and the lower phase C representing the aqueous phase, which only contains a small amount of the acid and amine.

[0061] Variant C: The aqueous phase containing the ACID to be removed and any other components (volume of the aqueous phase, concentration of the ACID in the aqueous PHASE A: see Table 1) was initially introduced, and AMINE (amine and volume of amine: see Table 1) was added, and the resulting mixture was mixed, if necessary, by stirring or shaking. This generally results in a single-phase mixture. The mixture was then adjusted to the desired pH value with BASE (base and amount of base: see Table 1) (pH value: see Table 1), and the resulting mixture was mixed intensively by stirring or shaking for 15 minutes at ambient temperature. After mixing was complete, two phases formed: the upper PHASE B containing the AMINE and the majority of the ACID, and the lower phase representing the aqueous PHASE C, which contains only a small portion of the ACID and AMINE.1 00108A -13- Item 1: In Table 1, the examples according to the invention (Example numbers E1 to E8) and those not according to the invention (Example numbers N1 to N2) are given in more detail with their enamometers. m 1 tt d.

[0062] 1 00108A -14-

[0063] B CH37.6 g 10 ml Cyclohexyl sodium hydroxide solution 9.5 g 14 7.6 g in 10 ml <0.01 g / 100 amine (32 wt %) ml

[0064] 1 00108A -15-

[0065] Naphthalene-2-sulfonic acid c(aq): 10.0 mg

[0066] / 100 mltraction number: >1,000

Claims

Patent claims 1. A process for separating sulfonic acids or their salts from aqueous phases, comprising the steps of a) adjusting the pH of the aqueous phase in which the at least one sulfonic acid or its salt is present to pH 13 to 15, and b) bringing the aqueous phase from step a) into contact with and mixing the aqueous phase with at least one amine selected from the group of alicyclic and aromatic amines having a number of carbon atoms in the molecule of 5 to 12 and a number of nitrogen atoms in the molecule of 1 to 2, whereby a mixture comprising at least one aqueous phase and an aminic phase is formed, wherein the aminic phase contains the at least one sulfonic acid or its salt to be separated, and c) separating the aqueous phase and the aminic phase.

2. Process according to claim 1, in which the sulfonic acids are a compound of formula (I), in which at least one of the radicals R 1, R 2 , R 3 or R 4 stands for SO3X, and in which the radicals R 1 , R 2 , R 3 , and R 4 which do not represent SO3X, each independently represent hydrogen, nitro, fluorine, chlorine, bromine or alkyl and in which R 5 and R 6 together with the carbon atoms to which they are connected, form a fused alicyclic 5-membered to 7-membered ring or a 6-membered aromatic or heteroaromatic ring which itself may be substituted one or more times with the radicals R 7 , R 8 , R 9 and R 10 can be substituted, whereby R 7 , R 8 , R 9 and R 10 each independently represents COOX, SO3X, hydroxy, amino, nitro, fluorine, chlorine, bromine or alkyl and in which X represents hydrogen, an alkali metal ion, an alkaline earth metal ion or an ammonium ion, 3. A process according to claim 1 or 2, in which a compound of formula (I) is incorporated (II), (II)., in which the radicals R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 have the meaning given for formula (I).

4. A process according to claim 1 or 2, wherein the compound of formula (I) is a compound of Formula (III), (III), in which the radicals R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 have the meaning given for formula (I).

5. A process according to claim 1 or 2, wherein the compound of formula (I) is a compound of Formula (IV), in which at least one of the residues R 1 , R 2 , R 3 or R 4 stands for SO3X, and in which the residues R 1 , R 2 , R 3 or R 4 which do not stand for SO3X, and the residues R 7 , R 8 and R 9 have the meaning given for formula (I).

6. A process according to claim 1 or 2, wherein the sulfonic acids of formula (I) are a compound of formula (IV), in which at least one of the radicals R 1 , R 2 or R 3 stands for SO3X, and in which the radicals R 1 , R 2 , R 3 which do not stand for SO3X, and the residues R 7 , R 8 and R 9 each independently represents hydrogen, COOX, SO3X, amino, nitro, fluorine, chlorine, bromine or alkyl, and in which R 4 represents amino, and in which X represents hydrogen, an alkali metal ion or an alkaline earth metal ion or an ammonium ion.

7. A process according to claim 1 or 2, wherein the sulfonic acids of formula (I) are a compound of formula (V), (V), or a compound of formula (VI) or their alkali metal salts, alkaline earth metal salts or ammonium salts.

8. A process according to any one of claims 2 to 6, in which alkyl in formulas (I), (II), (III) or (IV) represents linear or branched C1-C6-alkyl which may be unsubstituted, mono- or polysubstituted, or in which alkyl represents Cs-Cs-cycloalkyl which may be unsubstituted, mono- or polysubstituted, or in which alkyl represents aralkyl which may be unsubstituted, mono- or polysubstituted.

9. The method according to any one of claims 2 to 6, in which linear or branched C1-C6 alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, sec-pentyl, 3-pentyl, 2-methylbutyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl or 3-ethyl-1-butyl, where the linear or branched C1-C6-alkyl may be polysubstituted, for example 2-methoxy-1-ethyl, 2-ethoxy-1-ethyl, 3-methoxy-1-propyl, 3-ethoxy-1-propyl or 1-cyclopropylmethyl.

10. A process according to any one of claims 2 to 6, in which Ce-Ce-cycloalkyl is cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2-methylcycloheptyl, 3-methylcycloheptyl, 4-methylcycloheptyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-propylcyclobutyl, 3- Propylcyclobutyl, 2-propylcyclopentyl, 3-propylcyclopentyl, 2-butyl-cyclobutyl, 3-butyl-cyclobutyl, 2-hydroxycyclopropyl or 2-fluorocyclopropyl, where the C3-C8-cycloalkyl may be unsubstituted, mono- or polysubstituted.

11. A process according to any one of claims 2 to 6, wherein aralkyl represents benzyl, phenethyl, 2-furylmethyl, 3-furylmethyl, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, 1-naphthylmethyl or 2-naphthylmethyl, which may be unsubstituted, mono- or polysubstituted.

12. Process according to one of claims 1 to 11, in which in step a) the pH of the aqueous phase is adjusted by a base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, preferably sodium hydroxide and potassium hydroxide.

13. A process according to any one of claims 1 to 12, wherein in step b) the amine is selected from the group consisting of cyclohexylamine, isophoronediamine and aniline.

14. The process according to any one of claims 1 to 13, wherein steps a), b) and / or c) are carried out at a temperature of 0 to 70 °C, preferably 15 to 60 °C, particularly preferably 20 to 50 °C.

15. Process according to one of claims 1 to 14, in which in step b) the mass ratio between aqueous phase and amine is from 1:1 to 25:1, preferably from 3:1 to 15:1.

Images