WO1996000696A1 - Procede et installation de recuperation du brome dans un effluent liquide - Google Patents
Procede et installation de recuperation du brome dans un effluent liquide Download PDFInfo
- Publication number
- WO1996000696A1 WO1996000696A1 PCT/FR1995/000861 FR9500861W WO9600696A1 WO 1996000696 A1 WO1996000696 A1 WO 1996000696A1 FR 9500861 W FR9500861 W FR 9500861W WO 9600696 A1 WO9600696 A1 WO 9600696A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bromine
- liquid
- water
- distillation
- hetero
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
Definitions
- the invention relates to a method and an installation for recovering bromine in a liquid effluent.
- the subject of the invention is a method and an installation for incinerating liquid effluents containing bromine, this method and this installation being such that they make it possible to recover practically pure and directly reusable bromine, that they require an investment capable of to be amortized quickly, and that they produce only relatively small amounts of secondary waste.
- it proposes a process for recovering bromine contained in a liquid effluent, characterized in that it is carried out under pressure and consists in: incinerating the liquid effluent using pure oxygen as oxidant, - cooling the gases combustion by dilution with water,
- the invention also provides an installation for recovering bromine in a liquid effluent, characterized in that it is designed to operate under pressure and in that it comprises:
- means for hetero-azeotropic distillation of the cooled combustion gases comprising at least one distillation column associated with means for condensing the gaseous mixture leaving this column and with means for separating bromine by decantation at a determined temperature of the condensed mixture , and a second distillation column, which is supplied by the "bromine" outlet of the separation means by decantation and which supplies substantially pure bromine and a gas mixture returned to the abovementioned condensation means.
- Such an installation is designed to operate under a pressure of 5 to 20 bars, preferably 8 to 10 bars, and can therefore be compact.
- This installation essentially comprises a combustion chamber 10 under pressure of a liquid effluent 12 with a high bromine content (for example of the order of 50% by weight) which is fed continuously to the combustion chamber 10 with a continuous flow. 14 of oxygen under pressure serving as oxidizer. A supply 16 of a fuel such as fuel oil is provided for the start of the installation.
- the internal pressure in the combustion chamber and in the rest of the installation is preferably of the order of 8 to 10 bars, the combustion temperature of the liquid effluent being between 2,000 and 2,500 K degrees to obtain very quickly thermodynamic equilibrium at the end of combustion and being able to contain the reacting gases in a small chamber.
- a flow 18 of water in liquid phase at ambient temperature is brought inside the combustion chamber 10 to cool the walls of the latter. A small part of this water flow is used to maintain the gases at the desired temperature of 2,000 to 2,500 ° K. Most of the water is injected very quickly at the entry of a maturation chamber 20, arranged immediately downstream of the combustion chamber 10, to bring the gases to a temperature of the order of 430 ° C., without modifying their chemical composition at the end of combustion at high temperature (2,000 to 2,500 'K).
- a temperature of 400 to 600 ° C and a residence time in the chamber 20 of the order of 0.1 to 10 s at a pressure of 5 to 20 bars are conditions that maximize the formation of bromine (Br2) at the expense of bromine hydride (HBr) and thus increase the bromine recovery yield.
- the values of 400 to 450 ° C., 0.5 to 2 s and 8 to 10 bars will be chosen, which allow more than 80% conversion of bromine to Br2 (diatomic bromine) to be achieved.
- the maturation chamber 20 is followed by a gas-solid separator 22, constituted for example by ceramic dedusting filters, making it possible to separate the gases and the combustion ashes.
- the temperature inside the separator 22 is identical to that of the chamber 20.
- the gases leaving the separator 22 are then brought to a heat exchanger 24, of the water circulation type, where they are cooled to a temperature of the order of 180 to 220 degrees C.
- a heat exchanger 24 of the water circulation type, where they are cooled to a temperature of the order of 180 to 220 degrees C.
- Another possibility is to replace the elements 22 and 24 by a chamber 23 for dilution by a water flow 25 which will bring the gases to the same temperature from 180 ° to 220 ° C.
- This temperature preferably 200 ° C. at 10 bars, is chosen to limit the problems of corrosion by acidic liquids in hetero-azeotropic distillation while remaining above the dew point of the water-bromine mixture at the inlet of the distillation means.
- the outlet of the exchanger 24 or of the chamber 23 is connected to an inlet of a hetero-azeotropic distillation column 26, an upper outlet 28 of which makes it possible to obtain an azeotropic water-bromine mixture in phase gazeuze and a lower outlet 30 of which is connected on the one hand to an inlet of the combustion chamber 10 or of the maturation chamber 20 for recycling part of the liquid distillation residues and on the other hand to an inlet 32 of the column 26 by means of a boiler 34 comprising heating means, not shown, for example of the electric type.
- the recycling of the liquid residues to the chamber 10 or the chamber 20 makes it possible to re-transform part of the bromine hydride contained in the liquid into bromine and therefore to increase overall the recovery rate of the bromine.
- the outlet 28 of the distillation column 26 is connected to condensing means comprising two condensers 36 and 38 connected in series, the first of which is supplied with water at room temperature and the second of which is supplied with glycol water or the like at a temperature less than zero degrees C, for example from -20 degrees C approximately.
- the outlet of the second condenser 38 is connected to a settling tank 40 in which the bromine is separated from the water by demixing at a temperature of the order of 5 degrees C, the settling tank containing an upper layer 42 of a light liquid consisting essentially of water with traces of bromine, and a lower layer 44 of a heavy liquid consisting essentially of bromine with traces of water.
- the temperature of 5 ° C. and the pressure level of 8 to 10 bars are chosen so as to maximize the bromine condensation and to favor the appearance by demixing of a phase very rich in bromine which it will be easy to purify by distillation to reach at least 99.9% purity.
- the lower part of the settling tank 40 is connected to an inlet 46 of a second distillation column 48, an upper outlet 50 of which is connected with the upper outlet 28 of the first column 26 to the inlet of the first condenser 36 and of which a lower outlet 52 is connected to a boiler 54, a lower outlet 56 of which provides pure bromine in the liquid phase and an outlet 58 of which is connected to a lower inlet 60 of the column 48.
- This installation also includes means for treating and eliminating secondary waste resulting from the recovery of bromine in the liquid effluent 12.
- These means comprise columns 62 of absorption of activated carbon, which are installed in parallel and fed by a gas outlet 64 of the settling tank 40, the ' outlets of the columns d absorption 62 being connected by a pressure reducer 66 to gas rejection means.
- the boiler 34 of the first distillation column 26 comprises a "liquid" outlet 68 which is connected to a neutralization chamber 70 supplied with soda or other basic product from a tank 72, the outlet from the chamber 70 being connected to a regulator 74 comprising a "gas” outlet 76 and a "liquid” outlet 78.
- the settling tank 40 comprises an intermediate outlet 80 connected to the distillation column 26 for re-injecting therein the liquid of the layer 42, consisting essentially of water with traces of bromine.
- a flow rate of liquid 12 highly charged with bromine for example of the order of 100 kg / h, is brought under a pressure of 8 to 10 bars and at ambient temperature in the combustion chamber 10, with a flow of pure oxygen of the order of 110 kg / h under a pressure of 8 to 10 bars at room temperature to be burned at a temperature of the order of 2,000 to 2,500 ° K, the combustion gases being diluted and cooled to a temperature of the order of 430 degrees C by mixing with the injected and vaporized water in the combustion chamber 10 and the dilution chamber 20.
- the combustion gases are separated from the ashes in the separator 22, then cooled to a temperature of the order of 200 degrees C by one exchanger 24, this temperature of 200 degrees C being higher than the vaporization temperature of the water under a pressure of 10 bars.
- the gases are cooled by dilution with water in chamber 23, the ashes being recovered at the bottom of column 26 by solid / liquid separation on outlet 30.
- the gas mixture supplied to the first column of distillation 26 comprises an azeotropic water-bromine mixture, which has the same composition in liquid phase and in vapor phase and the constituents of which cannot be separated by distillation.
- the distillation of the combustion gases in the active column therefore makes it possible to recover, at the upper outlet 28 of the column, a water-bromine mixture in the vapor phase and, at the outlet 30 of the column, a liquid consisting in particular of water and hydrobromic acid which is partly returned to the combustion chamber 10 and partly supplied to the boiler 34 one outlet of which supplies the distillation column 26 and another outlet of which supplies the chamber 70 where the acidic liquid is neutralized by sodium hydroxide , before being brought back to atmospheric pressure by the regulator 74 producing steam and a liquid subsequently treated by purification means.
- the water-bromine mixture in the vapor phase obtained at the outlet 28 of the first distillation column 26 is condensed by passing through the condensers 36 and 38 and brought to a temperature of the order of 5 degrees C in the settling tank 40, where water and bromine are separated by density difference into an upper layer 42 and a lower layer 44, due to a phenomenon of demixing of bromine and water at the aforementioned temperature of 5 degrees C.
- the lower part of the settling tank 40 essentially contains bromine with traces of water, which is brought to the second distillation column 48 to be purified there by vaporizing the water at a temperature of the order of 100 degrees C. , the pure bromine then passing through the boiler 54 and being recovered at the outlet 56 thereof.
- the steam leaving at 50 from the second distillation column 48 is mixed with the steam leaving at 28 from the first distillation column 26 to be condensed again in the condensing means 36, 38.
- the incondensable gases which are in the upper part of the settling tank 40 are brought to one of the two purification columns 62 (which are used alternately), then the purified gases are expanded at 66 before being discharged to the atmosphere.
- An installation according to the invention having a treatment capacity of 100 kg / h of liquid loaded with bromine, has a small bulk due to its internal operating pressure, the distillation column 26 having for example a diameter of the order of 30 centimeters for a height of 2 meters.
- the components of this installation are made for example of tantalum, glass or enamelled steel which resist bromine well, and are designed for an operating pressure of the order of ten bars.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95924378A EP0715601A1 (fr) | 1994-06-29 | 1995-06-28 | Procede et installation de recuperation du brome dans un effluent liquide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9408002A FR2721919B1 (fr) | 1994-06-29 | 1994-06-29 | Procede et installation de recuperation du brome dans un effluent liquide |
FR94/08002 | 1994-06-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996000696A1 true WO1996000696A1 (fr) | 1996-01-11 |
Family
ID=9464783
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1995/000861 WO1996000696A1 (fr) | 1994-06-29 | 1995-06-28 | Procede et installation de recuperation du brome dans un effluent liquide |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0715601A1 (fr) |
FR (1) | FR2721919B1 (fr) |
IL (1) | IL114298A0 (fr) |
WO (1) | WO1996000696A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6811679B2 (en) | 2003-03-28 | 2004-11-02 | Council Of Scientific & Industrial Research | Process for electrochemical oxidation of bromide to bromine |
US8815050B2 (en) † | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
CN106390683A (zh) * | 2016-08-30 | 2017-02-15 | 天津长芦海晶集团有限公司 | 蒸馏制溴尾气自动控制吸收工艺 |
CN110562925A (zh) * | 2019-09-27 | 2019-12-13 | 金盛海洋科技有限公司 | 一种利用制盐废液提溴的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2536457A (en) * | 1944-08-29 | 1951-01-02 | Distillers Co Yeast Ltd | Recovery of bromine from hydrogen bromide |
US3353916A (en) * | 1966-04-25 | 1967-11-21 | Universal Oil Prod Co | Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide |
DE2136587A1 (de) * | 1971-07-22 | 1973-02-01 | Kali & Salz Ag | Verfahren zur herstellung von hochreinem brom |
FR2283089A1 (fr) * | 1974-08-02 | 1976-03-26 | Ugine Kuhlmann | Procede de fabrication du brome |
EP0516917A2 (fr) * | 1991-06-06 | 1992-12-09 | Praxair Technology, Inc. | Procédé pour la combustion des déchets contenant de l'hydrocarbure halogéné |
-
1994
- 1994-06-29 FR FR9408002A patent/FR2721919B1/fr not_active Expired - Fee Related
-
1995
- 1995-06-23 IL IL11429895A patent/IL114298A0/xx unknown
- 1995-06-28 WO PCT/FR1995/000861 patent/WO1996000696A1/fr not_active Application Discontinuation
- 1995-06-28 EP EP95924378A patent/EP0715601A1/fr not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2536457A (en) * | 1944-08-29 | 1951-01-02 | Distillers Co Yeast Ltd | Recovery of bromine from hydrogen bromide |
US3353916A (en) * | 1966-04-25 | 1967-11-21 | Universal Oil Prod Co | Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide |
DE2136587A1 (de) * | 1971-07-22 | 1973-02-01 | Kali & Salz Ag | Verfahren zur herstellung von hochreinem brom |
FR2283089A1 (fr) * | 1974-08-02 | 1976-03-26 | Ugine Kuhlmann | Procede de fabrication du brome |
EP0516917A2 (fr) * | 1991-06-06 | 1992-12-09 | Praxair Technology, Inc. | Procédé pour la combustion des déchets contenant de l'hydrocarbure halogéné |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6811679B2 (en) | 2003-03-28 | 2004-11-02 | Council Of Scientific & Industrial Research | Process for electrochemical oxidation of bromide to bromine |
US8815050B2 (en) † | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
CN106390683A (zh) * | 2016-08-30 | 2017-02-15 | 天津长芦海晶集团有限公司 | 蒸馏制溴尾气自动控制吸收工艺 |
CN110562925A (zh) * | 2019-09-27 | 2019-12-13 | 金盛海洋科技有限公司 | 一种利用制盐废液提溴的方法 |
CN110562925B (zh) * | 2019-09-27 | 2022-07-22 | 金盛海洋科技有限公司 | 一种利用制盐废液提溴的方法 |
Also Published As
Publication number | Publication date |
---|---|
IL114298A0 (en) | 1995-10-31 |
EP0715601A1 (fr) | 1996-06-12 |
FR2721919A1 (fr) | 1996-01-05 |
FR2721919B1 (fr) | 1996-09-13 |
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