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WO2003078332A1 - Procede de desinfection d'eaux usees et appareil a cet effet - Google Patents

Procede de desinfection d'eaux usees et appareil a cet effet 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
Authority
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
English (en)
Inventor
Mario Belluati
Daniele Copetti
Enrico Danesi
Giorgio Colombi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Caffaro SpA
Original Assignee
Caffaro SpA
Priority date (The priority date 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 date listed.)
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/fr
Publication of WO2003078332A1 publication Critical patent/WO2003078332A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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.

Landscapes

  • 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

Cette invention a trait à un procédé de désinfection d'eaux usées, publiques ou industrielles, d'eaux de refroidissement, d'eau potable et d'eaux de traitement. Ce procédé consiste à produire in situ des peroxyacides, la réaction de peroxydation se faisant par adjonction d'au moins un acide inorganique à un acide carboxylique, en présence de peroxyde d'hydrogène et en l'absence de résines échangeuses d'ions.
PCT/EP2003/001591 2002-03-18 2003-02-18 Procede de desinfection d'eaux usees et appareil a cet effet Ceased WO2003078332A1 (fr)

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 (fr) 2002-03-18 2003-02-18 Procede de desinfection d'eaux usees et appareil a cet effet

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2002A000568 2002-03-18
IT2002MI000568A ITMI20020568A1 (it) 2002-03-18 2002-03-18 Procedimento e apparecchiatura per la disinfezione delle acque

Publications (1)

Publication Number Publication Date
WO2003078332A1 true WO2003078332A1 (fr) 2003-09-25

Family

ID=11449532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/001591 Ceased WO2003078332A1 (fr) 2002-03-18 2003-02-18 Procede de desinfection d'eaux usees et appareil a cet effet

Country Status (4)

Country Link
EP (1) EP1485326A1 (fr)
AU (1) AU2003205774A1 (fr)
IT (1) ITMI20020568A1 (fr)
WO (1) WO2003078332A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20110253A1 (it) * 2011-05-06 2012-11-07 Barchemicals Biopharma S R L Procedimento per il trattamento di acqua

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 (fr) * 1993-12-14 1995-06-21 Chemoxal Sa Composition liquide désinfectante et ses utilisations
US5779914A (en) * 1996-07-03 1998-07-14 Bio-Lab, Inc. Methods for sanitizing water
DE19935912A1 (de) * 1999-07-30 2001-02-01 Degussa Verfahren zum Dotieren eines flüssigen Mediums mit einem flüssigen Dotierungsmittel und Vorrichtung zu seiner Durchführung

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 (fr) * 1993-12-14 1995-06-21 Chemoxal Sa Composition liquide désinfectante et ses utilisations
US5779914A (en) * 1996-07-03 1998-07-14 Bio-Lab, Inc. Methods for sanitizing water
DE19935912A1 (de) * 1999-07-30 2001-02-01 Degussa Verfahren zum Dotieren eines flüssigen Mediums mit einem flüssigen Dotierungsmittel und Vorrichtung zu seiner Durchführung

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 (it) * 2011-05-06 2012-11-07 Barchemicals Biopharma S R L Procedimento per il trattamento di acqua

Also Published As

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

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