CA2377243A1 - Method for producing peroxycarboxylic acid solutions, especially equilibrium peracetic acid and perpropionic acid - Google Patents
Method for producing peroxycarboxylic acid solutions, especially equilibrium peracetic acid and perpropionic acid Download PDFInfo
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- CA2377243A1 CA2377243A1 CA002377243A CA2377243A CA2377243A1 CA 2377243 A1 CA2377243 A1 CA 2377243A1 CA 002377243 A CA002377243 A CA 002377243A CA 2377243 A CA2377243 A CA 2377243A CA 2377243 A1 CA2377243 A1 CA 2377243A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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Abstract
The invention relates to a method for producing a peroxyacetic acid or peroxypropionic acid solution by reacting acetic acid or propionic acid with hydrogen peroxide in the presence of a polyphosphoric acid catalyst. The catalyst used in the inventive method is a water-free solution that is obtained by dissolving 0.1 to 99 % by weight, especially 1 to 35 % by weight (based on the solution) of a polyphosphoric acid in the carboxylic acid that is to be converted to the peroxycarboxylic acid. The catalyst solution is preferably produced using molten polyphosphoric acid on the site of producti on of the same.
Description
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w~ ~l/44176 CA 02377243 2001-12-12 A process for preparing peroxycarboxylic acid solutions, in particular eguilibrium peracetic and perpropionic acids Description The invention provides a process for preparing peroxycarboxylic acid solutions, in particular so-called equilibrium peroxycarboxylic acid solutions which contain peroxyacetic acid or peroxypropionic acid. The process is based on reaction of the corresponding carboxylic acid with an aqueous hydrogen peroxide solution in the presence of polyphosphoric acid as catalyst.
Peroxycarboxylic acid solutions, often also called percarboxylic acid solutions, including solutions of peroxyacetic acid and peroxypropionic acid and in particular so-called equilibrium solutions which contain, apart from the peroxycarboxylic acid, also the parent carboxylic acid, hydrogen peroxide and water in an equilibrium condition, are used in a wide variety of applications. These types of solutions are used, for example, in detergents, bleaches and cleansing agents and also in microbiocidal compositions for disinfectant purposes and also for destroying lower plant and animal organisms.
To prepare an aqueous peroxycarboxylic acid solution, the carboxylic acid is usually reacted, in the presence or absence of an organic solvent, with hydrogen peroxide, normally using an aqueous hydrogen peroxide solution in the presence of a strongly acidic catalyst. Provided reaching the equilibrium point is not affected by external factors, such as azeotropic dewatering, when using an organic solvent, the reaction proceeds to the equilibrium point and the reaction mixture obtained is called the equilibrium peroxycarboxylic acid solution. The time required to reach the equilibrium point depends on the concentration of the w~ 01/44176 CA 02377243 2001-12-12 ~~~/11~0 reaction partners and the amount and strength of the acid added as catalyst. Since stability-impairing factors during the preparation, storage and handling of aqueous peroxycarboxylic acid solutions can never be excluded in practice, one or more stabilisers, preferably a synergistic combination of stabilisers, are added in an amount of normally less than 0.1 wt.%, with respect to the solution, during and/or after preparation.
German patent DE 195 17 465 discloses peroxycarboxylic acid solutions, including equilibrium peroxyacetic acid and equilibrium peroxypropionic acid, the preparation of which takes place in the presence of a polyphosphoric acid of the formula Hn,~Pa03n~1, in which n is greater than or equal to 2.3. The polyphosphoric acid is used in an amount of 0.2 to 10 wt.%, in particular 0.5 to l0 wt.%. Expediently, the solutions also contain one or more stabilisers from the group consisting of chelating agents, pyrophosphoric acid and its salts, radical traps and tin compounds. The amount of stabiliser added is generally less than 0.5 wt.%, with respect to the solution, in particular in the range l0 to 1000 ppm. A particularly effective stabiliser combination is known from WO 91/13058 and this combination consists of dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid.
Polyphosphoric acid, which is extremely hygroscopic, is present in the form of a solidified melt at room temperature, so this product has to be either crushed or melted, involving some costs, prior to use; the melting point is usually about 80°C in the case of an average degree of polymerisation. An alternative form of supply of polyphosphoric acid is that of the molten material. The requirement for heatable delivery and storage containers and of heatable pipes from the storage container to the point of use makes the preparation of peroxycarboxylic acid solutions more costly.
wo omm6 rcr~rooms3o German patent DE 195 17 465 discloses adding the catalyst polyphosphoric acid either to the carboxylic acid to be reacted or to the aqueous hydrogen peroxide prior to reaction; as an alternative to this, the catalyst may also be added to the reaction mixture of carboxylic acid and aqueous hydrogen peroxide. A substantial disadvantage of this process is that the handling of polyphosphoric acid is very difficult due to its high degree of hygroscopicity and its solidification point, which is above room temperature.
l0 Although commercially available polyphosphoric acid can be added as a liquid by heating it to about 80°C, the production costs increase as a result. Another problem when preparing stabilised peroxycarboxylic acid solutions using powdered dipicolinic acid or salts thereof, on their own or in combination with a chelating agent based on hydroxy and aminophosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, comprises the low solubility of dipicolinic acid and its salts which means that the reaction mixture consisting of the carboxylic acid, aqueous hydrogen peroxide solution, catalyst and stabilisers has to be agitated for several hours.
There is, therefore, interest in i~roving the process for preparing lower peroxycarboxylic acid solutions using polyphosphoric acid as catalyst, to the effect that the problems involved when metering out the polyphosphoric acid need to be solved. The invention is also aimed at enabling preparation of the peroxycarboxylic acid solution in a simple manner at the point of use in order to avoid transporting highly concentrated peroxycarboxylic acid solutions over long distances, and thus the risks involved in transport. In addition, there is interest in any case in increasing the space-time yield of the process in which a stabiliser system which contains dipicolinic acid is used.
It was found that solutions of acetic acid or propionic acid with polyphosphoric acid are surprisingly stable, ~
W~ ~l/~176 CA 02377243 2001-12-12 wherein the expression stability does not refer to chemical stability but refers to the fact that the catalytic activity of the mixture is the same as or greater than that of pure polyphosphoric acid. On the basis of this finding, it is possible to prepare solutions of polyphosphoric acid in acetic acid or propionic acid immediately after the process for preparing the polyphosphoric acid, by dissolving the latter in the carboxylic acid, preferably before it solidifies; this solution (= catalyst solution) can be stored and delivered to the site of preparation of the peroxycarboxylic acid solution with no problem. In principle, solid, for example, solidified, polyphosphoric acid can also be dissolved in the carboxylic acid and the solution stored.
Thus, the invention provides a process for preparing a peroxycarboxylic acid solution from the group consisting of peroxyacetic acid and peroxypropionic acid solutions, in particular equilibrium peroxycarboxylic acid solutions;
comprising reacting a carboxylic acid from the group consisting of acetic acid and propionic acid with an aqueous hydrogen peroxide solution in the presence of a catalyst based on polyphosphoric acid, which is characterised in that an anhydrous solution which has been obtained by dissolving 0.1 to 99 wt.% (with respect to the solution) of polyphosphoric acid in the carboxylic acid which is to be converted into a peroxycarboxylic acid is used as catalyst. The subclaims provide preferred types of embodiments. Preparation of the catalyst solution is preferably performed at the site of preparation of the polyphosphoric acid.
The catalyst solution to be used in the process according to the invention contains the carboxylic acid and polyphosphoric acid or secondary products formed therefrom in an amount of preferably 1 to 35 wt.% and in particular of 5 to 20 wt.%, calculated as polyphosphoric acid. It is - ' WO 01/44176 CA 02377243 2001-12-12 PG"T/EP09/11830 assumed that a mixture results from the mixture of polyphosphoric acid and acetic acid or propionic acid, when prepared with the use of a hot, molten polyphosphoric acid and/or after storage for one or more days, which contains, 5 apart from the starting components, the carboxylic anhydride, polyphosphoric acid with a reduced degree of polymerisation and/or mixed anhydrides of the carboxylic acid and polyphosphoric acid. In accordance with a preferred embodiment of the process, a solution with an amount of polyphosphoric acid such that this corresponds fully to the concentration of catalyst required in the reaction mixture and also to the required concentration of carboxylic acid is used. Obviously, the catalyst-containing carboxylic acid solution may be diluted further with the corresponding carboxylic acid prior to use, or the latter may be added to the reaction mixture of catalyst-containing carboxylic acid and aqueous hydrogen peroxide.
The degree of polymerisation of the polyphosphoric acid to be used is greater than 2, in particular 2.3 to 10. The principle in accordance with the invention may also be used to prepare other peroxycarboxylic acids, including those of higher aliphatic and aromatic carboxylic acids, which may also be substituted.
The solution of a carboxylic acid and polyphosphoric acid to be used according to the invention is liquid at room temperature and the solution can be transported and stored for an extended period in containers for liquids with no problem. Due to being in a liquid state, the solution can also be metered out with no problem by using conventional, simple devices for metering out liquids. The peroxycarboxylic acid solution can be prepared either in a conventional reaction tank or else directly in a transport tank for the peroxycarboxylic acid solution to be prepared.
Containers made of a plastics material or stainless steel are suitable as reaction and transport tanks. The _ ~ WO ~l/44176 CA 02377243 2001-12-12 PCT/EP00/11830 polyphosphoric acid or secondary products thereof contained in the peroxycarboxylic acid solution act as corrosion inhibitors.
To prepare the peroxycarboxylic solution, the catalyst solution, undiluted or diluted with more carboxylic acid, is reacted with aqueous hydrogen peroxide. If required, water and/or carboxylic acid may also be added to the reaction system. A person skilled in the art can determine the amounts of feedstocks to use to prepare a solution with the desired concentrations of peroxycarboxylic acid, carboxylic acid and non-reacted hydrogen peroxide in preliminary trials. The equilibrium point is reached by allowing the reaction mixture to stand at room temperature or a slightly elevated temperature.
As a result of the step according to the invention of using a catalyst.solution prepared off-site and consisting of polyphosphoric acid and a carboxylic acid from the group consisting of acetic acid and propionic acid, the corresponding peroxycarboxylic acid solutions, in particular equilibrium solutions, can be prepared in a simple manner and without incurring high costs. As already mentioned, no special devices are required for handling and metering out the carboxylic acid solutions which contain polyphosphoric acid which are prepared off-site, usually at the site for preparing the polyphosphoric acid. This simplifies the method of preparation. The simplicity of the process enables the preparation of peroxycarboxylic acid solutions in simple devices at the location where they are needed, which means that coats and problems which are associated with the transport of in particular highly concentrated peracetic acid and perpropionic acid solutions are avoided.
One or more stabilisers from the group consisting of a) chelating agents based on hydroxy and aminophosphonic acids, amino and hydroxycarboxylic acids, N-heterocyclic ~
W~ 01/44176 CA 02377243 2001-12-12 PC"T/EPOOI11830 carboxylic acids and salts of the acids mentioned, b) pyrophosphoric acid and its salts, c) radical traps based on alkylated hydroxyaromatic compounds and d) tin compounds are usually added in effective amounts during or after preparation of a peroxycarboxylic acid solution. It is particularly expedient to use a synergistic combination of stabilisers consisting of dipicolinic acid or a salt of same and at least one chelating agent from at least one of the previously mentioned classes. The problem described at the beginning which stems from the very low solubility of dipicolinic acid and its salts can be overcome in a simple manner by adding the dipicolinic acid or a salt of same and a chelating agent which is synergistic therewith, in the form of a single aqueous solution, to the reaction mixture of polyphosphoric acid-containing carboxylic acid and aqueous hydrogen peroxide at the beginning of, during or after preparation of the peroxycarboxylic acid solution.
The aqueous stabiliser solution, which is storage stable per se, contains 0.1 to 2 wt.% of dipicolinic acid or a salt of same and 0.1 to 10 wt.% of a chelating agent from the group consisting of hydroxy and aminophosphonic acids, amino and hydroxycarboxylic acids, N-heterocyclic carboxylic acids and salts of the acids mentioned. In accordance with a particularly suitable embodiment, the aqueous stabiliser solution contains dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid. The stabiliser solution is added to the system in an effective amount. In accordance with a particularly preferred embodiment, the Stabiliser solution is added to the reaction mixture in an amount such that this contains 5 to 200 ppm of dipicolinic acid or an alkali metal or ammonium salt of same and 50 to 1000 ppm of one or more chelating agents. Due to the use of an aqueous solution of a synergistic stabiliser combination, the stirring or recirculation of the reaction mixture, which has hitherto been conventional, can be omitted so that the time required to prepare the peroxycarboxylic solution can be considerably shortened.
CA 02377243 2001-12-12 ~/~~/1183~
w~ ~l/44176 CA 02377243 2001-12-12 A process for preparing peroxycarboxylic acid solutions, in particular eguilibrium peracetic and perpropionic acids Description The invention provides a process for preparing peroxycarboxylic acid solutions, in particular so-called equilibrium peroxycarboxylic acid solutions which contain peroxyacetic acid or peroxypropionic acid. The process is based on reaction of the corresponding carboxylic acid with an aqueous hydrogen peroxide solution in the presence of polyphosphoric acid as catalyst.
Peroxycarboxylic acid solutions, often also called percarboxylic acid solutions, including solutions of peroxyacetic acid and peroxypropionic acid and in particular so-called equilibrium solutions which contain, apart from the peroxycarboxylic acid, also the parent carboxylic acid, hydrogen peroxide and water in an equilibrium condition, are used in a wide variety of applications. These types of solutions are used, for example, in detergents, bleaches and cleansing agents and also in microbiocidal compositions for disinfectant purposes and also for destroying lower plant and animal organisms.
To prepare an aqueous peroxycarboxylic acid solution, the carboxylic acid is usually reacted, in the presence or absence of an organic solvent, with hydrogen peroxide, normally using an aqueous hydrogen peroxide solution in the presence of a strongly acidic catalyst. Provided reaching the equilibrium point is not affected by external factors, such as azeotropic dewatering, when using an organic solvent, the reaction proceeds to the equilibrium point and the reaction mixture obtained is called the equilibrium peroxycarboxylic acid solution. The time required to reach the equilibrium point depends on the concentration of the w~ 01/44176 CA 02377243 2001-12-12 ~~~/11~0 reaction partners and the amount and strength of the acid added as catalyst. Since stability-impairing factors during the preparation, storage and handling of aqueous peroxycarboxylic acid solutions can never be excluded in practice, one or more stabilisers, preferably a synergistic combination of stabilisers, are added in an amount of normally less than 0.1 wt.%, with respect to the solution, during and/or after preparation.
German patent DE 195 17 465 discloses peroxycarboxylic acid solutions, including equilibrium peroxyacetic acid and equilibrium peroxypropionic acid, the preparation of which takes place in the presence of a polyphosphoric acid of the formula Hn,~Pa03n~1, in which n is greater than or equal to 2.3. The polyphosphoric acid is used in an amount of 0.2 to 10 wt.%, in particular 0.5 to l0 wt.%. Expediently, the solutions also contain one or more stabilisers from the group consisting of chelating agents, pyrophosphoric acid and its salts, radical traps and tin compounds. The amount of stabiliser added is generally less than 0.5 wt.%, with respect to the solution, in particular in the range l0 to 1000 ppm. A particularly effective stabiliser combination is known from WO 91/13058 and this combination consists of dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid.
Polyphosphoric acid, which is extremely hygroscopic, is present in the form of a solidified melt at room temperature, so this product has to be either crushed or melted, involving some costs, prior to use; the melting point is usually about 80°C in the case of an average degree of polymerisation. An alternative form of supply of polyphosphoric acid is that of the molten material. The requirement for heatable delivery and storage containers and of heatable pipes from the storage container to the point of use makes the preparation of peroxycarboxylic acid solutions more costly.
wo omm6 rcr~rooms3o German patent DE 195 17 465 discloses adding the catalyst polyphosphoric acid either to the carboxylic acid to be reacted or to the aqueous hydrogen peroxide prior to reaction; as an alternative to this, the catalyst may also be added to the reaction mixture of carboxylic acid and aqueous hydrogen peroxide. A substantial disadvantage of this process is that the handling of polyphosphoric acid is very difficult due to its high degree of hygroscopicity and its solidification point, which is above room temperature.
l0 Although commercially available polyphosphoric acid can be added as a liquid by heating it to about 80°C, the production costs increase as a result. Another problem when preparing stabilised peroxycarboxylic acid solutions using powdered dipicolinic acid or salts thereof, on their own or in combination with a chelating agent based on hydroxy and aminophosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, comprises the low solubility of dipicolinic acid and its salts which means that the reaction mixture consisting of the carboxylic acid, aqueous hydrogen peroxide solution, catalyst and stabilisers has to be agitated for several hours.
There is, therefore, interest in i~roving the process for preparing lower peroxycarboxylic acid solutions using polyphosphoric acid as catalyst, to the effect that the problems involved when metering out the polyphosphoric acid need to be solved. The invention is also aimed at enabling preparation of the peroxycarboxylic acid solution in a simple manner at the point of use in order to avoid transporting highly concentrated peroxycarboxylic acid solutions over long distances, and thus the risks involved in transport. In addition, there is interest in any case in increasing the space-time yield of the process in which a stabiliser system which contains dipicolinic acid is used.
It was found that solutions of acetic acid or propionic acid with polyphosphoric acid are surprisingly stable, ~
W~ ~l/~176 CA 02377243 2001-12-12 wherein the expression stability does not refer to chemical stability but refers to the fact that the catalytic activity of the mixture is the same as or greater than that of pure polyphosphoric acid. On the basis of this finding, it is possible to prepare solutions of polyphosphoric acid in acetic acid or propionic acid immediately after the process for preparing the polyphosphoric acid, by dissolving the latter in the carboxylic acid, preferably before it solidifies; this solution (= catalyst solution) can be stored and delivered to the site of preparation of the peroxycarboxylic acid solution with no problem. In principle, solid, for example, solidified, polyphosphoric acid can also be dissolved in the carboxylic acid and the solution stored.
Thus, the invention provides a process for preparing a peroxycarboxylic acid solution from the group consisting of peroxyacetic acid and peroxypropionic acid solutions, in particular equilibrium peroxycarboxylic acid solutions;
comprising reacting a carboxylic acid from the group consisting of acetic acid and propionic acid with an aqueous hydrogen peroxide solution in the presence of a catalyst based on polyphosphoric acid, which is characterised in that an anhydrous solution which has been obtained by dissolving 0.1 to 99 wt.% (with respect to the solution) of polyphosphoric acid in the carboxylic acid which is to be converted into a peroxycarboxylic acid is used as catalyst. The subclaims provide preferred types of embodiments. Preparation of the catalyst solution is preferably performed at the site of preparation of the polyphosphoric acid.
The catalyst solution to be used in the process according to the invention contains the carboxylic acid and polyphosphoric acid or secondary products formed therefrom in an amount of preferably 1 to 35 wt.% and in particular of 5 to 20 wt.%, calculated as polyphosphoric acid. It is - ' WO 01/44176 CA 02377243 2001-12-12 PG"T/EP09/11830 assumed that a mixture results from the mixture of polyphosphoric acid and acetic acid or propionic acid, when prepared with the use of a hot, molten polyphosphoric acid and/or after storage for one or more days, which contains, 5 apart from the starting components, the carboxylic anhydride, polyphosphoric acid with a reduced degree of polymerisation and/or mixed anhydrides of the carboxylic acid and polyphosphoric acid. In accordance with a preferred embodiment of the process, a solution with an amount of polyphosphoric acid such that this corresponds fully to the concentration of catalyst required in the reaction mixture and also to the required concentration of carboxylic acid is used. Obviously, the catalyst-containing carboxylic acid solution may be diluted further with the corresponding carboxylic acid prior to use, or the latter may be added to the reaction mixture of catalyst-containing carboxylic acid and aqueous hydrogen peroxide.
The degree of polymerisation of the polyphosphoric acid to be used is greater than 2, in particular 2.3 to 10. The principle in accordance with the invention may also be used to prepare other peroxycarboxylic acids, including those of higher aliphatic and aromatic carboxylic acids, which may also be substituted.
The solution of a carboxylic acid and polyphosphoric acid to be used according to the invention is liquid at room temperature and the solution can be transported and stored for an extended period in containers for liquids with no problem. Due to being in a liquid state, the solution can also be metered out with no problem by using conventional, simple devices for metering out liquids. The peroxycarboxylic acid solution can be prepared either in a conventional reaction tank or else directly in a transport tank for the peroxycarboxylic acid solution to be prepared.
Containers made of a plastics material or stainless steel are suitable as reaction and transport tanks. The _ ~ WO ~l/44176 CA 02377243 2001-12-12 PCT/EP00/11830 polyphosphoric acid or secondary products thereof contained in the peroxycarboxylic acid solution act as corrosion inhibitors.
To prepare the peroxycarboxylic solution, the catalyst solution, undiluted or diluted with more carboxylic acid, is reacted with aqueous hydrogen peroxide. If required, water and/or carboxylic acid may also be added to the reaction system. A person skilled in the art can determine the amounts of feedstocks to use to prepare a solution with the desired concentrations of peroxycarboxylic acid, carboxylic acid and non-reacted hydrogen peroxide in preliminary trials. The equilibrium point is reached by allowing the reaction mixture to stand at room temperature or a slightly elevated temperature.
As a result of the step according to the invention of using a catalyst.solution prepared off-site and consisting of polyphosphoric acid and a carboxylic acid from the group consisting of acetic acid and propionic acid, the corresponding peroxycarboxylic acid solutions, in particular equilibrium solutions, can be prepared in a simple manner and without incurring high costs. As already mentioned, no special devices are required for handling and metering out the carboxylic acid solutions which contain polyphosphoric acid which are prepared off-site, usually at the site for preparing the polyphosphoric acid. This simplifies the method of preparation. The simplicity of the process enables the preparation of peroxycarboxylic acid solutions in simple devices at the location where they are needed, which means that coats and problems which are associated with the transport of in particular highly concentrated peracetic acid and perpropionic acid solutions are avoided.
One or more stabilisers from the group consisting of a) chelating agents based on hydroxy and aminophosphonic acids, amino and hydroxycarboxylic acids, N-heterocyclic ~
W~ 01/44176 CA 02377243 2001-12-12 PC"T/EPOOI11830 carboxylic acids and salts of the acids mentioned, b) pyrophosphoric acid and its salts, c) radical traps based on alkylated hydroxyaromatic compounds and d) tin compounds are usually added in effective amounts during or after preparation of a peroxycarboxylic acid solution. It is particularly expedient to use a synergistic combination of stabilisers consisting of dipicolinic acid or a salt of same and at least one chelating agent from at least one of the previously mentioned classes. The problem described at the beginning which stems from the very low solubility of dipicolinic acid and its salts can be overcome in a simple manner by adding the dipicolinic acid or a salt of same and a chelating agent which is synergistic therewith, in the form of a single aqueous solution, to the reaction mixture of polyphosphoric acid-containing carboxylic acid and aqueous hydrogen peroxide at the beginning of, during or after preparation of the peroxycarboxylic acid solution.
The aqueous stabiliser solution, which is storage stable per se, contains 0.1 to 2 wt.% of dipicolinic acid or a salt of same and 0.1 to 10 wt.% of a chelating agent from the group consisting of hydroxy and aminophosphonic acids, amino and hydroxycarboxylic acids, N-heterocyclic carboxylic acids and salts of the acids mentioned. In accordance with a particularly suitable embodiment, the aqueous stabiliser solution contains dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid. The stabiliser solution is added to the system in an effective amount. In accordance with a particularly preferred embodiment, the Stabiliser solution is added to the reaction mixture in an amount such that this contains 5 to 200 ppm of dipicolinic acid or an alkali metal or ammonium salt of same and 50 to 1000 ppm of one or more chelating agents. Due to the use of an aqueous solution of a synergistic stabiliser combination, the stirring or recirculation of the reaction mixture, which has hitherto been conventional, can be omitted so that the time required to prepare the peroxycarboxylic solution can be considerably shortened.
CA 02377243 2001-12-12 ~/~~/1183~
It is also possible, in accordance with another alternative, to add the stabiliser dipicolinic acid or a salt of same directly to the catalyst solution during preparation of this solution. By adding, for example, molten polyphosphoric acid heated to 80°C and powdered dipicolinic acid or a salt thereof to the carboxylic acid, a clear and colourless solution is obtained after stirring for a short time.
By using a solution, prepared off-site, of polyphosphoric acid and a carboxylic acid from the group consisting of acetic acid and propionic acid to be used according to the invention and which optionally also already contains dipicolinic acid or a salt of same, the process for preparing stabilised equilibrium peracetic acid and equilibrium perpropionic acid solutions can be considerably simplified. If the catalyst solution does not contain any stabiliser from the group consisting of dipicolinic acid and salts of same, it is advantageous to add an aqueous solution of one of the previously mentioned synergistic stabiliser combinations to this within the scope of preparing the peroxycarboxylic acid. The production costs can be reduced by using easy-to-meter solutions and the time of preparation can also be reduced. The process can be performed very simply at the location where the peroxycarboxylic acid solution is needed.
The invention is explained further by means of the following example.
~ ' ~ W~ ~l/~1~16 CA 02377243 2001-12-12 Example a) Preparing the catalyst solution 16.8 g of polyphosphoric acid, heated to 80°C, and 0.7 g of dipicolinic acid were introduced into 83.0 g of acetic acid. After stirring the mixture for two hours at about 30°C, this was a clear, colourless solution. (Stage a) corresponds to "off-site preparation" of the catalyst solution).
b) Preparing a 5 wt.% strength peroxyacetic acid 380 g of hydrogen peroxide (50 wt.%) and 220 g of water were added to the catalyst solution prepared in accordance with a). The mixture was allowed to stand and reach equilibrium after stirring once.
By using a solution, prepared off-site, of polyphosphoric acid and a carboxylic acid from the group consisting of acetic acid and propionic acid to be used according to the invention and which optionally also already contains dipicolinic acid or a salt of same, the process for preparing stabilised equilibrium peracetic acid and equilibrium perpropionic acid solutions can be considerably simplified. If the catalyst solution does not contain any stabiliser from the group consisting of dipicolinic acid and salts of same, it is advantageous to add an aqueous solution of one of the previously mentioned synergistic stabiliser combinations to this within the scope of preparing the peroxycarboxylic acid. The production costs can be reduced by using easy-to-meter solutions and the time of preparation can also be reduced. The process can be performed very simply at the location where the peroxycarboxylic acid solution is needed.
The invention is explained further by means of the following example.
~ ' ~ W~ ~l/~1~16 CA 02377243 2001-12-12 Example a) Preparing the catalyst solution 16.8 g of polyphosphoric acid, heated to 80°C, and 0.7 g of dipicolinic acid were introduced into 83.0 g of acetic acid. After stirring the mixture for two hours at about 30°C, this was a clear, colourless solution. (Stage a) corresponds to "off-site preparation" of the catalyst solution).
b) Preparing a 5 wt.% strength peroxyacetic acid 380 g of hydrogen peroxide (50 wt.%) and 220 g of water were added to the catalyst solution prepared in accordance with a). The mixture was allowed to stand and reach equilibrium after stirring once.
Claims (5)
1. A process for preparing a peroxycarboxylic acid solution from the group consisting of peroxyacetic and peroxypropionic acid solutions, in particular equilibrium peroxycarboxylic acid solutions, comprising reacting a carboxylic acid solution from the group consisting of acetic acid and propionic acid with an aqueous hydrogen peroxide solution in the presence of a catalyst based on polyphosphoric acid, characterised in that, an anhydrous solution which has been obtained by dissolving 0.1 to 99 wt.% (with respect to the solution) of polyphosphoric acid in the carboxylic acid which is to be converted into a peroxycarboxylic acid is used as catalyst.
2. A process according to Claim 1, characterised in that, a solution of acetic acid or propionic acid and 1 to 35 wt.% of molten polyphosphoric acid (with respect to the solution) prepared at the site of preparation of the polyphosphoric acid is used as catalyst.
3. A process according to Claim 1 or 2, characterised in that, a 30 to 85 wt.% strength aqueous hydrogen peroxide solution is used and the reaction mixture is allowed to stand until it reaches equilibrium.
4. A process according to one of Claims 1 to 3, characterised in that, the peroxycarboxylic acid solution is stabilised during or after preparation by adding an effective amount of an aqueous stabiliser solution with a concentration of dipicolinic acid or a salt of same and at least one chelating agent from the group consisting of hydroxy and aminophosphonic acids, pyrophosphoric acid, amino and hydroxycarboxylic acids, N-heterocyclic carboxylic acids and salts of the acids mentioned and also hydroxyethylidendiphosphonic acid.
5. A process according to one of Claims 1 to 4, characterised in that, a catalyst solution which contains 0.1 to 2 wt.% of dipicolinic acid or a salt of same is used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19960994A DE19960994A1 (en) | 1999-12-17 | 1999-12-17 | Process for the preparation of peroxycarboxylic acid solutions, in particular equilibrium peracetic acid and perpropionic acid |
| DE19960994.2 | 1999-12-17 | ||
| PCT/EP2000/011830 WO2001044176A1 (en) | 1999-12-17 | 2000-11-18 | Method for producing peroxycarboxylic acid solutions, especially equilibrium peracetic acid and perpropionic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2377243A1 true CA2377243A1 (en) | 2001-06-21 |
Family
ID=7933099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002377243A Abandoned CA2377243A1 (en) | 1999-12-17 | 2000-11-18 | Method for producing peroxycarboxylic acid solutions, especially equilibrium peracetic acid and perpropionic acid |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1237861A1 (en) |
| AU (1) | AU2359801A (en) |
| BR (1) | BR0012905A (en) |
| CA (1) | CA2377243A1 (en) |
| DE (1) | DE19960994A1 (en) |
| IL (1) | IL147003A0 (en) |
| PL (1) | PL354398A1 (en) |
| WO (1) | WO2001044176A1 (en) |
| ZA (1) | ZA200110146B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2930732A1 (en) * | 2008-04-30 | 2009-11-06 | Arkema France | COMPOSITION AND METHOD FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSOUFRES POLLUTANTS |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| CA2867565C (en) | 2012-03-30 | 2021-01-19 | Victor KEASLER | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| EP3841059A1 (en) | 2018-08-22 | 2021-06-30 | Ecolab USA Inc. | Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid at c-3, -4 or -5 |
| WO2021026410A1 (en) | 2019-08-07 | 2021-02-11 | Ecolab Usa Inc. | Polymeric and solid-supported chelators for stabilization of peracid-containing compositions |
| CN114190379A (en) * | 2021-11-17 | 2022-03-18 | 陕西环玉食品科技有限公司 | Universal high-stability monoperoxyacetic acid disinfectant and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9004080D0 (en) * | 1990-02-23 | 1990-04-18 | Interox Chemicals Ltd | Solutions of peracids |
| DE4317420C1 (en) * | 1993-05-26 | 1994-11-03 | Degussa | Stabilized percarboxylic acid solutions and process for their preparation |
| DE19517465C1 (en) * | 1995-05-12 | 1997-01-23 | Degussa | Percarboxylic acid solutions with improved stability in contact with stainless steel |
-
1999
- 1999-12-17 DE DE19960994A patent/DE19960994A1/en not_active Withdrawn
-
2000
- 2000-11-18 IL IL14700300A patent/IL147003A0/en unknown
- 2000-11-18 BR BR0012905-4A patent/BR0012905A/en not_active Application Discontinuation
- 2000-11-18 EP EP00987305A patent/EP1237861A1/en not_active Withdrawn
- 2000-11-18 AU AU23598/01A patent/AU2359801A/en not_active Abandoned
- 2000-11-18 PL PL00354398A patent/PL354398A1/en not_active Application Discontinuation
- 2000-11-18 WO PCT/EP2000/011830 patent/WO2001044176A1/en not_active Application Discontinuation
- 2000-11-18 CA CA002377243A patent/CA2377243A1/en not_active Abandoned
-
2001
- 2001-12-10 ZA ZA200110146A patent/ZA200110146B/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2930732A1 (en) * | 2008-04-30 | 2009-11-06 | Arkema France | COMPOSITION AND METHOD FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND / OR ORGANOSOUFRES POLLUTANTS |
| WO2009141548A2 (en) * | 2008-04-30 | 2009-11-26 | Arkema France | Composition and process for the destruction of organophosphorus and/or organosulphur pollutants |
| WO2009141548A3 (en) * | 2008-04-30 | 2010-03-25 | Arkema France | Composition and process for the destruction of organophosphorus and/or organosulphur pollutants |
| JP2011522066A (en) * | 2008-04-30 | 2011-07-28 | アルケマ フランス | Compositions and processes for destroying organophosphorus and / or organosulfur contaminants |
Also Published As
| Publication number | Publication date |
|---|---|
| IL147003A0 (en) | 2002-08-14 |
| BR0012905A (en) | 2002-05-21 |
| EP1237861A1 (en) | 2002-09-11 |
| WO2001044176A1 (en) | 2001-06-21 |
| DE19960994A1 (en) | 2001-06-21 |
| ZA200110146B (en) | 2003-03-10 |
| PL354398A1 (en) | 2004-01-12 |
| AU2359801A (en) | 2001-06-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |