EP0715533A1 - Abfallbehandlung - Google Patents

Abfallbehandlung

Info

Publication number
EP0715533A1
EP0715533A1 EP95925047A EP95925047A EP0715533A1 EP 0715533 A1 EP0715533 A1 EP 0715533A1 EP 95925047 A EP95925047 A EP 95925047A EP 95925047 A EP95925047 A EP 95925047A EP 0715533 A1 EP0715533 A1 EP 0715533A1
Authority
EP
European Patent Office
Prior art keywords
solution
organic species
aqueous solution
hydrogen peroxide
organic
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Withdrawn
Application number
EP95925047A
Other languages
English (en)
French (fr)
Inventor
Graham Victor Hutson
Philip Henry Jordan
Norma Rumney
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.)
Sellafield Ltd
Original Assignee
British Nuclear Fuels PLC
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 British Nuclear Fuels PLC filed Critical British Nuclear Fuels PLC
Publication of EP0715533A1 publication Critical patent/EP0715533A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/26—Organic substances containing nitrogen or phosphorus
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

  • the present invention relates to a process for the destruction of waste organic liquids.
  • Waste organic liquids are necessary by-product of many operations in chemical, nuclear and related industries.
  • Such wastes are increasingly becoming a disposal problem since their traditional methods of disposal, for example, incineration, landfill and discharge to sewer, are becoming unacceptable due to increasingly stringent environmental protection legislation.
  • organic complexing agents are used in many chemical processes and in the nuclear industry for decontamination and other purposes.
  • the spent complexing agent solutions often contain toxic heavy metals and/or radioactive nuclides.
  • the chemical nature of these solutions mean that they cannot, in significant concentrations and without some form of initial treatment, be directed to normal effluent treatment plants, such as precipitation, ion exchange or evaporation plants. In fact, the addition of these solutions to such effluent treatment plants, could well cause the operation of the plants to be less efficient.
  • alkylphosphates can be destroyed by reaction with hydrogen peroxide in the presence of a chromium catalyst.
  • the two phase decomposition reaction is carried out at a temperature of at least 60°C and the pH of the reaction mixture is controlled within specified limits.
  • the alkylphosphates are present in an organic phase and are decomposed by the hydrogen peroxide which is in aqueous solution. During the reaction the alkylphosphates are decomposed to inorganic phosphate, carbon dioxide and water, whilst the hydrophobic solvent remains unaffected.
  • a process for decomposing one or more organic species in aqueous solution comprising reacting the organic species with an aqueous solution of hydrogen peroxide in the -presence of a transition metal catalyst comprising chromium, the hydrogen peroxide being added progressively to the organic species and the reaction being carried out within a temperature range of ambient temperature to reflux temperature of the aqueous solution.
  • the aqueous solution to be treated may be an aqueous solution containing significantly less than 1% of the organic species.
  • an aqueous solution to be treated may contain from 0.05% by volume of the organic species.
  • the organic species may comprise organic liquids.
  • the catalyst used in the process may be a chromate, particularly sodium chromate or potassium chromate.
  • the process is suitable for the treatment of a wide range of organic substrates but typically the organic species may include complexants in dilute aqueous solution or waste solvents, such as dibutoxydiethyl ether (Butex) , lubricating oils or cutting oils.
  • dibutoxydiethyl ether butex
  • the process is particularly useful for destroying complexants, including carboxylic acids, such as citric acid, and ethylene dia ine tetra-acetic acid (EDTA) which are major constituents of decontamination solutions widely used in the nuclear industry.
  • carboxylic acids such as citric acid
  • EDTA ethylene dia ine tetra-acetic acid
  • the decomposition reaction may be carried out over the temperature range of ambient temperature to reflux temperature (about 100°C) and preferably, the hydrogen peroxide may be in a concentration range of 10% to 50% v/v and may be added over a period of 1 hour.
  • the precise temperature, hydrogen peroxide concentration, or rate of addition of hydrogen peroxide are not crucial to the decomposition reaction.
  • the pH of the reaction mixture may fall due to the formation of acidic intermediates. Should this fall in pH occur to an undesirable extent (for example, below pH 3.5), the pH may be corrected by the addition of an appropriate quantity of dilute alkali, such as sodium hydroxide, to the reaction mixture.
  • dilute alkali such as sodium hydroxide
  • the process of the present invention may be used for the destruction of a class of chemical compounds having properties quite different from those of alkylphosphates (as treated in the prior art) , which compounds having significantly different uses to those of alkylphosphates.
  • two or more different organic species, present together as a mixture or in solution may each be destroyed.
  • citric acid and EDTA may be treated in this way, such species typically being present together in some commercially available decontamination agents.
  • the process converts organic complexing agents into small molecules such as carbon dioxide, water and other species with no significant complexing activity, and hence makes the streams containing them suitable for further treatment, to remove heavy metals and radionuclides, by conventional aqueous treatment plants, such as precipitation, ion exchange or evaporation plants, and thereby minimises the amount of harmful species discharged to the environment.
  • chromium from the catalyst will be present in the resulting aqueous solution. However, if the chromium is conditioned so that it is converted to CrIII, it may be removed by a precipitation process in common with the other heavy metals present. The chromium may also be removed by ion exchange.
  • An advantage of the process of the present invention is that it operates using a stoichiometric quantity or a modest excess of hydrogen peroxide and can be performed in a simple stirred tank reactor.
  • Example 1 Embodiments of the present invention will now be described, by way of example only, by reference to the following Examples: Example 1
  • the apparatus used was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the apparatus was as in Example 2.
  • the present invention therefore provides a cost effective and environmentally acceptable process for converting waste organic liquids, having at least a limited solubility in aqueous solutions, into a form acceptable for discharge (to the environment) and renders any associated metals, be they toxic, radioactive or any other undesirable species, into a form readily treatable by conventional aqueous effluent treatment facilities.

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Removal Of Specific Substances (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
EP95925047A 1994-06-24 1995-06-23 Abfallbehandlung Withdrawn EP0715533A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9412794 1994-06-24
GB9412794A GB9412794D0 (en) 1994-06-24 1994-06-24 Waste treatment
PCT/GB1995/001479 WO1996000114A1 (en) 1994-06-24 1995-06-23 Waste treatment

Publications (1)

Publication Number Publication Date
EP0715533A1 true EP0715533A1 (de) 1996-06-12

Family

ID=10757329

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95925047A Withdrawn EP0715533A1 (de) 1994-06-24 1995-06-23 Abfallbehandlung

Country Status (5)

Country Link
EP (1) EP0715533A1 (de)
JP (1) JPH09502380A (de)
KR (1) KR960703641A (de)
GB (1) GB9412794D0 (de)
WO (1) WO1996000114A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57191599A (en) * 1981-05-22 1982-11-25 Japan Atomic Energy Res Inst Method of decomposing anion exchanging resin
GB8811784D0 (en) * 1988-05-18 1988-06-22 Interox Chemicals Ltd Waste treatment
US5139679A (en) * 1992-02-24 1992-08-18 The United States Of America As Represented By The Secretary Of The Navy Treatment of wastewater containing citric acid and triethanolamine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9600114A1 *

Also Published As

Publication number Publication date
GB9412794D0 (en) 1994-08-17
WO1996000114A1 (en) 1996-01-04
JPH09502380A (ja) 1997-03-11
KR960703641A (ko) 1996-08-31

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Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960304

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 19970611

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19971022