CN104250040A - Concentrated seawater bromine extraction and closed-loop air stripping system and method - Google Patents
Concentrated seawater bromine extraction and closed-loop air stripping system and method Download PDFInfo
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- CN104250040A CN104250040A CN201410246456.6A CN201410246456A CN104250040A CN 104250040 A CN104250040 A CN 104250040A CN 201410246456 A CN201410246456 A CN 201410246456A CN 104250040 A CN104250040 A CN 104250040A
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Abstract
The invention relates to a concentrated seawater treatment system, and especially relates to a concentrated seawater bromine extraction closed-loop stripping system and method. The invention mainly solves the technical problems of low bromine purity, low yield, easiness to cause environmental pollution and severe equipment corrosion in the prior art of seawater bromine extraction. The system includes a concentrated seawater tank (1) for introducing concentrated seawater, the concentrated seawater tank (1) through a circulating pump (2) is connected with a conversion storage tank (3), the conversion storage tank is connected with a bromine simple substance transforming agent tank (4) through a medicament pipe, the conversion storage tank is connected with a stripping tower (6) through a stripping liquid feed pump (5), the stripping tower is connected with an absorption tower (8) through a stripping pipeline (7), the upper end of the absorption tower is communicated with the bottom of the stripping tower through a closed loop pipeline (9) and a stripping fan (10), the stripping tower and the absorption tower is connected with a bromine simple substance extraction pool (12) through a conveying pipeline (11).
Description
Technical field
The present invention relates to a kind of concentrated seawater treatment system, especially relate to a kind of concentrated seawater and put forward bromine closed loop blow-removing system and method.
Background technology
Bromine and bromine product have important application in Economic development, bromine is widely used in the industries such as agricultural chemicals, medicine, oil, fuel, be the basic chemical raw materials producing fire retardant, fire-fighting medium and sensitive materials, the miscellaneous inorganic bromide be derived by it, bromate and brominated organic compound have special important value in national economy and development in science and technology.On the earth, the bromine of about 99% is present in seawater, and in seawater, brominated about 65mg/L, belongs to the trace element that abundance is larger.Supply falls short of demand for existing domestic old-fashioned production bromine, and therefore to carry bromine day by day urgent for seawater.The bromine resource of China is mainly distributed in the coastal region in east China, and seawater is carried bromine and produced starting material and generally take from the concentrated seawater produced in concentrated seawater in the process of evaporating brine or desalting process.Chinese patent discloses a kind of method (publication number: CN 102583240 A) utilizing alkaline waste heat concentrated seawater to carry bromine, evaporate brine, it utilizes the Lowlevel thermal energy waste heat produced in soda manufacture carbonation process process to heat circulating seawer, after obtain dense bittern through multistage evaporation is concentrated, then bromine being carried to dense bittern, finally evaporating brine carrying the dense bittern after bromine; Multistage evaporation be four to Pyatyi evaporation; Dense bittern is 14 ~ 15.The dense bittern of Be.But the bromine purity that this method proposes is not high, and output is lower, and easily causes environmental pollution, and equipment corrosion is also comparatively serious.
Summary of the invention
The present invention is to provide a kind of concentrated seawater and puies forward bromine closed loop blow-removing system and method, its bromine purity mainly solving the seawater method for extracting bromine proposition existing for prior art is not high, output is lower, and easily causes environmental pollution, and equipment corrosion is the comparatively serious technical problem waited also.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of concentrated seawater of the present invention carries bromine closed loop blow-removing system, comprise the concentrated seawater basin that can pass into concentrated seawater, described concentrated seawater storage tank connects conversion basin by recycle pump, transform basin and be connected with bromine simple substance transforming agent tank by medicament pipe, transform basin and be connected with stripping tower by stripping liquid feeding pump, stripping tower is connected with absorption tower by stripping pipeline, upper end, absorption tower is communicated with the bottom of stripping tower by closed loop pipeline, stripping blower fan, and stripping tower, absorption tower connect bromine simple substance abstraction pool by transfer line.
Stripping tower, absorption tower are the nucleus equipments in whole set process method, basic functional principle: in stripping tower, gas-liquid two-phase is in counter current contact process, and solute constantly will transfer to gas phase by liquid phase, thus reach the object of separation and concentration, and carrier gas used is air; Absorption tower absorption process is just in time contrary, and solute is transferred in the middle of liquid phase from gas phase, and absorb and assemble, absorption liquid generally adopts tetracol phenixin or tetrabromoethane etc.
Solvent-extracted ultimate principle is according to the similar intermiscibility of solute to solvent, and bromine solubleness is in organic solvent large, bromine is entered the extracting and separating such as organic solvent gathering and water.
As preferably, described stripping tower and the bottom on absorption tower, by pipeline connection, this pipeline are connected with recycle pump, stripping adjust liquid pump.
As preferably, described bromine simple substance abstraction pool connects tetracol phenixin by pipeline and adds tank.
As preferably, described conversion basin, bromine simple substance transforming agent tank, stripping tower, absorption tower are all that glass reinforced plastic is made.Bromine is strong oxidizer, and the strong skin ambustion of energy, has aggressive to metal, and present device adopts glass steel material to process preparation without exception, solves the etching problem of equipment in production.
A kind of concentrated seawater puies forward bromine closed loop stripping method, and described method comprises:
A. the concentrated seawater in be produced is passed into transform in basin and carries out acidifying oxidation, bromine simple substance transforming agent tank passes into bromine simple substance transforming agent, make the brominated scope control of concentrated seawater Br-: 50-350mg/L, add the acid waste water after hydrochloric acid and extracting and separating and carry out concentrated seawater acidifying, add oxychlorination according to concentrated seawater amount, pH value controls at 2-5.5, and joining chlorine rate is 100%-150% simultaneously, in concentrated seawater, bromide anion oxidation generates free bromine, and bromine transformation efficiency is 80%-95%;
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower by stripping liquid feeding pump through pipeline, utilize high atomization shower nozzle to carry out atomizing spray; Stripping tower inside subject component is provided with from top to bottom: mist eliminator, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 1-4 overlap according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to the dissociating power of bromine in water, kinetic energy consumption, heat energy consumption, and stripping temperature is 0 DEG C-80 DEG C; Stripping vapour-liquid ratio causes system pressure drop to increase impact according to running cost and vapour-liquid ratio increase, and vapour-liquid ratio is 50-200:1, free bromine blowout rate more than 90%;
C. concentrated seawater atomized fine particle is in the interval of stripping tower filler, through the air of stripping blower fan, free bromine accelerates dissociation release, bromine enters absorption tower with air through mist eliminator, absorption tower inside subject component is from top to bottom: mist eliminator, extraction agent atomizer, absorption tower filler, packing support, redistributor etc., stripping tower filler, packing support and redistributor are according to extraction agent spray flux, bromine dissolution rate is set to 1-3 cover, extraction agent spray flux is 1-5 times of bromine, the water smoke formed in the steam carried secretly of part and stripping in mist eliminator air-isolation, bromine water amount is obviously reduced, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing,
D. enter bottom, absorption tower through stripping pipeline containing bromine stripping air, the spray of counter current contact extraction agent from bottom to top from absorption tower, solvent is in extraction agent, and the dissolution rate of bromine in extraction agent reaches more than 98%;
E. the extraction agent dissolving bromine bottom absorption tower enters bromine simple substance abstraction pool, by standing, layering, separation, acid waste water delivers to recycle in concentrated seawater acidification technique with recycle pump, and the extraction liquid after separation carries out being separated, refining again, obtains the product bromine of high-quality.
The present invention utilizes concentrated seawater air stripping, organic solvent spray-absorption, extraction, refining, and tail gas closed loop cycle bromine technology, comprises acidifying oxidation, air stripping, organic solvent spray-absorption, extraction, tail gas closed loop cycle five steps.
1. concentrated seawater is carried in bromine and must first be calculated before oxidation, adds hydrochloric acid or sulfuric acid, and the waste water after extracting and separating of the present invention, in acid, carrys out acidifying concentrated seawater as raw material, recycle, energy-conserving and environment-protective;
2. the liquid fine particle that traditional atomizer is formed affects because of factors such as spray angle, gravity, inertia, sprays uneven, adopts Dynawave nozzle principle to solve in design;
3. stripping fan delivery is large, wind speed anxious, and air rises uneven in tower, and design air sparger solves;
4. temperature difference fluctuation or stripping run in tower temperature rise, free bromine blowout rate fluctuates, and designs automatic temperature-controlledly to be combined with stripping liquid feeding pump, control liquid inlet volume;
5. adopt glass reinforced plastic two dimension winding technology, Whole Equipment once shaped, intensity is large, more withstand voltage, anticorrosion;
As preferably, in described step a concentrated seawater brominated scope control Br-: 100-250mg/L, pH value controls at 2.5-4.0, and joining chlorine rate is 110-130%.
As preferably, in described step b, stripping temperature is 20 DEG C-40 DEG C, and vapour-liquid ratio is 100-120:1, and stripping tower filler, packing support and redistributor are set to 1-2 and overlap.
As preferably, in described step c, stripping tower filler, packing support and redistributor are set to 1-2 and overlap, extraction agent spray flux be the 1.5-3 of bromine doubly.
Therefore, the concentration and separation that the present invention adopts in stripping tower, absorption tower, gathering separation method, significantly reduce costs, obtain making full use of of resource, the closed loop cycle of tail gas utilizes, and avoids the environmental pollution in production technique, and in lectotype selection, considers the strong oxidizing property of bromine, the aggressive to hardware, same employing glass reinforced plastic equipment, solves the equipment corrosion problem in production.
Accompanying drawing explanation
Accompanying drawing 1 is a kind of structural representation of the present invention.
Component, position and numbering in figure: concentrated seawater basin 1, recycle pump 2, conversion basin 3, bromine simple substance transforming agent tank 4, stripping liquid feeding pump 5, stripping tower 6, stripping pipeline 7, absorption tower 8, closed loop pipeline 9, stripping blower fan 10, transfer line 11, bromine simple substance abstraction pool 12, recycle pump 13, stripping adjust liquid pump 14, tetracol phenixin to add tank 15.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment: a kind of concentrated seawater of this example carries bromine closed loop blow-removing system, as Fig. 1, comprise the concentrated seawater basin 1 that can pass into concentrated seawater, concentrated seawater storage tank connects conversion basin 3 by recycle pump 2, transform basin and be connected with bromine simple substance transforming agent tank 4 by medicament pipe, transform basin and be connected with stripping tower 6 by stripping liquid feeding pump 5, stripping tower is connected with absorption tower 8 by stripping pipeline 7, upper end, absorption tower is communicated with the bottom of stripping tower by closed loop pipeline 9, stripping blower fan 10, and stripping tower, absorption tower connect bromine simple substance abstraction pool 12 by transfer line 11.The bottom on stripping tower and absorption tower, by pipeline connection, this pipeline is connected with recycle pump 13, stripping adjusts liquid pump 14.Bromine simple substance abstraction pool connects tetracol phenixin by pipeline and adds tank 15.Conversion basin, bromine simple substance transforming agent tank, stripping tower, absorption tower are all that glass reinforced plastic is made.
A kind of concentrated seawater puies forward bromine closed loop stripping method, and step is:
A. the concentrated seawater in be produced is passed into transform in basin 3 and carries out acidifying oxidation, bromine simple substance transforming agent tank 4 passes into bromine simple substance transforming agent, make the brominated scope control of concentrated seawater Br-: 150mg/L, add the acid waste water after hydrochloric acid and extracting and separating and carry out concentrated seawater acidifying, add oxychlorination according to concentrated seawater amount, pH value controls 3, and joining chlorine rate is 120% simultaneously, in concentrated seawater, bromide anion oxidation generates free bromine, and bromine transformation efficiency is 80%-95%;
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower 6 by stripping liquid feeding pump 5 through pipeline, utilize high atomization shower nozzle to carry out atomizing spray; Stripping tower inside subject component is provided with from top to bottom: mist eliminator, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 2 covers according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to the dissociating power of bromine in water, kinetic energy consumption, heat energy consumption, and stripping temperature is 30 DEG C; Stripping vapour-liquid ratio causes system pressure drop to increase impact according to running cost and vapour-liquid ratio increase, and vapour-liquid ratio is 110:1, free bromine blowout rate more than 90%;
C. concentrated seawater atomized fine particle is in the interval of stripping tower filler, through the air of stripping blower fan 10, free bromine accelerates dissociation release, bromine enters absorption tower 8 with air through mist eliminator, absorption tower inside subject component is from top to bottom: mist eliminator, extraction agent atomizer, absorption tower filler, packing support, redistributor etc., stripping tower filler, packing support and redistributor are according to extraction agent spray flux, bromine dissolution rate is set to 2 covers, extraction agent spray flux is 2 times of bromine, the water smoke formed in the steam carried secretly of part and stripping in mist eliminator air-isolation, bromine water amount is obviously reduced, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing,
D. enter bottom, absorption tower 8 through stripping pipeline 7 containing bromine stripping air, the spray of counter current contact extraction agent from bottom to top from absorption tower, solvent is in extraction agent, and the dissolution rate of bromine in extraction agent reaches more than 98%;
E. the extraction agent dissolving bromine bottom absorption tower 8 enters bromine simple substance abstraction pool 12, by standing, layering, separation, acid waste water delivers to recycle in concentrated seawater acidification technique with recycle pump 13, and the extraction liquid after separation carries out being separated, refining again, obtains the product bromine of high-quality.
The foregoing is only specific embodiments of the invention, but constitutional features of the present invention is not limited thereto, any those skilled in the art is in the field of the invention, and the change done or modification are all encompassed among the scope of the claims of the present invention.
Claims (8)
1. a concentrated seawater carries bromine closed loop blow-removing system, comprise the concentrated seawater basin (1) that can pass into concentrated seawater, it is characterized in that described concentrated seawater storage tank (1) is connected by recycle pump (2) and transform basin (3), transform basin and be connected with bromine simple substance transforming agent tank (4) by medicament pipe, transform basin and be connected with stripping tower (6) by stripping liquid feeding pump (5), stripping tower is connected with absorption tower (8) by stripping pipeline (7), upper end, absorption tower is by closed loop pipeline (9), stripping blower fan (10) is communicated with the bottom of stripping tower, stripping tower, absorption tower connects bromine simple substance abstraction pool (12) by transfer line (11).
2. a kind of concentrated seawater according to claim 1 carries bromine closed loop blow-removing system, it is characterized in that described stripping tower (6) passes through pipeline connection with the bottom on absorption tower (8), this pipeline is connected with recycle pump (13), stripping adjusts liquid pump (14).
3. a kind of concentrated seawater according to claim 1 and 2 carries bromine closed loop blow-removing system, it is characterized in that described bromine simple substance abstraction pool (12) connects tetracol phenixin by pipeline and adds tank (15).
4. a kind of concentrated seawater according to claim 1 and 2 carries bromine closed loop blow-removing system, it is characterized in that described conversion basin (3), bromine simple substance transforming agent tank (4), stripping tower (6), absorption tower (8) be all that glass reinforced plastic is made.
5. concentrated seawater puies forward a bromine closed loop stripping method, it is characterized in that described method comprises:
A. the concentrated seawater in be produced is passed into transform in basin (3) and carries out acidifying oxidation, bromine simple substance transforming agent tank (4) passes into bromine simple substance transforming agent, make the brominated scope control of concentrated seawater Br-: 50-350mg/L, add the acid waste water after hydrochloric acid and extracting and separating and carry out concentrated seawater acidifying, add oxychlorination according to concentrated seawater amount, pH value controls at 2-5.5, and joining chlorine rate is 100%-150% simultaneously, in concentrated seawater, bromide anion oxidation generates free bromine, and bromine transformation efficiency is 80%-95%;
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower (6) by stripping liquid feeding pump (5) through pipeline, utilize high atomization shower nozzle to carry out atomizing spray; Stripping tower inside subject component is provided with from top to bottom: mist eliminator, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 1-4 overlap according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to the dissociating power of bromine in water, kinetic energy consumption, heat energy consumption, and stripping temperature is 0 DEG C-80 DEG C; Stripping vapour-liquid ratio causes system pressure drop to increase impact according to running cost and vapour-liquid ratio increase, and vapour-liquid ratio is 50-200:1, free bromine blowout rate more than 90%;
C. concentrated seawater atomized fine particle is in the interval of stripping tower filler, through the air of stripping blower fan (10), free bromine accelerates dissociation release, bromine enters absorption tower (8) with air through mist eliminator, absorption tower inside subject component is from top to bottom: mist eliminator, extraction agent atomizer, absorption tower filler, packing support, redistributor etc., stripping tower filler, packing support and redistributor are according to extraction agent spray flux, bromine dissolution rate is set to 1-3 cover, extraction agent spray flux is 1-5 times of bromine, the water smoke formed in the steam carried secretly of part and stripping in mist eliminator air-isolation, bromine water amount is obviously reduced, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing,
D. enter absorption tower (8) bottom through stripping pipeline (7) containing bromine stripping air, the spray of counter current contact extraction agent from bottom to top from absorption tower, solvent is in extraction agent, and the dissolution rate of bromine in extraction agent reaches more than 98%;
E. the extraction agent of absorption tower (8) bottom dissolving bromine enters bromine simple substance abstraction pool (12), by standing, layering, separation, acid waste water delivers to recycle in concentrated seawater acidification technique with recycle pump (13), extraction liquid after separation carries out being separated, refining again, obtains the product bromine of high-quality.
6. a kind of concentrated seawater according to claim 5 puies forward bromine closed loop stripping method, it is characterized in that the brominated scope control of concentrated seawater in described step a Br-: 100-250mg/L, pH value controls at 2.5-4.0, and joining chlorine rate is 110-130%.
7. a kind of concentrated seawater according to claim 5 puies forward bromine closed loop stripping method, and it is characterized in that in described step b, stripping temperature is 20 DEG C-40 DEG C, vapour-liquid ratio is 100-120:1, and stripping tower filler, packing support and redistributor are set to 1-2 and overlap.
8. a kind of concentrated seawater according to claim 5 puies forward bromine closed loop stripping method, to it is characterized in that in described step c that stripping tower filler, packing support and redistributor are set to 1-2 and overlaps, extraction agent spray flux be the 1.5-3 of bromine doubly.
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| CN203938541U (en) * | 2014-06-05 | 2014-11-12 | 浙江南化防腐设备有限公司 | A kind of concentrated seawater is carried bromine closed loop blow-removing system |
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2014
- 2014-06-05 CN CN201410246456.6A patent/CN104250040B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2663092A (en) * | 1991-09-16 | 1993-04-27 | Catalytica, Inc. | Process and catalyst for producing bromine |
| US20050135990A1 (en) * | 2002-10-07 | 2005-06-23 | Schaefer Jared J. | Conversion of sodium bromide to anhydrous hydrobromic acid and sodium bisulfate |
| CN101045529A (en) * | 2007-04-24 | 2007-10-03 | 天津长芦海晶集团有限公司 | Technology process for producing bromide using concentrated seawater |
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