EP0684859B1 - Procede d'elimination des dechets du p4s10 - Google Patents
Procede d'elimination des dechets du p4s10 Download PDFInfo
- 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
- Authority
- 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
Links
Images
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)
Description
Les déchets formés lors de la préparation et du conditionnement de P4S10 proviennent essentiellement du nettoyage des appareils tels que écailleuse, vis transporteuse, condenseurs,.... et se trouvent être sous forme de poudres ou d'écailles qui représentent au moins 10 % de la totalité des déchets ; de la vidange périodique du réacteur et se trouvent être sous forme de gros blocs qui représentent environ 25 % de la totalité des déchets ; du lavage des conteneurs de retour et se présentent sous forme initiale d'écailles ou poudres qui représentent la quantité la plus importante des déchets estimée à environ 55 % et des évents et effluents qui se trouvent être initialement sous forme de gaz contenant des poussières de P4S10, des traces de H2S. Cette dernière provenance représente quelques 10 % de la totalité des déchets.
- mettre en solution lesdits déchets par attaque alcaline, à
- collecter les différentes solutions obtenues dans un bac tampon, et à
- oxyder biologiquement les solutions ainsi obtenues maintenues à un pH supérieur à 7, contenant des thiophosphates de formule Me3 PSx O4-x dans laquelle Me représente NH4, un métal alcalin tel que Na, K et x est un nombre entier allant de 1 à 4, des phosphates, des sulfures et des phosphites avant rejet sous forme de solution constituée essentiellement par des sulfates et des phosphates.
et, de préférence, compris entre 15 et 32.
- la concentration en phosphates totaux
- la concentration en soude libre.
EFFLUENT N° | CONCENTRATION EN PHOSPHATES TOTAUX (g/l) | CONCENTRATION EN SOUDE LIBRE (g/l) |
1 | 42,9 | 50,8 |
2 | 36 | 13,4 |
3 | 32 | 22,7 |
4 | 52 | 16,9 |
5 | 50 | 16,9 |
6 | 37,5 | 25,8 |
7 | 48,8 | 25,6 |
8 | 47,5 | 11,6 |
- Na3PSxO4-x avec x allant de 1 à 4,
- Phosphates de sodium
- Na2S
- Na3PO3
- Sur ce graphique :
- P désigne la teneur en phosphates exprimée en mg/l,
J designe la durée des opérations en jour,
les astériques correspondent aux injections des effluents à traiter,
la ligne portant des carrés noirs désigne les phosphates totaux,
la ligne portant des carrés blancs désigne les phosphates solubles.
Claims (11)
- Procédé d'élimination des déchets formés au cours de la fabrication, du conditionnement et de l'utilisation de polysulfures de phosphore, caractérisé en ce qu'il consiste à :mettre en solution lesdits déchets par attaque alcaline, àcollecter les différentes solutions obtenues dans un bac tampon, et àoxyder biologiquement les solutions ainsi obtenues, maintenues à un pH supérieur à 7, contenant des thiophosphates de formule Me3 PSx O4-x dans laquelleMe représente NH4, un métal alcalin tel que Na, K etx est un nombre entier allant de 1 à 4, des phosphates, des sulfures et des phosphites avant rejet sous forme de solution constituée essentiellement par des sulfates et des phosphates.
- Procédé selon la revendication 1, caractérisé en ce que le polysulfure de phosphore est P4S10.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que l'attaque alcaline des déchets est effectuée par une solution de soude, de potasse ou une solution ammoniacale.
- Procédé selon la revendication 3, caractérisé en ce que la solution alcaline est une solution de soude.
- Procédé selon la revendication 4, caractérisé en ce que la solution de soude a une concentration pondérale en hydroxyde de sodium (NaOH) comprise entre 5 % et 30 % et, de préférence, entre 10 % et 20 %.
- Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les déchets sont introduits dans la solution alcaline sous agitation à une température comprise entre 20°C et 80°C et, de préférence, entre 25°C et 60°C.
- Procédé selon les revendications 1 à 6, caractérisé en ce que les solutions alcalines collectées sont des solutions de soude.
- Procédé selon la revendication 7, caractérisé en ce que les solutions de soude sont constituées essentiellement de thiophosphate de sodium de formule Na3PSxO4-x dans laquelle x est un nombre entier allant de 1 à 4, de Na2S, de phosphates de sodium et de phosphites de sodium.
- Procédé selon l'une des revendications 7 ou 8 caractérisé en ce que les solutions de soude sont introduites dans un réacteur à boues activées constituées de micro-organismes et de bactéries évoluant en milieu aérobie.
- Procédé selon la revendication 9, caractérisé en ce que le réacteur à boues activées est alimenté en air.
- Procédé selon l'une quelconque des revendications 1 à 10 caractérisé en ce que les déchets sont rejetés sous forme d'une solution contenant des sulfates et des phosphates.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9312633A FR2711558B1 (fr) | 1993-10-22 | 1993-10-22 | Procédé d'élimination des déchets du P4S10. |
FR9312633 | 1993-10-22 | ||
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 (fr) | 1995-12-06 |
EP0684859B1 true EP0684859B1 (fr) | 1998-07-29 |
Family
ID=9452133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94931626A Expired - Lifetime EP0684859B1 (fr) | 1993-10-22 | 1994-10-24 | Procede d'elimination des dechets du p4s10 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0684859B1 (fr) |
DE (1) | DE69412070T2 (fr) |
FR (1) | FR2711558B1 (fr) |
WO (1) | WO1995011061A1 (fr) |
Family Cites Families (3)
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 |
-
1993
- 1993-10-22 FR FR9312633A patent/FR2711558B1/fr not_active Expired - Fee Related
-
1994
- 1994-10-24 EP EP94931626A patent/EP0684859B1/fr not_active Expired - Lifetime
- 1994-10-24 WO PCT/FR1994/001236 patent/WO1995011061A1/fr active IP Right Grant
- 1994-10-24 DE DE69412070T patent/DE69412070T2/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
FR2711558A1 (fr) | 1995-05-05 |
EP0684859A1 (fr) | 1995-12-06 |
DE69412070T2 (de) | 1999-04-15 |
DE69412070D1 (de) | 1998-09-03 |
FR2711558B1 (fr) | 1996-01-05 |
WO1995011061A1 (fr) | 1995-04-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0413356B1 (fr) | Procédé pour le traitement d'eau usée | |
US7166227B2 (en) | Method of treating digested sludge | |
US3939068A (en) | Process for treating waste water containing cellulose nitrate particles | |
ITMI940245A1 (it) | Processo per il trattamento di rifiuti con impiego di ossidazione | |
FI97218C (fi) | Jäteveden puhdistusprosessi | |
US6802976B2 (en) | Organic sulfur reduction in wastewater | |
EP0512660A1 (fr) | Méthode et installation d'élimination par combinaison chimique-biologique des résidus contenant des explosives | |
US6077431A (en) | Process for decomposition and removal of dioxins contained in sludge | |
CZ278195A3 (en) | Process of treating waste water containing both organic and inorganic compounds, particularly waste water formed during preparation of epichlorhydrine | |
US4490257A (en) | Process for purification of waste waters accumulated from pulp production, particularly from chlorine bleaching of pulp | |
US5348724A (en) | Method of decomposing hydrogen peroxide | |
US10669175B2 (en) | Method for treating sulfides in waste streams | |
EP0684859B1 (fr) | Procede d'elimination des dechets du p4s10 | |
EP0564386B1 (fr) | Procédé de traitement des boues par oxydation combinée chimique et biologique et installations pour la mise en oeuvre d'un tel procédé | |
US4301014A (en) | Phosphorus pentasulfide waste water treatment | |
US5549833A (en) | Method of decomposing hydrogen peroxide | |
EP0952116A1 (fr) | Procédé de décomposition et d'élimination des dioxines contenus dans des boues | |
IE67375B1 (en) | Water purification process | |
EP2427407B1 (fr) | Procédé de récupération et de recyclage d'ammoniac | |
EP0336929B1 (fr) | Procede de purification d'eau | |
EP0634370A1 (fr) | Procédé de traitement d'effluents azotés avec des boues comme substrat | |
JPS591120B2 (ja) | 有機性排水の高度処理方法 | |
JP2627953B2 (ja) | 廃水の処理方法 | |
Boronin et al. | Electrochemical and Biological Approach to the Destruction of Lewisite and ‘Mustard’ | |
GB2155453A (en) | Treatment of "Stretford" redox solutions |
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 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19951229 |
|
17Q | First examination report despatched |
Effective date: 19970520 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19980810 |
|
REF | Corresponds to: |
Ref document number: 69412070 Country of ref document: DE Date of ref document: 19980903 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20011010 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20011024 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20011031 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20011105 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030501 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030501 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20021024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030630 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030501 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051024 |