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WO2003078332A1 - Method and apparatus for water disinfection - Google Patents

Method and apparatus for water disinfection Download PDF

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Publication number
WO2003078332A1
WO2003078332A1 PCT/EP2003/001591 EP0301591W WO03078332A1 WO 2003078332 A1 WO2003078332 A1 WO 2003078332A1 EP 0301591 W EP0301591 W EP 0301591W WO 03078332 A1 WO03078332 A1 WO 03078332A1
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WO
WIPO (PCT)
Prior art keywords
acid
peroxyacids
weight
hydrogen peroxide
reaction
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.)
Ceased
Application number
PCT/EP2003/001591
Other languages
French (fr)
Inventor
Mario Belluati
Daniele Copetti
Enrico Danesi
Giorgio Colombi
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Caffaro SpA
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Caffaro SpA
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Filing date
Publication date
Application filed by Caffaro SpA filed Critical Caffaro SpA
Priority to AU2003205774A priority Critical patent/AU2003205774A1/en
Priority to EP03702649A priority patent/EP1485326A1/en
Publication of WO2003078332A1 publication Critical patent/WO2003078332A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
    • C07C409/26—Peracetic acid
    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment

Definitions

  • the present invention relates to a method and to the corresponding apparatus for disinfecting civil and industrial wastewater, cooling water, potable water and process water in general by preparing peroxyacids at various concentrations and in situ, i.e., directly at the time of use and according to the specific requirements of the application.
  • Water disinfection is necessary to avoid microbiological proliferation phenomena (bacteria, fungi, algae), which can cause hygienic and sanitary problems or failures of equipment.
  • the described known art has the drawback that ion-exchange resins tend to lose their effectiveness over time, due to the oxidizing action of the reagents, to the generated product that is in contact with the resin, to the temperatures used, and to other factors.
  • the conventional use of ion-exchange resins moreover, has the drawback of requiring the replacement of spent resins and the addition of stabilizing agents suitable to extend the life of these resins.
  • the aim of the invention is to provide a method and a corresponding apparatus that are suitable to disinfect water of various kinds by preparing peroxyacids in situ, without the drawbacks linked to the conventional use of ion-exchange resins.
  • Another object of the invention is to provide an apparatus that is simpler and more economical than those currently in use to prepare peroxyacids, obviating the need to replace spent resins, perform maintenance thereon, and similar operations.
  • Another object of the invention is to provide a method for producing peroxyacids in situ which, differently from known ones, does not require the use of resin stabilizing agents.
  • the apparatus according to the invention is of the type suitable to disinfect water by producing in situ or at the time of use a solution of peroxyacid, alone or mixed with other peroxyacids, at the concentration required for the specific application: disinfection of wastewater and industrial water, cooling water, potable water and process water in general.
  • the apparatus 1 is substantially composed of an external housing 2, which internally accommodates a pump 3 for feeding one or more carboxylic acids mixed with one or more mineral acids, and a pump 4 for feeding the solution of hydrogen peroxide.
  • the reagents are drawn from respective tanks 5 and 6.
  • the pumps 3 and 4 are advantageously dosage pumps, suitable to adjust the flow-rates of the reagents to a static mixer 7, which is provided with an external heater 8. Intimate contact between the reagents and their heating to the reaction temperature are achieved inside said mixer.
  • the resulting mixture is sent to a thermally insulated reactor 9, which is advantageously of the variable-volume type, suitable to make the hourly output of the apparatus compatible with optimum reaction times and to avoid degradation of the finished product already inside the reactor.
  • the resulting peroxyacid exits from a duct 10 of the apparatus and from there it receives the appropriate addition of a current of water 11 and is drawn for use from an outlet 12.
  • the apparatus 1 is furthermore integrated with an electrical panel 13 and with a computerized system 14 for controlling its various functions.
  • the carboxylic acids are preferably formic acid (HCOOH), acetic acid (CH 3 COOH) and propionic acid (C 2 H 5 -COOH).
  • the mineral acids suitable for the invention are o-phosphoric acid and sulfuric acid.
  • the sulfuric acid has a 70- 96% concentration and the phosphoric acid has a 60-85% concentration.
  • the hydrogen peroxide is constituted by aqueous solutions at 20-70% by weight, preferably between 30 and 60% by weight.
  • the hydrogen peroxide is constituted by aqueous solutions at 30-55% by weight.
  • the peroxidation reaction entails the use of 0.5-5 moles of H 2 O 2 per mole of carboxylic acid in the presence of the diluted mineral acid.
  • carboxylic acids and the mineral acids form a mixture that has the following composition (percentages by weight):
  • the reaction between the carboxylic acids and the hydrogen peroxide occurs at temperatures between 20 and 60 °C.
  • the reaction time is controlled by the retention time of the reagents in the reaction chamber up to a maximum of 60 minutes. More preferably, the retention time is in the 15- to 30-minute range.
  • the reaction is continuous and proceeds at ambient pressure.
  • the peroxyacid and/or the mixture of peroxyacids are produced in concentrated form, in an aqueous solution at concentrations between 10 and 25% and more preferably between 18 and 22% by weight.
  • the resulting peroxyacids are diluted in line with water and then dosed.
  • a mixture is prepared which is constituted by 80% acetic acid, 14% sulfuric acid, and water for the remaining fraction, and a solution of 55% hydrogen peroxide is prepared.
  • the two solutions are introduced in the respective tanks of the apparatus.
  • the flow of the two reagents is adjusted so as to have a 1 :1 molar ratio between acetic acid and hydrogen peroxide.
  • the two reagents are sent to the heater in order to bring them under ther ostatic control to the intended temperature, and from there they enter the variable-volume reaction chamber, where they remain for the time required to complete the reaction, up to final concentrations of peracetic acid that are comprised between 20 and 22% by weight and with an hourly output that is a function of the water to be treated. This result is achieved under the following conditions:
  • the resulting peracetic acid is dosed by appropriately mixing on the water that leaves the secondary sedimentation basin of a conditioning system at the beginning of the disinfection tank, in a quantity that is variable according to requirements so as to obtain, after the allowed contact time, the degree of bacterial load that is suitable for discharge.
  • a mixture is prepared which is constituted by 80% 0 acetic acid, 7% sulfuric acid, 8.5% phosphoric acid, and water for the remaining fraction, and a solution of 55% hydrogen peroxide is prepared.
  • the two solutions are introduced in the respective tanks.
  • the flow of the two reagents is regulated so as to have a 1 :1 molar ratio between acetic acid and hydrogen peroxide.
  • the two reagents are sent to the heater in order to bring them under thermostatic control to the intended temperature and from there they enter the variable-volume reaction chamber, where they remain for the time required to complete the reaction, up to final peracetic acid concentrations of 20 to 22% by weight. This result is achieved under the following conditions:
  • the resulting peracetic acid is dosed by appropriate mixing at the beginning of the once-through cooling circuit in a stream of seawater in a quantity that can vary according to requirements so as to obtain the degree of bacterial load that is suitable to prevent the growth of fouling along the walls of the circuit.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method and an apparatus for disinfecting civil or industrial wastewater, cooling water, potable water and process in general by preparing in situ peroxyacids in which the peroxidation reaction is performed by adding at least one mineral acid to a carboxylic acid, in the presence of hydrogen peroxide and in the absence of ion-exchange resins.

Description

METHOD AND APPARATUS FOR WATER DISINFECTION
The present invention relates to a method and to the corresponding apparatus for disinfecting civil and industrial wastewater, cooling water, potable water and process water in general by preparing peroxyacids at various concentrations and in situ, i.e., directly at the time of use and according to the specific requirements of the application.
Water disinfection is necessary to avoid microbiological proliferation phenomena (bacteria, fungi, algae), which can cause hygienic and sanitary problems or failures of equipment.
For this type of application it is known to produce the peroxyacid by reaction, within a reactor of a suitable type, of carboxylic acid with hydrogen peroxide, in contact with ion-exchange resins suitable to provide the required degree of acidity to the solution.
The described known art has the drawback that ion-exchange resins tend to lose their effectiveness over time, due to the oxidizing action of the reagents, to the generated product that is in contact with the resin, to the temperatures used, and to other factors. The conventional use of ion-exchange resins, moreover, has the drawback of requiring the replacement of spent resins and the addition of stabilizing agents suitable to extend the life of these resins.
The aim of the invention is to provide a method and a corresponding apparatus that are suitable to disinfect water of various kinds by preparing peroxyacids in situ, without the drawbacks linked to the conventional use of ion-exchange resins.
Another object of the invention is to provide an apparatus that is simpler and more economical than those currently in use to prepare peroxyacids, obviating the need to replace spent resins, perform maintenance thereon, and similar operations.
Another object of the invention is to provide a method for producing peroxyacids in situ which, differently from known ones, does not require the use of resin stabilizing agents.
This aim and these and other objects that will become better apparent hereinafter are achieved with the method and the apparatus of claims 1 to 11 respectively. Preferred embodiments of the method and the apparatus according to the invention are given in the remaining claims. With respect to known embodiments in the field, the embodiment according to the invention has the advantage of allowing to obtain peroxyacids more simply and cheaply. Moreover, the invention no longer requires the use of stabilizing agents or maintenance or replacement of resins. This aim and these and other objects and advantages are apparent from the description that follows of the method and the apparatus according to the invention, said apparatus being illustrated only by way of non-limitative example in the accompanying figure.
The apparatus according to the invention, generally designated by the reference numeral 1 in the figure, is of the type suitable to disinfect water by producing in situ or at the time of use a solution of peroxyacid, alone or mixed with other peroxyacids, at the concentration required for the specific application: disinfection of wastewater and industrial water, cooling water, potable water and process water in general.
The apparatus 1 is substantially composed of an external housing 2, which internally accommodates a pump 3 for feeding one or more carboxylic acids mixed with one or more mineral acids, and a pump 4 for feeding the solution of hydrogen peroxide. The reagents are drawn from respective tanks 5 and 6. The pumps 3 and 4 are advantageously dosage pumps, suitable to adjust the flow-rates of the reagents to a static mixer 7, which is provided with an external heater 8. Intimate contact between the reagents and their heating to the reaction temperature are achieved inside said mixer.
The resulting mixture is sent to a thermally insulated reactor 9, which is advantageously of the variable-volume type, suitable to make the hourly output of the apparatus compatible with optimum reaction times and to avoid degradation of the finished product already inside the reactor. The resulting peroxyacid exits from a duct 10 of the apparatus and from there it receives the appropriate addition of a current of water 11 and is drawn for use from an outlet 12.
The apparatus 1 is furthermore integrated with an electrical panel 13 and with a computerized system 14 for controlling its various functions.
In this invention, the carboxylic acids are preferably formic acid (HCOOH), acetic acid (CH3COOH) and propionic acid (C2H5-COOH). The mineral acids suitable for the invention are o-phosphoric acid and sulfuric acid. Preferably, the sulfuric acid has a 70- 96% concentration and the phosphoric acid has a 60-85% concentration. The hydrogen peroxide is constituted by aqueous solutions at 20-70% by weight, preferably between 30 and 60% by weight. The hydrogen peroxide is constituted by aqueous solutions at 30-55% by weight.
The peroxidation reaction entails the use of 0.5-5 moles of H2O2 per mole of carboxylic acid in the presence of the diluted mineral acid.
The carboxylic acids and the mineral acids form a mixture that has the following composition (percentages by weight): Carboxylic acids:
Acetic acid: 40-80%
Formic acid: 0-40%
Propionic acid: 0-10%
Mineral acids: Phosphoric acid: 0-20%
Sulfuric acid: 0-20%
The reaction between the carboxylic acids and the hydrogen peroxide occurs at temperatures between 20 and 60 °C. The reaction time is controlled by the retention time of the reagents in the reaction chamber up to a maximum of 60 minutes. More preferably, the retention time is in the 15- to 30-minute range. The reaction is continuous and proceeds at ambient pressure.
The peroxyacid and/or the mixture of peroxyacids are produced in concentrated form, in an aqueous solution at concentrations between 10 and 25% and more preferably between 18 and 22% by weight. For their use, the resulting peroxyacids are diluted in line with water and then dosed.
All the materials in contact with the reagents must be chemically compatible; in particular, Teflon and high-density polyethylene are used. Example 1
A mixture is prepared which is constituted by 80% acetic acid, 14% sulfuric acid, and water for the remaining fraction, and a solution of 55% hydrogen peroxide is prepared. The two solutions are introduced in the respective tanks of the apparatus. By means of the dosage pumps, the flow of the two reagents is adjusted so as to have a 1 :1 molar ratio between acetic acid and hydrogen peroxide. The two reagents are sent to the heater in order to bring them under ther ostatic control to the intended temperature, and from there they enter the variable-volume reaction chamber, where they remain for the time required to complete the reaction, up to final concentrations of peracetic acid that are comprised between 20 and 22% by weight and with an hourly output that is a function of the water to be treated. This result is achieved under the following conditions:
Figure imgf000006_0001
The resulting peracetic acid, conveniently diluted to concentrations equal to 1 g/l, is dosed by appropriately mixing on the water that leaves the secondary sedimentation basin of a conditioning system at the beginning of the disinfection tank, in a quantity that is variable according to requirements so as to obtain, after the allowed contact time, the degree of bacterial load that is suitable for discharge.
Figure imgf000006_0002
Example 2
A mixture is prepared which is constituted by 80%0 acetic acid, 7% sulfuric acid, 8.5% phosphoric acid, and water for the remaining fraction, and a solution of 55% hydrogen peroxide is prepared. The two solutions are introduced in the respective tanks.
By means of the dosage pumps, the flow of the two reagents is regulated so as to have a 1 :1 molar ratio between acetic acid and hydrogen peroxide. The two reagents are sent to the heater in order to bring them under thermostatic control to the intended temperature and from there they enter the variable-volume reaction chamber, where they remain for the time required to complete the reaction, up to final peracetic acid concentrations of 20 to 22% by weight. This result is achieved under the following conditions:
Figure imgf000007_0001
The resulting peracetic acid, diluted appropriately, is dosed by appropriate mixing at the beginning of the once-through cooling circuit in a stream of seawater in a quantity that can vary according to requirements so as to obtain the degree of bacterial load that is suitable to prevent the growth of fouling along the walls of the circuit.
Figure imgf000007_0002

Claims

1. A method for disinfecting civil or industrial wastewater, cooling water, potable water and process water in general by producing peroxyacids or mixtures thereof, characterized in that it provides for an in situ reaction of peroxidation of at least one carboxylic acid with at least one mineral acid and with hydrogen peroxide, in the absence of ion-exchange resins.
2. The method according to claim 1, characterized in that said at least one mineral acid is present in solution with the carboxylic acid or with mixtures of carboxylic acids.
3. The method according to claim 1 or 2, characterized in that said at least one carboxylic acid is chosen among formic acid, acetic acid and propionic acid.
4. The method according to claim 1 or 2, characterized in that said at least one mineral acid is constituted by o-phosphoric acid or sulfuric acid.
5. The method according to one or more of the preceding claims, characterized in that said reaction is performed in the presence of hydrogen peroxide in a 20-70% solution by weight, preferably 30-60% by weight.
6. The method according to claim 5, characterized in that it provides for the addition of 0.5-5 moles of H2O2 per mole of carboxylic acid.
7. The method according to one or more of the preceding claims, characterized in that the reaction among said carboxylic acids and the hydrogen peroxide occurs at a temperature between 20 and 60 °C.
8. The method according to claim 7, characterized in that the reaction time is at most 60 minutes, preferably 15-30 minutes.
9. The method according to one or more of the preceding claims, characterized in that said peroxyacids are produced in an aqueous solution at a concentration comprised between 10 and 25% by weight, preferably 18 to 22% by weight.
10. The method according to one or more of the preceding claims, characterized in that said peroxyacid mixture has the following composition by weight:
Carboxylic acids:
Acetic acid: 40-80% Formic acid: 0-40% Propionic acid: 0-10%
Mineral acids:
Phosphoric acid: 0-20%
Sulfuric acid: 0-20%
Hvdroαen peroxide:
0.5-5 moles per mole of carboxylic acid
11. An apparatus for disinfecting civil or industrial wastewater, cooling water, potable water and process water in general by in situ preparation of peroxyacids with the method according to one or more of the preceding claims, characterized in that it comprises:
-- pumps, preferably dosage pumps, respectively a pump (3) for feeding one or more carboxylic acids mixed with one or more mineral acids, and a pump (4) for feeding the hydrogen peroxide solution; - a static mixer (7); -- a reactor (9).
12. The apparatus according to claim 11 , characterized in that said static mixer (7) is provided with a heater (8), and in that said reactor (9) is thermally insulated.
13. The apparatus according to claims 11 or 12, characterized in that said reactor is of the variable-volume type.
14. An aqueous solution of peroxyacids or mixtures of peroxyacids, obtained with the method and with the apparatus according to the preceding claims for preparing it in situ and at the time of use.
15. The solution according to claim 14, characterized in that it contains no stabilizing agents.
PCT/EP2003/001591 2002-03-18 2003-02-18 Method and apparatus for water disinfection Ceased WO2003078332A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003205774A AU2003205774A1 (en) 2002-03-18 2003-02-18 Method and apparatus for water disinfection
EP03702649A EP1485326A1 (en) 2002-03-18 2003-02-18 Method and apparatus for water disinfection

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2002A000568 2002-03-18
IT2002MI000568A ITMI20020568A1 (en) 2002-03-18 2002-03-18 PROCEDURE AND EQUIPMENT FOR WATER DISINFECTION

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WO2003078332A1 true WO2003078332A1 (en) 2003-09-25

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EP (1) EP1485326A1 (en)
AU (1) AU2003205774A1 (en)
IT (1) ITMI20020568A1 (en)
WO (1) WO2003078332A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20110253A1 (en) * 2011-05-06 2012-11-07 Barchemicals Biopharma S R L PROCEDURE FOR WATER TREATMENT

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409713A (en) * 1993-03-17 1995-04-25 Ecolab Inc. Process for inhibition of microbial growth in aqueous transport streams
EP0658309A1 (en) * 1993-12-14 1995-06-21 Chemoxal Sa Liquid disinfectant composition and its uses
US5779914A (en) * 1996-07-03 1998-07-14 Bio-Lab, Inc. Methods for sanitizing water
DE19935912A1 (en) * 1999-07-30 2001-02-01 Degussa Method for doping a liquid medium with a liquid dopant and device for carrying it out

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409713A (en) * 1993-03-17 1995-04-25 Ecolab Inc. Process for inhibition of microbial growth in aqueous transport streams
EP0658309A1 (en) * 1993-12-14 1995-06-21 Chemoxal Sa Liquid disinfectant composition and its uses
US5779914A (en) * 1996-07-03 1998-07-14 Bio-Lab, Inc. Methods for sanitizing water
DE19935912A1 (en) * 1999-07-30 2001-02-01 Degussa Method for doping a liquid medium with a liquid dopant and device for carrying it out

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FRASER J A L: "Novel applications of peracetic acid in industrial disinfection", SPECIALITY CHEMICALS, REDHILL, GB, vol. 7, no. 3, 1987, pages 178 - 186, XP002177366, ISSN: 0262-2262 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20110253A1 (en) * 2011-05-06 2012-11-07 Barchemicals Biopharma S R L PROCEDURE FOR WATER TREATMENT

Also Published As

Publication number Publication date
AU2003205774A1 (en) 2003-09-29
EP1485326A1 (en) 2004-12-15
ITMI20020568A0 (en) 2002-03-18
ITMI20020568A1 (en) 2003-09-18

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