WO1995011061A1 - Procede d'elimination des dechets du p4s¿10? - Google Patents
Procede d'elimination des dechets du p4s¿10? Download PDFInfo
- Publication number
- WO1995011061A1 WO1995011061A1 PCT/FR1994/001236 FR9401236W WO9511061A1 WO 1995011061 A1 WO1995011061 A1 WO 1995011061A1 FR 9401236 W FR9401236 W FR 9401236W WO 9511061 A1 WO9511061 A1 WO 9511061A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- waste
- solution
- sodium hydroxide
- solutions
- alkaline
- Prior art date
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
- A62D3/35—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 P4S-
- P4S10 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 making it possible to retain the impurities liable to come from the reagents as well as the by-products liable to form during the reaction.
- the waste formed during the preparation and packaging of P4S10 comes essentially from the cleaning of devices such as scaly, conveyor screw, condensers, etc. and are found to be in the form of powders or flakes which represent at least 10% of all of the waste; periodic emptying of the reactor and happen to be in the form of large blocks which represent approximately 25% of the total waste; washing of the return containers and are in the initial form of flakes or powders which represent the largest amount of waste estimated at around 55% and of the vents and effluents which happen to be initially in the form of gases containing P4S10 dust . traces of H2S. The latter source represents some 10% of all waste.
- P4S10 consist mainly of P4S10 associated with small quantities of phosphorus polysulfides such as P4S9, P4S7.
- Organic impurities and metallic impurities such as iron, arsenic, nickel, chromium, antimony are also detected there.
- 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 (H2S) and toxic materials likely to irreparably contaminate groundwater.
- H2S gas
- Patent DD 122 058 teaches that the waste originating from the synthesis of P4S10 can be treated by washing with soda and then injecting chlorine.
- This treatment makes it possible to transform the waste essentially consisting of P4S10 into a mixture of products consisting of phosphates, phosphites, thiophosphates, sulfates and chlorides.
- this method has a number of drawbacks.
- the waste is treated with sodium hydroxide solution and then undergoes a treatment with chlorine so as to obtain a pH close to 7-8. Chlorination is continued while adding sodium hydroxide in order to maintain said pH at 7-8.
- this method has the disadvantage of generating significant amounts of elemental sulfur and also has the disadvantage of using chlorine.
- US Pat. No. 4,301,014 relates to the treatment of water resulting from the elimination of waste from the manufacture of P S-
- an oxidant such as chlorine or calcium hypochlorite at a pH close to 9 in order to reduce the "chemical demand for oxygen "(COD) before rejection.
- the waste can be put into alkaline solution in different ways depending on the one hand, their source 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 H2S are generally knocked down by an alkaline solution which consists of washing against the current with an alkaline solution (A).
- the waste from washing the containers with pressurized water is introduced into an alkaline solution (B).
- Solid waste in different forms (more or less coarse blocks, powders, scales) from both washing of devices such as scaly, conveyor screw, reactor, condensers and out of specification products are collected and then introduced into a solution alkaline (C).
- C solution alkaline
- the various alkaline solutions (A), (B) and (C) are generally sodium hydroxide solutions, potassium hydroxide solutions or ammoniacal solutions. These solutions can have identical or different concentrations of alkaline agent.
- sodium hydroxide solutions having a NaOH concentration by weight of between 5% and 30% and preferably between 10% and
- the molar ratio Rm is at least equal to 13
- NaOH sodium sulfate
- the waste is treated separately or simultaneously, it is preferably carried out 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. It is generally a function of the physical state of the waste. It is at least equal to 30 minutes and, preferably, between 2 and 6 hours.
- the different solutions (A), (B) and (C) are collected, in particular in a so-called “buffer” tank.
- the solution obtained is generally clear.
- the solution of the buffer tank consists of sodium thiophosphates of formula Na ⁇ PS X 04_ x ; x being an integer ranging from 1 to 4, Na2S, sodium phosphates and sodium phosphite.
- the final solution obtained must be at a pH greater than 7 in order to avoid any release of H2S.
- This alkaline solution operation is generally carried out in reactors provided with a stirring system, a temperature measurement, heating and cooling systems.
- separation can be carried out by known methods such as filtration or centrifugation.
- the alkaline solution thus obtained is then biologically oxidized.
- the solution is introduced into a so-called "activated sludge" reactor of a biological station treating wastewater coming in particular from an industrial site.
- activated sludges are made up of microorganisms and bacteria which, in aerobic environment, destroy carbonaceous pollution of industrial effluent (reduction of COD) and also oxidize sulfides and thiophosphates.
- the "activated sludge" reactor is supplied with air or pure oxygen, thus allowing the aeration of the medium.
- the pH of the medium must be as stable as possible and as close as possible to neutrality, see slightly basic. Therefore, although the effluent to be treated generally constitutes only a small part of the diet of the biological station, it is necessary to avoid a free soda content of this effluent that is too high.
- the effluent After passing through the reactor, the effluent is separated from the sludge which consists of microorganisms and bacteria, in a clarifier before discharge.
- the decanted sludge is largely recycled in the reactor, part of the decanted sludge is sent to a thickener where the maximum amount of water is extracted.
- the water is recycled to the reactor while the sludge is eliminated in a landfill.
- the advantage of the process according to the present invention is to eliminate the waste in the form of aqueous effluents essentially consisting 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 H2S.
- 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 made up of Na2S). 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 made up of Na2S
- Activated sludge consists of microorganisms and bacteria evolving in an aerobic environment.
- the aeration 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.
- Soluble phosphates are analyzed regularly during biological oxidation operations and 15 days after the treatment of the last effluent (No. 8) in the discharges (11) from the biological station.
- J denotes the duration of the operations in days
- the asterisks correspond to the injections of the effluents to be treated
- the line carrying black squares designates the total phosphates
- the line carrying white squares designates the soluble phosphates.
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)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94931626A EP0684859B1 (fr) | 1993-10-22 | 1994-10-24 | Procede d'elimination des dechets du p4s10 |
DE69412070T DE69412070T2 (de) | 1993-10-22 | 1994-10-24 | Verfahren zur entsorgung von abfällen von p4s10 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9312633A FR2711558B1 (fr) | 1993-10-22 | 1993-10-22 | Procédé d'élimination des déchets du P4S10. |
FR93/12633 | 1993-10-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995011061A1 true WO1995011061A1 (fr) | 1995-04-27 |
Family
ID=9452133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1994/001236 WO1995011061A1 (fr) | 1993-10-22 | 1994-10-24 | Procede d'elimination des dechets du p4s¿10? |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0684859B1 (fr) |
DE (1) | DE69412070T2 (fr) |
FR (1) | FR2711558B1 (fr) |
WO (1) | WO1995011061A1 (fr) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2294987A1 (fr) * | 1974-12-18 | 1976-07-16 | University Patents Inc | Elimination biologique du phosphore d'eaux residuaires |
US4301014A (en) * | 1980-06-05 | 1981-11-17 | Hooker Chemicals & Plastics Corp. | Phosphorus pentasulfide waste water treatment |
EP0408878A1 (fr) * | 1989-07-21 | 1991-01-23 | Biospherics Incorporated | Elimination de phosphates perfectionnée pour le traitement d'eau usÀ©es à boues activées |
-
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 DE DE69412070T patent/DE69412070T2/de not_active Expired - Fee Related
- 1994-10-24 WO PCT/FR1994/001236 patent/WO1995011061A1/fr active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2294987A1 (fr) * | 1974-12-18 | 1976-07-16 | University Patents Inc | Elimination biologique du phosphore d'eaux residuaires |
US4301014A (en) * | 1980-06-05 | 1981-11-17 | Hooker Chemicals & Plastics Corp. | Phosphorus pentasulfide waste water treatment |
EP0408878A1 (fr) * | 1989-07-21 | 1991-01-23 | Biospherics Incorporated | Elimination de phosphates perfectionnée pour le traitement d'eau usÀ©es à boues activées |
Also Published As
Publication number | Publication date |
---|---|
FR2711558B1 (fr) | 1996-01-05 |
EP0684859A1 (fr) | 1995-12-06 |
EP0684859B1 (fr) | 1998-07-29 |
FR2711558A1 (fr) | 1995-05-05 |
DE69412070T2 (de) | 1999-04-15 |
DE69412070D1 (de) | 1998-09-03 |
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