EP1237861A1 - Procede de preparation de solutions d'acide peroxycarboxylique, en particulier d'acide peracetique et d'acide perprionique en etat d'equilibre - Google Patents
Procede de preparation de solutions d'acide peroxycarboxylique, en particulier d'acide peracetique et d'acide perprionique en etat d'equilibreInfo
- Publication number
- EP1237861A1 EP1237861A1 EP00987305A EP00987305A EP1237861A1 EP 1237861 A1 EP1237861 A1 EP 1237861A1 EP 00987305 A EP00987305 A EP 00987305A EP 00987305 A EP00987305 A EP 00987305A EP 1237861 A1 EP1237861 A1 EP 1237861A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- solution
- polyphosphoric
- catalyst
- peroxycarboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 42
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 9
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 34
- 239000003381 stabilizer Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- -1 amine phosphonic acids Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical class [H]O* 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims 1
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Definitions
- the invention is directed to a method for producing peroxycarboxylic acid solutions, in particular so-called equilibrium peroxycarboxylic acid solutions, containing peroxyacetic acid or peroxypropionic acid.
- the process is based on the reaction of the corresponding carboxylic acid with an aqueous oxygenated peroxide solution in the presence of polyphosphoric acid as a catalyst.
- Peroxycarboxylic acid solutions often also referred to as percarboxylic acid solutions, including solutions of peroxyacetic acid and peroxypropionic acid and especially so-called
- Equilibrium solutions which contain not only the peroxycarboxylic acid but also the carboxylic acid, hydrogen peroxide and water on which it is based, are used in many ways. Such solutions are used, for example, in detergents, bleaching agents and cleaning agents and in microbiocidal compositions for disinfection purposes and for killing lower plant and animal organisms.
- an aqueous peroxycarboxylic acid solution the carboxylic acid is usually reacted with hydrogen peroxide in the presence or absence of an organic solvent, usually using an aqueous hydrogen peroxide solution in the presence of a strongly acidic catalyst. If the establishment of equilibrium is not influenced by external measures, such as azeotropic dewatering, with an organic solvent, the reaction proceeds until equilibrium is established and the reaction mixture obtained is treated as an equilibrium. Peroxycarboxylic acid solution called. The time required to reach equilibrium depends on the concentration of the reactants, the amount and the acid strength of the catalyst added.
- one or more stabilizers preferably a synergistically effective combination of stabilizers, are usually used in and / or after manufacture 0.1 wt .-%, based on the solution, added.
- DE patent 195 17 465 teaches peroxycarboxylic acid solutions, including equilibrium peroxyacetic acid and equilibrium peroxypropionic acid, whose preparation in the presence of a polyphosphoric acid of the formula H n + 2 P n 0 3n + ⁇ , in which n is equal to or greater than 2.3, he follows.
- the polyphosphoric acid is used in an amount of 0.2 to 10% by weight, in particular 0.5 to 10% by weight.
- the solutions additionally contain one or more stabilizers from the series of chelating agents, pyrophosphoric acid and their
- Salts radical scavengers and tin compounds.
- the amount of stabilizers used is generally less than 0.5% by weight, based on the solution, in particular in the range from 10 to 1000 ppm.
- a particularly effective stabilizer 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 highly hygroscopic, is in the form of a solidified melt at room temperature, so that this product must either be comminuted or melted before use with some effort; The melting point is usually around 80 ° C with a medium degree of polymerization.
- An alternative form of delivery of polyphosphoric acid is as a melt. The need for heatable delivery and storage containers as well as heatable pipes from the storage container to the place of use make the production of the peroxycarboxylic acid solutions more expensive.
- DE patent 195 17 465 teaches to add the catalyst polyphosphoric acid either to the carboxylic acid to be reacted or to the aqueous hydrogen peroxide before the reaction; alternatively, the catalyst can also be added to the reaction mixture of carboxylic acid and aqueous hydrogen peroxide.
- a major disadvantage of this process is that the handling of the polyphosphoric acid is difficult due to its strong hygroscopicity and its solidification point above room temperature. By heating commercially available polyphosphoric acid to about 80 ° C, it can be metered in liquid, but this increases the complexity of the plant.
- the peroxycarboxylic acid solution should be able to be prepared in a simple manner at the place of use in order to avoid transporting highly concentrated peroxycarboxylic acid solutions over long distances and thus to avoid the risk of transportation.
- stabilizer systems comprising dipicolinic acid were used. tem is stabilized to increase the space-time yield of the process.
- solutions of acetic acid or propionic acid with polyphosphoric acid are surprisingly stable, the term stability not referring to chemical stability but to the fact that the catalytic activity of the mixture against pure polyphosphoric acid is maintained or exceeded.
- this solution catalyst solution
- solid, for example solidified, polyphosphoric acid can also be dissolved in the carboxylic acid and the solution can be stored.
- the invention accordingly relates to a process for the preparation of a peroxycarboxylic acid solution from the series of peroxyacetic acid and peroxypropionic acid solutions, in particular equilibrium peroxycarboxylic acid solutions, comprising reacting a carboxylic acid from the series of acetic acid and propionic acid with an aqueous hydrogen peroxide solution in the presence of a catalyst based on polyphosphoric acid characterized in that the catalyst used is an anhydrous solution which was obtained by dissolving 0.1 to 99% by weight (based on the solution) of polyphosphoric acid in the carboxylic acid to be converted into the peroxycarboxylic acid.
- the subclaims are directed to preferred embodiments.
- the catalyst solution is preferably prepared at the location where the polyphosphoric acid is prepared.
- the catalyst solution to be used in the process according to the invention contains the carboxylic acid and polyphosphoric acid successive products formed therefrom preferably in an amount of 1 to 35% by weight and in particular 5 to 20% by weight, calculated as polyphosphoric acid. It is assumed that the mixture of polyphosphoric acid and acetic acid or propionic acid in the production using a warm polyphosphoric acid melt and / or after storage for one or more days results in a mixture which, in addition to the starting components carboxylic acid anhydride, polyphosphoric acid reduced in the degree of polymerization and / or contains mixed anhydrides from the carboxylic acid and polyphosphoric acid.
- a solution is used with an amount of polyphosphoric acid such that it fully corresponds to the desired catalyst content in the reaction mixture and additionally to the desired carboxylic acid content.
- the catalyst-containing carboxylic acid solution can be further diluted with the corresponding carboxylic acid before use, or the latter is added to the reaction mixture of catalyst-containing carboxylic acid and aqueous hydrogen peroxide.
- the degree of polymerization of the polyphosphoric acid to be used is greater than 2, in particular 2.3 to 10.
- the principle according to the invention can also be used to prepare other peroxycarboxylic acids, including those of higher aliphatic and aromatic carboxylic acids, which in turn can 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 easily transported and stored in containers for liquids over a long period of time. Due to the liquid state of aggregation, the solution can also be dosed easily using conventional, simple devices for dosing liquids.
- the peroxycarboxylic acid solution can be prepared either in a conventional reaction vessel or directly in a transport container for the peroxycarboxylic acid solution to be produced. Both plastic containers and stainless steel containers are suitable as reaction and transport containers.
- the polyphosphoric acid or derived products contained in the peroxycarboxylic acid solution act as corrosion inhibitors.
- the undiluted or diluted with further carboxylic acid catalyst solution is reacted with aqueous hydrogen peroxide.
- water and / or carboxylic acid can also be added to the reaction system. The person skilled in the art will determine the amounts used for producing a solution with desired concentrations of peroxycarboxylic acid, carboxylic acid and unreacted hydrogen peroxide by preliminary tests. By allowing the reaction mixture to stand
- the equilibrium is reached at room temperature or a slightly elevated temperature.
- the inventive measure of using a catalyst solution prepared off-site from polyphosphoric acid and carboxylic acid from the series of acetic acid and propionic acid enables the corresponding peroxycarboxylic acid solutions, in particular equilibrium solutions, to be prepared in a simple manner and without great technical outlay.
- no special devices for handling and metering the carboxylic acid solutions containing polyphosphoric acid, which are produced off-site, usually at the place of manufacture of the polyphosphoric acid, are required. This simplifies the manufacturing process.
- the simplicity of the process makes it possible to prepare peroxycarboxylic acid solutions in simple devices where they are needed, thus avoiding the costs and problems associated with the transportation of particularly highly concentrated peracetic acid and perpropionic acid solutions.
- one or more stabilizers are formed during or after the preparation of a peroxycarboxylic acid solution the series of (a) chelating agents based on hydroxy and amino phosphonic acids, amino and hydroxy carboxylic acids, N-heterocyclic carboxylic acids and salts of the acids mentioned, (b) pyrophosphoric acid and its salts, (c) radical scavengers based on alkylated hydroxyaromatic compounds and (d) effective addition of tin compounds. It is particularly expedient to use a synergistically effective stabilizer combination of dipicolinic acid or a salt thereof and at least one chelate complexing agent from at least one of the aforementioned classes.
- dipicolinic acid and salts thereof can be solved in a simple manner by containing the dipicolinic acid or a salt thereof and a chelate complexing agent which is synergistically effective in the form of a single aqueous solution of the reaction mixture of polyphosphoric acid Carboxylic acid and aqueous hydrogen peroxide are added at the beginning, during or after the preparation of the peroxycarboxylic acid solution.
- the aqueous stabilizer solution which is stable on its own, contains 0.1 to 2% by weight of dipicolinic acid or a salt thereof and 0.1 to 10% by weight of a chelating agent from the series of the hydroxy and amino phosphonic acids, amino and hydroxy carboxylic acids , N-heterocyclic carboxylic acids and salts of the acids mentioned.
- the aqueous stabilizer solution contains dipicolinic acid and 1-hydroxyethane-1,1-diphosphonic acid. The stabilizer solution is fed into the system in an effective amount.
- the stabilizer solution is added to the reaction mixture in such an amount that it contains 5 to 200 ppm of dipicolinic acid or an alkali metal or ammonium salt thereof and 50 to 1000 ppm of one or more chelate complexing agents.
- dipicolinic acid stabilizer or a salt thereof directly to the catalyst solution in the preparation thereof.
- a polyphosphoric acid melt at 80 ° C. and powdered dipicolinic acid or salt thereof to the carboxylic acid a clear and colorless solution is obtained after brief stirring.
- Step a corresponds to the "off-site production" of the catalyst solution).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Procédé de préparation d'une solution d'acide peroxyacétique ou d'acide peroxypropionique qui consiste à mettre en réaction de l'acide acétique ou de l'acide propionique avec du peroxyde d'hydrogène en présence d'un catalyseur à base d'acide polyphosphorique. Selon la présente invention, le catalyseur utilisé est une solution exempte d'eau obtenue par dissolution de 0,1 à 99 % en poids, en particulier de 1 à 35 % en poids (par rapport à la solution), d'acide polyphosphorique dans l'acide carboxylique à convertir en acide peroxycarboxylique. La préparation de la solution de catalyse est effectuée de préférence à l'aide d'acide polyphosphorique fondu sur le lieu même de production dudit acide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19960994A DE19960994A1 (de) | 1999-12-17 | 1999-12-17 | Verfahren zur Herstellung von Peroxycarbonsäurelösungen insbesondere Gleichgewichts-Peressigsäure und -Perpropionsäure |
| DE19960994 | 1999-12-17 | ||
| PCT/EP2000/011830 WO2001044176A1 (fr) | 1999-12-17 | 2000-11-18 | Procede de preparation de solutions d'acide peroxycarboxylique, en particulier d'acide peracetique et d'acide perprionique en etat d'equilibre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1237861A1 true EP1237861A1 (fr) | 2002-09-11 |
Family
ID=7933099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00987305A Withdrawn EP1237861A1 (fr) | 1999-12-17 | 2000-11-18 | Procede de preparation de solutions d'acide peroxycarboxylique, en particulier d'acide peracetique et d'acide perprionique en etat d'equilibre |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1237861A1 (fr) |
| AU (1) | AU2359801A (fr) |
| BR (1) | BR0012905A (fr) |
| CA (1) | CA2377243A1 (fr) |
| DE (1) | DE19960994A1 (fr) |
| IL (1) | IL147003A0 (fr) |
| PL (1) | PL354398A1 (fr) |
| WO (1) | WO2001044176A1 (fr) |
| ZA (1) | ZA200110146B (fr) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2930732B1 (fr) * | 2008-04-30 | 2010-05-14 | Arkema France | Composition et procede pour la destruction de polluants organophosphores et/ou organosoufres |
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| EP2831000A4 (fr) | 2012-03-30 | 2016-03-30 | Ecolab Usa Inc | Utilisation de l'acide peracétique/peroxyde d'hydrogène et d'agents réducteurs de peroxyde pour le traitement des fluides de forage, des fluides frac, des eaux refoulées et des eaux usées |
| 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 |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| EP3841059A1 (fr) | 2018-08-22 | 2021-06-30 | Ecolab USA Inc. | Stabilisation de peroxyde d'hydrogène et de peracide avec des molécules à base d'acide pyridine carboxylique en c -3, -4 ou -5 |
| CN113811762A (zh) | 2019-05-31 | 2021-12-17 | 埃科莱布美国股份有限公司 | 通过电导率测量和过酸组合物监测过酸浓度的方法 |
| WO2021026410A1 (fr) | 2019-08-07 | 2021-02-11 | Ecolab Usa Inc. | Chélateurs à support solide et polymère pour la stabilisation de compositions contenant un peracide |
| CN114190379A (zh) * | 2021-11-17 | 2022-03-18 | 陕西环玉食品科技有限公司 | 一种通用型高稳定性一元过氧乙酸消毒剂及其制备方法 |
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 (de) * | 1993-05-26 | 1994-11-03 | Degussa | Stabilisierte Percarbonsäurelösungen und Verfahren zu deren Herstellung |
| DE19517465C1 (de) * | 1995-05-12 | 1997-01-23 | Degussa | Percarbonsäurelösungen mit verbesserter Stabilität im Kontakt mit Edelstahl |
-
1999
- 1999-12-17 DE DE19960994A patent/DE19960994A1/de not_active Withdrawn
-
2000
- 2000-11-18 WO PCT/EP2000/011830 patent/WO2001044176A1/fr not_active Ceased
- 2000-11-18 EP EP00987305A patent/EP1237861A1/fr not_active Withdrawn
- 2000-11-18 PL PL00354398A patent/PL354398A1/xx not_active Application Discontinuation
- 2000-11-18 BR BR0012905-4A patent/BR0012905A/pt not_active Application Discontinuation
- 2000-11-18 CA CA002377243A patent/CA2377243A1/fr not_active Abandoned
- 2000-11-18 AU AU23598/01A patent/AU2359801A/en not_active Abandoned
- 2000-11-18 IL IL14700300A patent/IL147003A0/xx unknown
-
2001
- 2001-12-10 ZA ZA200110146A patent/ZA200110146B/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0144176A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19960994A1 (de) | 2001-06-21 |
| IL147003A0 (en) | 2002-08-14 |
| CA2377243A1 (fr) | 2001-06-21 |
| ZA200110146B (en) | 2003-03-10 |
| AU2359801A (en) | 2001-06-25 |
| PL354398A1 (en) | 2004-01-12 |
| BR0012905A (pt) | 2002-05-21 |
| WO2001044176A1 (fr) | 2001-06-21 |
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