CA2085144A1 - Method for processing waste waters containing organic phosphorus compounds, in particular sulfonted arylphosphines - Google Patents
Method for processing waste waters containing organic phosphorus compounds, in particular sulfonted arylphosphinesInfo
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- CA2085144A1 CA2085144A1 CA002085144A CA2085144A CA2085144A1 CA 2085144 A1 CA2085144 A1 CA 2085144A1 CA 002085144 A CA002085144 A CA 002085144A CA 2085144 A CA2085144 A CA 2085144A CA 2085144 A1 CA2085144 A1 CA 2085144A1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
Frankfurt, Dec. 16, 1991 PAT/rcht-sei Hoe91/Y017 Hoechst Aktienqesellschaft, Frankfurt am Main 80 A b s t r a c t Waste waters containing, in addition to water-soluble inorganic salts, water-soluble organic phosphorus com-pounds, in particular sulfonated arylphosphines, and possibly further organic contaminants, are treated with an inorganic acid and subsequently extracted with a water-insoluble amine. In a particular embodiment, the inorganic acid is used in the form of a salt of the amine used as the extractant.
Description
Method for Processina waste waters containing ~
, .,~
oraanic phosphorus com~ounds in particular sulfonated arylphosphines Tne invention rela~es IO the processin~ of waste waters containing water-soluble organic phosphorus compounds, in particular sulfonated arylphosphines, and possibly further organic contaminants, as well as water-soluble sulfates. The object of the novel method is to free the waste waters from unwanted impurities to the extent that they may be passed to conventional purification installations or may be recycled to chemical reactions as process water.
Triarylphosphines sulfonated in the aryl groups have found widespread use, particularly when dissolved in water together with rhodium compounds, as catalysts in chemical industry. Inter alia, they are used successfully in hydroformyla~ion of olefins (cf. DE 26 27 354 B1);
cyclic amines are added to conjugated dienes in their presence (cf. EP 01 76 398 A1); or they are used as catalysts for hydrogenation of organic compounds.
The preparation of sulfonated triarylphosphines according to a proven method (DE 32 35 030 Al) uses triarylphos-phines as starting materials which are reacted with oleum. The sulfonation mixture is hydrolyzed and extrac-ted with a wa~er-insoluble amine dissolved in a water-insoluble organic solvent. From the organic phase the sulfonated triarylphosphine is isolated by treatment with the aqueous solution of basic reagents. Suitable bases for the transfer of the arylphosphinesulfonic acid into the aqueous phase and, at the same time, for conversion into the salt required as the end product are the hydr-oxides of the alkali and alkaline earth metals, in particular an alkali metal hydroxide, ammonia, and also the alkali metal carbonates. However, water-soluble amines may also be used, such as methylamine, ethylamine, propylamine, butylamine or ethanolamine. In order to obtain compounds as uniform as possible, i.e. compounds sulfonated to the same degree, the reaction with the base is preferably carried out at different discrete pH
values. The useful products are obtained in a pH range of about 4.5 to 7. Below a pH of 4.5 and above a pH of 7 to pH 12, it is predominantly by-products and secondary products of sulfone reaction that are extracted; the aqueous solutions produced in these pH ranges constitute the waste water.
Depending on the water-soluble basic extractant used, the waste water contains between 1 and 8~ by weight of alkali metal salts, alkaline earth metal salts, ammonium salts or alkylammonium salts. It is loaded with water-soluble phosphorus compounds, in particular sulfonated arylphosphines, and further organic substances, which account for the COD value (about 5 to 25 g/l).
The COD value - the abbreviation COD stands for chemical oxygen demand - is a characteristic value for the loading of waters by organic substances. It is the amount of potassium dichromate, expressed as the oxygen equivalent, which is consumed by the oxidizable substances contained in a liter of water. The determination of the COD value is carried out accord~ng to a standardized procedure. I~
is described, for example, in Ullmanns Encyclopadie der Technischen Chemie (Encyclopedia of Industrial Chemistry), 4th Edition (1981), Volume 6, pp. 376 et seq.
As used herein, water-soluble organic phosphorus compounds are in particular sulfonated triarylphosphines, the term phosphines in the present instance being used in an extended sense including phosphine oxides and phosphine sulfides. If the sulfonated triarylphosphine is, for example, the sulfonation product of triphenylphosphine, then the waste water contains (the abbreviations used hereinafter of the compounds are shown in parentheses) inter alia the phosphines tris(m-sulfophenyl)phosphine (TPPTS) bis(~-sulfophenyl)phenylphosphine (TPPDS) ~?h-~-Y'(~.-s 'f^~henyl)phosphine (~
in addition the phosphine oxides formed by oxidation tris(m-sulfophenyl)phosphine oxide (TPPOTS) bis(m-sulfophenyl)phenylphosphine oxide (TPPODS) and in small amounts the phosphine sulfides produced by reduction processes tris(m-sulfophenyl)phosphine sulfide (TPPSTS) bis(m-sulfophenyl)phenylphosphine sulfide (TPPSDS) EP 41 134 A2 discloses the separation of water-soluble salts of aromatic sulfonic acids from sulfonation mix-tures with the help of water-insoluble amines. To this end, the sulfonation mixture is diluted with water and subsequently mixed with an amount of a solvent-free amine equivalent to the sulfonic acid. The sulfonic acid forms a lipophilic ammonium salt which separates spontaneously from the aqueous phase. This preparative method pre-supposes that the sulfonation mixture is essentially free of unsulfonated starting material and other neutral substances. Waste products of chemical processes do not ~enerally meet this requirement, as the formation of neutral substances as contaminants, albeit only in small amounts, by side reactions and secondary reac~ions can never be excluded. Furthermore, purification operations are not based on preparative methods; rather should khey be described as analytical processes which must detect and separate off even those substances which are only present in trace amounts.
It is an object of the invention to provide a method which allows the reliable removal of water-soluble organic phosphorus compounds and other contaminants from ;~r~
waste waters. This method shall not be sub~ect to any constraints and shall be economical. It is to produce w~ ' e- C r such pl_ity ~2' ' he W~ _e- -.ay be p2ssed o conventional purification installations or outfalls or, in order to eliminate waste waters wholly or partly, may be recycled into chemical reactions.
According to the invention this object is achieved by a method for processing waste waters which contain, in addition to water-soluble inorganic salts, water-soluble organic phosphorus compounds, in particular sulfonated arylphosphines, and possibly further organic contaminants, which comprises the addition of an inorganic acid to the waste waters in such an amount that per mole of sulfonate groups ( -S03- ) present in solution at least 1.1 mole of hydrogen ions are present, the subsequent extraction using at least one mole of an amine sparingly soluble or insoluble in water per mole of dissolved sulfonate groups, the mutual separation of the organic and the aqueous phase, and further processing of the organic phase.
The method according to the invention ensures that organic phosphorus compounds dissolved in the waste water, in particular sulfonated arylphosphines and further organic contaminants, which in total are measured as the COD value, are substantially removed. The purified waste waters do not pollute the environment and may be used as process water for chemical reactions.
The method according to the invention is applied to waste waters produced in the preparation of sulfonated aryl-phosphines. Which specific process variants are appliedin an individual case is immaterial in this context. The method cited in the context of the description of the prior art is only mentioned as an example; other prepara-tion methods are possible. An important characteristic of the waste waters employed according to the invention, ~r~
because of their impact on the environment, is the concentration of the phosphorus compounds dissolved in 'hem. In typical waste wate_s said concent.a~ion is 400 to 1500 ppm by weight, in particular 600 to 1200 ppm by weight, and results, for example in the case of the TPPTS synthesis, from the content of TPPTS, TPPDS, TPPOTS, TPPODS. TPPSTS and TPPSDS. Including said phosphorus compounds, the waste waters contain in total 1 to 30 g/l, in particular 5 to 25 g/l, of compounds which are measured as the COD value.
The waste waters to be reprocessed according to the novel method are first acidified. To this end they are treated, according to the invention, with an amount of an inorganic acid such that per mole of sulfonate groups present in solution at least 1.1 mol, in particular 1.5 to 3.0 mol of hydrogen ions are present. A higher excess of acid does no harm but is unnecessary, for example for economic reasons, but in particular also to avoid unnecessary pollution of the waste water. If free base is still present in the waste waters in addition to the sulfonate, the amount of hydrogen ions required for its neutralization shall be added to the amount of hydrogen ions to be used according to the invention.
The hydrogen ions are added to the waste waters in the form of strong inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Particu-larly suitable are sulfuric acid and phosphoric acid. If polybasic acids such as sulfuric or phosphoric acid are used, the amount of hydrogen ion added to the waste water depends on the acidity constant of the individual dissociation steps. It can be assumed that up to an acidity constant of about 0.7 x I 0 -2 complete dissociation of the hydrogen ions takes place, and that therefore one mole of acid produces one mole of hydrogen ions.
Accordingly, one mole of sulfuric acid as a dibasic acid with an acidity constant in the second dissociation step - 6 - ~ 4 of 1.2 x 10-2 produces two moles of hydrogen ions, while the tribasic phosphoric acid, in accordance with the acidlty cor.stant in the -_st dissociation step of 0.75 x 10-Z, only produces one mole of hydrogen ions.
After acidification, in a second step the contaminants contained in the waste waters are extracted using an amine which is sparingly soluble or insoluble in water.
The required amount of amine also depends on the amount of sulfonate groups contained in the waste water. Per mole of sulfonate groups present in solution at least one mole of amine and preferably 1 to 4 mol of amine are added to the waste water.
Instead of first adding acid to the waste waters and subsequently extracting the contaminants with an amine, it is a particular embodiment of the method according to the invention that the required amount of acid and amine be added in the form of an amine salt. It is evident that in this case the molar quantities of acid and amine are equal. ~s the acid is always used in excess, based on dissolved sulfonate, there will then equally always be an excess of amine.
Conveniently, the amine used for the extraction is liquid under the conditions of the extraction. Its effect is, inter alia, due to the fact that it reacts with the acidic components of the waste water to form salts. The amine salts must also be sparingly soluble in water, but readily soluble in organic solvents. Another mode of action of the amine is based on the purely physical solution of contaminants contained in the waste wat0rs.
Possible amines forming, with acids, salts which are sparingly soluble in water but which are lipophilic are acyclic or cyclic aliphatic, aromatic, araliphatic and heterocyclic primary, secondary or tertiary, preferably secondary or tertiary amines. Preferred are acyclic, ~'r`~3~ k ~
branched or nonbranched aliphatic amines having, in total, 10 to 60, in particular 13 to 36 carbon atoms.
Exa~ples of such compounds are tri-n-hexylamine, tri-n-octylamine, triisooctylamine, bis(2-ethylhexyl)amine, S triisononylamine (in the form of the isomer mixture), isotridecylamine (in the form of the isomer mixture), diisononyl(2-phenylpropyl)amine, isononylbis(2-phenyl-propyl)aminel triisotridecylamine (in the form of the isomer mixture), N,N-dimethylhexadecylamine, N,N-dimethyloctadecylamine. The extractants that were found particularly useful are isotridecylamine, tri-n-octylamine and triisooctylamine.
In principle, the amines may be used undiluted for the purpose of extraction. More advantageously, however, they are used as a solution in an organic solvent which is immiscible or only sparingly miscible with water. The concentration of the amine in the solution can extend over a wide range. It is mainly limited by the solubility of the amine salts in the solvent and by the viscosity of the salt solution produced. Accordingly, the solutions usually contain 10 to 50, preferably 15 to 35~ by weight of amine. In the selection of the solvent, predominant consideration is given to its physical properties.
Desirable characteristics are sparing solubility in water, low volatility and little or no tendency to form emulsions. In addition, the solvent should be inert, non-toxic and inexpensive, have good hydrodynamic properties and should also be effective in extractinq other con-taminants dissolved in the waste waters. Suitable sol-vents are kerosine-like fractions, i.e. hydrocarbons with boiling points between 175 and 325C, aromatic fractions, C4-C20-alcohols, C~-C20-ethers. Preferred are kerosine-like fractions and toluene. Amine salts are always used in the form of solutions, the same solutions being used as for the amines. The concentration of the salts in the solu-tion is normally also 10 to 50, preferably 15 to 35% by weight.
The extraction is, as a rule, carried out at normal temperature and normal pressure, without however excluding conditions different from these, for example superatmospheric pressure.
Further processing of the organic phase in a third step, for the purpose of transferring the contaminants into a concentrated aqueous solution and regenerating the amine, can be carried out in several ways. It has been found useful, for example, to re-extract the amine phase with the aqueous solution of an inorganic base. Suitable compounds are the hydroxides of the alkali and alkaline earth metals, in particular sodium hydroxide, as well as the alkali metal carbonates. The base is employed as a 5 to 30% by weight solution and, relative to the amine, is used preferably in a stoichiometric amount or, where appropriate, in an excess of up to 20~. A greater excess of the base adds a further unwanted solution component to the aqueous solution which contains the contaminants in concentrated form, and should therefore be avoided.
Another successfully applied method for further reprocessing of the amine phase is its treatment with steam. To this end, steam of at least 1.8 MPa is passed into the amine solution. The contaminants then pass into the aqueous phase which is separated from the amine phase, for example by decanting.
The amine recovered after treatment with a base or with steam may, together with the solvent used where required, be reused for extractive treatment of waste waters according to the me~hod according to the invention. From time to time, like the solvent, it may be purified, for example by distillation.
The method according to the invention is carried out discontinuously and, preferably, continuously, the apparatus generally employed for extractive separation of materials, such as extraction columns and mixer-settlers, being used. Single-step or multi-s~ep operation is possible.
The following examples describe the invention, but do not limit it to these particular embodiments.
Examples l to 7 In the following examples, waste waters are used whose phosphorus content and COD value are shown in the follow-ing table.
Waste water, sulfuric acid (29.9% by weight, based on the aqueous solution) and a solution of triisooctylamine in toluene (approxima~ely 20~ by weight, based on the solution) as the extractant are successively introduced into a stirred reactor. The mixture is stirred for 30 minutes at room temperature, and the water phase, i.e.
the purified waste water, is separated from the amine phase. The amine phase is re-extracted by stirring for 30 minutes with aqueous NaOH solution. The aqueous phase obtained after phase separation contains in concentrated form nearly all the contaminants of the waste water, while the amine phase can be reused as the extractant.
The reaction conditions and the results of the waste water processing are also summarized in the table.
Examples 1 to 4 describe the novel method; the opera-tional conditions of Examples 5 to 7 do not correspond to those of the invention.
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oraanic phosphorus com~ounds in particular sulfonated arylphosphines Tne invention rela~es IO the processin~ of waste waters containing water-soluble organic phosphorus compounds, in particular sulfonated arylphosphines, and possibly further organic contaminants, as well as water-soluble sulfates. The object of the novel method is to free the waste waters from unwanted impurities to the extent that they may be passed to conventional purification installations or may be recycled to chemical reactions as process water.
Triarylphosphines sulfonated in the aryl groups have found widespread use, particularly when dissolved in water together with rhodium compounds, as catalysts in chemical industry. Inter alia, they are used successfully in hydroformyla~ion of olefins (cf. DE 26 27 354 B1);
cyclic amines are added to conjugated dienes in their presence (cf. EP 01 76 398 A1); or they are used as catalysts for hydrogenation of organic compounds.
The preparation of sulfonated triarylphosphines according to a proven method (DE 32 35 030 Al) uses triarylphos-phines as starting materials which are reacted with oleum. The sulfonation mixture is hydrolyzed and extrac-ted with a wa~er-insoluble amine dissolved in a water-insoluble organic solvent. From the organic phase the sulfonated triarylphosphine is isolated by treatment with the aqueous solution of basic reagents. Suitable bases for the transfer of the arylphosphinesulfonic acid into the aqueous phase and, at the same time, for conversion into the salt required as the end product are the hydr-oxides of the alkali and alkaline earth metals, in particular an alkali metal hydroxide, ammonia, and also the alkali metal carbonates. However, water-soluble amines may also be used, such as methylamine, ethylamine, propylamine, butylamine or ethanolamine. In order to obtain compounds as uniform as possible, i.e. compounds sulfonated to the same degree, the reaction with the base is preferably carried out at different discrete pH
values. The useful products are obtained in a pH range of about 4.5 to 7. Below a pH of 4.5 and above a pH of 7 to pH 12, it is predominantly by-products and secondary products of sulfone reaction that are extracted; the aqueous solutions produced in these pH ranges constitute the waste water.
Depending on the water-soluble basic extractant used, the waste water contains between 1 and 8~ by weight of alkali metal salts, alkaline earth metal salts, ammonium salts or alkylammonium salts. It is loaded with water-soluble phosphorus compounds, in particular sulfonated arylphosphines, and further organic substances, which account for the COD value (about 5 to 25 g/l).
The COD value - the abbreviation COD stands for chemical oxygen demand - is a characteristic value for the loading of waters by organic substances. It is the amount of potassium dichromate, expressed as the oxygen equivalent, which is consumed by the oxidizable substances contained in a liter of water. The determination of the COD value is carried out accord~ng to a standardized procedure. I~
is described, for example, in Ullmanns Encyclopadie der Technischen Chemie (Encyclopedia of Industrial Chemistry), 4th Edition (1981), Volume 6, pp. 376 et seq.
As used herein, water-soluble organic phosphorus compounds are in particular sulfonated triarylphosphines, the term phosphines in the present instance being used in an extended sense including phosphine oxides and phosphine sulfides. If the sulfonated triarylphosphine is, for example, the sulfonation product of triphenylphosphine, then the waste water contains (the abbreviations used hereinafter of the compounds are shown in parentheses) inter alia the phosphines tris(m-sulfophenyl)phosphine (TPPTS) bis(~-sulfophenyl)phenylphosphine (TPPDS) ~?h-~-Y'(~.-s 'f^~henyl)phosphine (~
in addition the phosphine oxides formed by oxidation tris(m-sulfophenyl)phosphine oxide (TPPOTS) bis(m-sulfophenyl)phenylphosphine oxide (TPPODS) and in small amounts the phosphine sulfides produced by reduction processes tris(m-sulfophenyl)phosphine sulfide (TPPSTS) bis(m-sulfophenyl)phenylphosphine sulfide (TPPSDS) EP 41 134 A2 discloses the separation of water-soluble salts of aromatic sulfonic acids from sulfonation mix-tures with the help of water-insoluble amines. To this end, the sulfonation mixture is diluted with water and subsequently mixed with an amount of a solvent-free amine equivalent to the sulfonic acid. The sulfonic acid forms a lipophilic ammonium salt which separates spontaneously from the aqueous phase. This preparative method pre-supposes that the sulfonation mixture is essentially free of unsulfonated starting material and other neutral substances. Waste products of chemical processes do not ~enerally meet this requirement, as the formation of neutral substances as contaminants, albeit only in small amounts, by side reactions and secondary reac~ions can never be excluded. Furthermore, purification operations are not based on preparative methods; rather should khey be described as analytical processes which must detect and separate off even those substances which are only present in trace amounts.
It is an object of the invention to provide a method which allows the reliable removal of water-soluble organic phosphorus compounds and other contaminants from ;~r~
waste waters. This method shall not be sub~ect to any constraints and shall be economical. It is to produce w~ ' e- C r such pl_ity ~2' ' he W~ _e- -.ay be p2ssed o conventional purification installations or outfalls or, in order to eliminate waste waters wholly or partly, may be recycled into chemical reactions.
According to the invention this object is achieved by a method for processing waste waters which contain, in addition to water-soluble inorganic salts, water-soluble organic phosphorus compounds, in particular sulfonated arylphosphines, and possibly further organic contaminants, which comprises the addition of an inorganic acid to the waste waters in such an amount that per mole of sulfonate groups ( -S03- ) present in solution at least 1.1 mole of hydrogen ions are present, the subsequent extraction using at least one mole of an amine sparingly soluble or insoluble in water per mole of dissolved sulfonate groups, the mutual separation of the organic and the aqueous phase, and further processing of the organic phase.
The method according to the invention ensures that organic phosphorus compounds dissolved in the waste water, in particular sulfonated arylphosphines and further organic contaminants, which in total are measured as the COD value, are substantially removed. The purified waste waters do not pollute the environment and may be used as process water for chemical reactions.
The method according to the invention is applied to waste waters produced in the preparation of sulfonated aryl-phosphines. Which specific process variants are appliedin an individual case is immaterial in this context. The method cited in the context of the description of the prior art is only mentioned as an example; other prepara-tion methods are possible. An important characteristic of the waste waters employed according to the invention, ~r~
because of their impact on the environment, is the concentration of the phosphorus compounds dissolved in 'hem. In typical waste wate_s said concent.a~ion is 400 to 1500 ppm by weight, in particular 600 to 1200 ppm by weight, and results, for example in the case of the TPPTS synthesis, from the content of TPPTS, TPPDS, TPPOTS, TPPODS. TPPSTS and TPPSDS. Including said phosphorus compounds, the waste waters contain in total 1 to 30 g/l, in particular 5 to 25 g/l, of compounds which are measured as the COD value.
The waste waters to be reprocessed according to the novel method are first acidified. To this end they are treated, according to the invention, with an amount of an inorganic acid such that per mole of sulfonate groups present in solution at least 1.1 mol, in particular 1.5 to 3.0 mol of hydrogen ions are present. A higher excess of acid does no harm but is unnecessary, for example for economic reasons, but in particular also to avoid unnecessary pollution of the waste water. If free base is still present in the waste waters in addition to the sulfonate, the amount of hydrogen ions required for its neutralization shall be added to the amount of hydrogen ions to be used according to the invention.
The hydrogen ions are added to the waste waters in the form of strong inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Particu-larly suitable are sulfuric acid and phosphoric acid. If polybasic acids such as sulfuric or phosphoric acid are used, the amount of hydrogen ion added to the waste water depends on the acidity constant of the individual dissociation steps. It can be assumed that up to an acidity constant of about 0.7 x I 0 -2 complete dissociation of the hydrogen ions takes place, and that therefore one mole of acid produces one mole of hydrogen ions.
Accordingly, one mole of sulfuric acid as a dibasic acid with an acidity constant in the second dissociation step - 6 - ~ 4 of 1.2 x 10-2 produces two moles of hydrogen ions, while the tribasic phosphoric acid, in accordance with the acidlty cor.stant in the -_st dissociation step of 0.75 x 10-Z, only produces one mole of hydrogen ions.
After acidification, in a second step the contaminants contained in the waste waters are extracted using an amine which is sparingly soluble or insoluble in water.
The required amount of amine also depends on the amount of sulfonate groups contained in the waste water. Per mole of sulfonate groups present in solution at least one mole of amine and preferably 1 to 4 mol of amine are added to the waste water.
Instead of first adding acid to the waste waters and subsequently extracting the contaminants with an amine, it is a particular embodiment of the method according to the invention that the required amount of acid and amine be added in the form of an amine salt. It is evident that in this case the molar quantities of acid and amine are equal. ~s the acid is always used in excess, based on dissolved sulfonate, there will then equally always be an excess of amine.
Conveniently, the amine used for the extraction is liquid under the conditions of the extraction. Its effect is, inter alia, due to the fact that it reacts with the acidic components of the waste water to form salts. The amine salts must also be sparingly soluble in water, but readily soluble in organic solvents. Another mode of action of the amine is based on the purely physical solution of contaminants contained in the waste wat0rs.
Possible amines forming, with acids, salts which are sparingly soluble in water but which are lipophilic are acyclic or cyclic aliphatic, aromatic, araliphatic and heterocyclic primary, secondary or tertiary, preferably secondary or tertiary amines. Preferred are acyclic, ~'r`~3~ k ~
branched or nonbranched aliphatic amines having, in total, 10 to 60, in particular 13 to 36 carbon atoms.
Exa~ples of such compounds are tri-n-hexylamine, tri-n-octylamine, triisooctylamine, bis(2-ethylhexyl)amine, S triisononylamine (in the form of the isomer mixture), isotridecylamine (in the form of the isomer mixture), diisononyl(2-phenylpropyl)amine, isononylbis(2-phenyl-propyl)aminel triisotridecylamine (in the form of the isomer mixture), N,N-dimethylhexadecylamine, N,N-dimethyloctadecylamine. The extractants that were found particularly useful are isotridecylamine, tri-n-octylamine and triisooctylamine.
In principle, the amines may be used undiluted for the purpose of extraction. More advantageously, however, they are used as a solution in an organic solvent which is immiscible or only sparingly miscible with water. The concentration of the amine in the solution can extend over a wide range. It is mainly limited by the solubility of the amine salts in the solvent and by the viscosity of the salt solution produced. Accordingly, the solutions usually contain 10 to 50, preferably 15 to 35~ by weight of amine. In the selection of the solvent, predominant consideration is given to its physical properties.
Desirable characteristics are sparing solubility in water, low volatility and little or no tendency to form emulsions. In addition, the solvent should be inert, non-toxic and inexpensive, have good hydrodynamic properties and should also be effective in extractinq other con-taminants dissolved in the waste waters. Suitable sol-vents are kerosine-like fractions, i.e. hydrocarbons with boiling points between 175 and 325C, aromatic fractions, C4-C20-alcohols, C~-C20-ethers. Preferred are kerosine-like fractions and toluene. Amine salts are always used in the form of solutions, the same solutions being used as for the amines. The concentration of the salts in the solu-tion is normally also 10 to 50, preferably 15 to 35% by weight.
The extraction is, as a rule, carried out at normal temperature and normal pressure, without however excluding conditions different from these, for example superatmospheric pressure.
Further processing of the organic phase in a third step, for the purpose of transferring the contaminants into a concentrated aqueous solution and regenerating the amine, can be carried out in several ways. It has been found useful, for example, to re-extract the amine phase with the aqueous solution of an inorganic base. Suitable compounds are the hydroxides of the alkali and alkaline earth metals, in particular sodium hydroxide, as well as the alkali metal carbonates. The base is employed as a 5 to 30% by weight solution and, relative to the amine, is used preferably in a stoichiometric amount or, where appropriate, in an excess of up to 20~. A greater excess of the base adds a further unwanted solution component to the aqueous solution which contains the contaminants in concentrated form, and should therefore be avoided.
Another successfully applied method for further reprocessing of the amine phase is its treatment with steam. To this end, steam of at least 1.8 MPa is passed into the amine solution. The contaminants then pass into the aqueous phase which is separated from the amine phase, for example by decanting.
The amine recovered after treatment with a base or with steam may, together with the solvent used where required, be reused for extractive treatment of waste waters according to the me~hod according to the invention. From time to time, like the solvent, it may be purified, for example by distillation.
The method according to the invention is carried out discontinuously and, preferably, continuously, the apparatus generally employed for extractive separation of materials, such as extraction columns and mixer-settlers, being used. Single-step or multi-s~ep operation is possible.
The following examples describe the invention, but do not limit it to these particular embodiments.
Examples l to 7 In the following examples, waste waters are used whose phosphorus content and COD value are shown in the follow-ing table.
Waste water, sulfuric acid (29.9% by weight, based on the aqueous solution) and a solution of triisooctylamine in toluene (approxima~ely 20~ by weight, based on the solution) as the extractant are successively introduced into a stirred reactor. The mixture is stirred for 30 minutes at room temperature, and the water phase, i.e.
the purified waste water, is separated from the amine phase. The amine phase is re-extracted by stirring for 30 minutes with aqueous NaOH solution. The aqueous phase obtained after phase separation contains in concentrated form nearly all the contaminants of the waste water, while the amine phase can be reused as the extractant.
The reaction conditions and the results of the waste water processing are also summarized in the table.
Examples 1 to 4 describe the novel method; the opera-tional conditions of Examples 5 to 7 do not correspond to those of the invention.
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Claims (11)
1. A method for processing waste waters which contain, in addition to water-soluble inorganic salts, water-soluble organic phosphorus compounds, in particular sulfonated arylphosphines and possibly further organic contaminants, which comprises the addition of an inorganic acid to the waste waters in such an amount that per mole of sulfonate groups (-S03-?) present in solution at least 1.1 mol of hydrogen ions are present, the subsequent extraction using at least one mol of an amine sparingly soluble or insoluble in water per mole of dissolved sul-fonate groups, the mutual separation of the organic and the aqueous phase, and further processing of the organic phase.
2. The method as claimed in claim 1, wherein 1.5 to
3.0 mol of hydrogen ions per mole of dissolved sulfonate groups and/or carboxylate groups are present in the waste waters.
3. The method as claimed in claim 1 or 2, wherein sulfuric acid or phosphoric acid is used as the inorganic acid.
3. The method as claimed in claim 1 or 2, wherein sulfuric acid or phosphoric acid is used as the inorganic acid.
4. The method as claimed in one or more of claims 1 to 3, wherein the extraction is carried out with 1 to 4 mol of amine.
5. The method as claimed in one or more of claims 1 to 4, wherein the extraction is carried out with an acyclic branched or nonbranched, secondary or tertiary aliphatic amine having, in total, 10 to 60, in particular 13 to 36 carbon atoms.
6. The method as claimed in claim 5, wherein triiso-octylamine is used as the amine.
7. The method as claimed in claim 1, wherein inorganic acid and amine are added to the waste waters in the form of an amine salt.
8. The method as claimed in one or more of claims 1 and 4 to 7, wherein the amine or the amine salt is dissolved in an organic solvent.
9. The method as claimed in claim 8, wherein the amine or the amine salt is dissolved in kerosine-like fractions or in toluene.
10. The method as claimed in one or more of claims 1 and 4 to 9, wherein the concentration of the amine or the amine salt in the solvent is 10 to 50, in particular 15 to 35% by weight, based on the solution.
11. The method as claimed in claim 1, wherein the organic phase is further processed by treatment with an alkali metal hydroxide or alkaline earth metal hydroxide or an alkali metal carbonate, or by treatment with steam of at least 1.8 MPa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4141772A DE4141772A1 (en) | 1991-12-18 | 1991-12-18 | METHOD FOR PROCESSING ORGANIC PHOSPHORIC COMPOUNDS, IN PARTICULAR WASTEWATER CONTAINING SULFONED ARYLPHOSPHINS |
| DEP4141772.0 | 1991-12-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2085144A1 true CA2085144A1 (en) | 1993-06-19 |
Family
ID=6447361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002085144A Abandoned CA2085144A1 (en) | 1991-12-18 | 1992-12-11 | Method for processing waste waters containing organic phosphorus compounds, in particular sulfonted arylphosphines |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0547487A1 (en) |
| JP (1) | JPH05317848A (en) |
| KR (1) | KR930012594A (en) |
| CN (1) | CN1073665A (en) |
| AU (1) | AU3029192A (en) |
| BR (1) | BR9205030A (en) |
| CA (1) | CA2085144A1 (en) |
| DE (1) | DE4141772A1 (en) |
| MX (1) | MX9207179A (en) |
| TW (1) | TW210325B (en) |
| ZA (1) | ZA929646B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4140062A1 (en) * | 1991-12-05 | 1993-06-09 | Hoechst Ag, 6230 Frankfurt, De | METHOD FOR PROCESSING RHODIUM COMPOUNDS, DERIVATIVES OF ORGANIC PHOSPHINS AND OTHER POLLUTANTS IN SOLVED WATER |
| DE19732074A1 (en) * | 1997-07-25 | 1999-01-28 | Bayer Ag | Process for the purification of waste water containing organic and possibly inorganic sulfur compounds |
| US10578230B2 (en) | 2010-07-09 | 2020-03-03 | Wayne Fueling Systems Sweden Ab | Fuel dispensing unit comprising a locking member for retaining a fuel conduit in a locked position |
| BR112013000655B1 (en) | 2010-07-09 | 2020-11-17 | Dresser Wayne Ab | FUEL DISTRIBUTION UNIT |
| CN103011326B (en) * | 2012-12-14 | 2017-10-24 | 中国环境科学研究院 | A kind of method of organic matter in reduction amantadine production wastewater |
| CN102963948A (en) * | 2012-12-14 | 2013-03-13 | 中国环境科学研究院 | Method for treating adamantanamined waste water through extraction method |
| CN106348376A (en) * | 2015-07-17 | 2017-01-25 | 诚信工业有限公司 | Method of separating pollutants from waste water and system thereof |
| CN116323629A (en) * | 2020-10-28 | 2023-06-23 | 韩华思路信(株) | Process for preparing sulphonated arylphosphines |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55109213A (en) * | 1979-02-10 | 1980-08-22 | Nippon Soretsukusu Kk | Recovering phosphate ion |
| CH663781A5 (en) * | 1985-07-05 | 1988-01-15 | Ciba Geigy Ag | METHOD FOR WASTEWATER CLEANING. |
| DE3718725A1 (en) * | 1987-06-04 | 1988-12-22 | Hoechst Ag | METHOD FOR SEPARATING HALOGENATED HYDROXY AROMATES FROM AQUEOUS SOLUTIONS |
| EP0396790B1 (en) * | 1989-05-09 | 1992-12-23 | Bayer Antwerpen N.V. | Process for the removal of nitrate and organic pollutants from effluents |
-
1991
- 1991-12-18 DE DE4141772A patent/DE4141772A1/en not_active Withdrawn
-
1992
- 1992-10-30 TW TW081108644A patent/TW210325B/zh active
- 1992-11-30 KR KR1019920022913A patent/KR930012594A/en not_active Application Discontinuation
- 1992-12-09 EP EP92120951A patent/EP0547487A1/en not_active Withdrawn
- 1992-12-11 ZA ZA929646A patent/ZA929646B/en unknown
- 1992-12-11 CA CA002085144A patent/CA2085144A1/en not_active Abandoned
- 1992-12-11 MX MX9207179A patent/MX9207179A/en unknown
- 1992-12-11 JP JP4332012A patent/JPH05317848A/en active Pending
- 1992-12-16 AU AU30291/92A patent/AU3029192A/en not_active Abandoned
- 1992-12-16 BR BR9205030A patent/BR9205030A/en unknown
- 1992-12-17 CN CN92114473A patent/CN1073665A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU3029192A (en) | 1993-06-24 |
| CN1073665A (en) | 1993-06-30 |
| BR9205030A (en) | 1993-06-22 |
| ZA929646B (en) | 1993-06-09 |
| EP0547487A1 (en) | 1993-06-23 |
| JPH05317848A (en) | 1993-12-03 |
| TW210325B (en) | 1993-08-01 |
| MX9207179A (en) | 1993-06-01 |
| DE4141772A1 (en) | 1993-06-24 |
| KR930012594A (en) | 1993-07-20 |
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