EP0684859B1 - Verfahren zur entsorgung von abfällen von p4s10 - Google Patents

Verfahren zur entsorgung von abfällen von p4s10 Download PDF

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Publication number
EP0684859B1
EP0684859B1 EP94931626A EP94931626A EP0684859B1 EP 0684859 B1 EP0684859 B1 EP 0684859B1 EP 94931626 A EP94931626 A EP 94931626A EP 94931626 A EP94931626 A EP 94931626A EP 0684859 B1 EP0684859 B1 EP 0684859B1
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EP
European Patent Office
Prior art keywords
process according
waste
sodium hydroxide
solution
phosphates
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.)
Expired - Lifetime
Application number
EP94931626A
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English (en)
French (fr)
Other versions
EP0684859A1 (de
Inventor
Paul Bourdauducq
L. Bâtiment Bahamas PENEL
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.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Publication date
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Publication of EP0684859A1 publication Critical patent/EP0684859A1/de
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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
    • A62D3/35—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by hydrolysis
    • 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
    • A62D2101/40—Inorganic substances
    • A62D2101/45—Inorganic 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
    • A62D2101/40—Inorganic substances
    • A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • the present invention relates to a process for eliminating waste formed during the manufacture, packaging and use of phosphorus polysulphides and in particular of P 4 S 10 .
  • P 4 S 10 is prepared from liquid sulfur and liquid phosphorus in substantially stoichiometric quantities at temperatures between 300 ° C and 515 ° C.
  • the products obtained generally pass through a packed column allowing to retain the impurities likely to come from the reagents as well as by-products likely to form during the reaction.
  • P 4 S 10 consist mainly of P 4 S 10 associated with small quantities of phosphorus polysulphides such as P 4 S 9 , P 4 S 7 . It also detects organic impurities and metallic impurities such as iron, arsenic, nickel, chromium, antimony.
  • This waste is more or less sensitive to hydrolysis and cannot be stored in landfills or buried because the slow hydrolysis of this waste is likely to produce significant quantities of gas (H 2 S) and toxic materials likely to irreparably contaminate groundwater.
  • gas H 2 S
  • Patent DD 122 058 teaches that the waste originating from the synthesis of P 4 S 10 can be treated with a sodium hydroxide solution and then injection of chlorine.
  • This treatment makes it possible to transform the waste essentially consisting of P 4 S 10 into a mixture of products consisting of phosphates, phosphites, thiophosphates, sulfates and chlorides.
  • the waste is treated with sodium hydroxide solution and then undergoes a chlorine treatment in order to obtain a pH close to 7-8. Chlorination is continued while adding sodium hydroxide to maintain said pH at 7-8.
  • this method has the disadvantage of generating quantities significant elemental sulfur and also has the disadvantage of using chlorine.
  • US Patent 4,301,014 relates to the treatment of water resulting from the elimination of waste from the manufacture of P 4 S 10 .
  • This waste is hydrolyzed with water, then brought into contact with lime in order to precipitate the sulphides, sulphites, sulphates and phosphates in the form of calcium salts, then to treat the solution freed from these salts by an oxidant such as calcium chlorine or hypochlorite at a pH close to 9 in order to reduce the "chemical oxygen demand" (DOC) before discharge.
  • DOC chemical oxygen demand
  • this process requires many filtration operations: filtration after hydrolysis, filtration after precipitation with lime, filtration after chlorination, which are likely to increase the cost and complexity of the operation of the process.
  • This process is particularly applicable to waste from the manufacture, packaging and use of P 4 S 10 .
  • the waste can be dissolved alkaline in different ways depending on the one hand, their origin and, on the other hand their physical state.
  • vents and / or gaseous effluents originating in particular from the reactor and from the conditioning consisting essentially of suspended powders and traces of H 2 S are generally killed by an alkaline solution which consists of backwashing with an alkaline solution (A) .
  • Waste from washing containers with pressurized water are introduced into an alkaline solution (B).
  • Solid waste in different forms plus blocks or less coarse, powders, scales
  • washing devices such as scaly, conveyor screw, reactor, condensers and products outside specifications are collected and then introduced into an alkaline solution (C).
  • the different alkaline solutions (A), (B) and (C) are generally soda, potash or ammonia solutions. These solutions may have the same or different concentrations of alkaline agent. Of preferably, sodium hydroxide solutions with a weight concentration will be used in NaOH of between 5% and 30% and preferably between 10% and 20%.
  • the molar ratio Rm P 4 S 10 NaOH is at least 13 and preferably between 15 and 32.
  • the waste is treated separately or simultaneously, we operate preferably by introducing the waste into the alkaline solution with stirring at a temperature between 20 ° C and 80 ° C and preferably between 25 ° C and 60 ° C.
  • the duration of the dissolution can vary to a large extent. She is generally based on the physical state of the waste.
  • the buffer tank solution consists of sodium thiophosphates of formula Na 3 PS x O 4-x ; x being an integer ranging from 1 to 4, Na 2 S, sodium phosphates and sodium phosphite.
  • the final solution obtained must be at a pH greater than 7 in order to avoid any release of H 2 S.
  • This alkaline solution operation is generally carried out in reactors with stirring system, temperature measurement, heating and cooling systems.
  • the alkaline solution thus obtained is then biologically oxidized.
  • the solution is introduced into a so-called "activated sludge” reactor.
  • a biological station treating wastewater coming in particular from a site industrial.
  • activated sludges are made up of microorganisms and bacteria which, in an aerobic environment, destroy the carbon pollution of industrial effluent (decrease in COD) and also oxidize sulfides and thiophosphates.
  • the "activated sludge" reactor is supplied with air or pure oxygen thus allowing the ventilation of the medium.
  • the pH of the medium must be as stable as possible and as close as possible of neutrality, see slightly basic.
  • the effluent After passing through the reactor, the effluent is separated from the sludge which is made up of micro-organisms and bacteria, in a clarifier before rejection.
  • the decanted sludge is largely recycled in the reactor, a part of the settled sludge is conveyed to a thickener where the maximum water.
  • the water is recycled to the reactor while the sludge is disposed of in a landfill.
  • the advantage of the process according to the present invention is that it eliminates waste in the form of aqueous effluents consisting essentially of sulfates and phosphates in accordance with the standards in force concerning discharges.
  • the introduction of the waste is regulated in such a way that the temperature does not exceed 50 ° C.
  • the duration of the operation is approximately 6 hours.
  • water is introduced to complete the level up to 15 m 3 .
  • the quantity of sodium hydroxide used is greater than the stoichiometric quantity of sodium hydroxide necessary for the hydrolysis so as to obtain an effluent containing free sodium hydroxide making it possible to avoid any release of H 2 S.
  • Each aqueous effluent (1) previously prepared is sent to a biological treatment station. It is deposited in a tank (2) continuously supplied with effluents of the same nature (3) (sodium hydroxide solutions consisting of Na 2 S). The content of this tank is then injected continuously (4) into the "active" sludge reactor (5) at the same time as all of the wastewater from an industrial site (6).
  • effluents of the same nature (3) sodium hydroxide solutions consisting of Na 2 S
  • Activated sludge consists of microorganisms and bacteria evolving in aerobic environment.
  • the ventilation of the medium is ensured by an air supply (7) and also by a supply of pure oxygen (8).
  • Oxidation takes place at atmospheric pressure, at room temperature and at a pH of around 8.
  • Decanted sludge is largely recycled to the reactor (5) via (12). Part of these go to a thickener (13) in which we extract a maximum amount of water which is recycled to the reactor (5) via (14), the sludge thickened are disposed of in a landfill (15).
  • Soluble phosphates are analyzed regularly during biological oxidation operations and 15 days after the treatment of the last effluent (No. 8) in the releases (11) from the biological station.

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)
  • Removal Of Specific Substances (AREA)
  • Activated Sludge Processes (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (11)

  1. Verfahren zur Beseitigung von bei der Herstellung Aufbereitung und Verwendung von Phosphorpolysulfiden gebildeten Abfällen, dadurch gekennzeichnet, daß
    man die Abfälle durch Einwirkung von Alkalien in Lösung bringt,
    man die verschiedenen erhaltenen Lösungen in einem Pufferbehältnis sammelt, und
    man die so erhaltenen, bei einem pH-Wert von mehr als 7 konstant gehaltenen Lösungen, welche Thiophosphate der Formel Me3PSxO4-x, wobei Me NH4 oder ein Alkalimetall wie Na oder K darstellt und x eine ganze Zahl von 1 bis 4 ist, Phosphate, Sulfide und Phosphite enthalten, biologisch oxidiert, bevor sie in Form einer Lösung, die im wesentlichen aus Sulfaten und Phosphaten besteht, entsorgt werden.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Phosphorpolysulfid P4S10 ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Einwirkung von Alkalien auf die Abfälle durch eine Natriumhydroxidlösung, eine Kaliumhydroxidlösung oder eine ammoniakalische Lösung erfolgt.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die alkalische Lösung eine Natriumhydroxidlösung ist.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Natriumhydroxidlösung eine gewichtsbezogene Konzentration an Natriumhydroxid (NaOH) zwischen 5 % und 30 %, vorzugsweise zwischen 10 % und 20 %, aufweist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Abfälle unter Rühren bei einer Temperatur zwischen 20 °C und 80 °C, vorzugsweise zwischen 25 °C und 60 °C, in die Alkalilösung eingetragen werden.
  7. Verfahren nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die gesammelten Alkalilösungen Natriumhydroxidlösungen sind.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Natriumhydroxidlösungen im wesentlichen aus Natriumthiophosphat der Formel Na3PSxO4-x, worin x eine ganze Zahl von 1 bis 4 ist, Na2S, Natriumphosphaten und Natriumphosphiten bestehen.
  9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Natriumhydroxidlösungen in einen Reaktor mit Aktivschlamm, der im wesentlichen aus Mikroorganismen und Bakterien besteht, die ein aerobes Milieu erzeugen, eingetragen werden.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß dem Reaktor mit dem Aktivschlamm Luft zugeführt wird.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Abfälle in Form einer Lösung, die Sulfate und Phosphate enthält, entsorgt werden.
EP94931626A 1993-10-22 1994-10-24 Verfahren zur entsorgung von abfällen von p4s10 Expired - Lifetime EP0684859B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9312633 1993-10-22
FR9312633A FR2711558B1 (fr) 1993-10-22 1993-10-22 Procédé d'élimination des déchets du P4S10.
PCT/FR1994/001236 WO1995011061A1 (fr) 1993-10-22 1994-10-24 Procede d'elimination des dechets du p4s¿10?

Publications (2)

Publication Number Publication Date
EP0684859A1 EP0684859A1 (de) 1995-12-06
EP0684859B1 true EP0684859B1 (de) 1998-07-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP94931626A Expired - Lifetime EP0684859B1 (de) 1993-10-22 1994-10-24 Verfahren zur entsorgung von abfällen von p4s10

Country Status (4)

Country Link
EP (1) EP0684859B1 (de)
DE (1) DE69412070T2 (de)
FR (1) FR2711558B1 (de)
WO (1) WO1995011061A1 (de)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980557A (en) * 1974-12-18 1976-09-14 University Patents, Inc. Phosphorus removal from wastewater
US4301014A (en) * 1980-06-05 1981-11-17 Hooker Chemicals & Plastics Corp. Phosphorus pentasulfide waste water treatment
US4956094A (en) * 1988-12-22 1990-09-11 Biospherics Incorporated Enhanced phosphate removal from bod-containing wastewater

Also Published As

Publication number Publication date
EP0684859A1 (de) 1995-12-06
FR2711558A1 (fr) 1995-05-05
WO1995011061A1 (fr) 1995-04-27
DE69412070T2 (de) 1999-04-15
DE69412070D1 (de) 1998-09-03
FR2711558B1 (fr) 1996-01-05

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