CN104250040B - A kind of concentrated seawater puies forward bromine closed loop blow-removing system and method - Google Patents
A kind of concentrated seawater puies forward bromine closed loop blow-removing system and method Download PDFInfo
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- CN104250040B CN104250040B CN201410246456.6A CN201410246456A CN104250040B CN 104250040 B CN104250040 B CN 104250040B CN 201410246456 A CN201410246456 A CN 201410246456A CN 104250040 B CN104250040 B CN 104250040B
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Abstract
The present invention relates to a kind of concentrated seawater processing system, especially relate to a kind of concentrated seawater and put forward bromine closed loop blow-removing system and method.Its bromine purity that mainly solution sea water method for extracting bromine existing for prior art proposes is the highest, and yield is relatively low, and easily causes environmental pollution, the most serious technical problem waited of equipment corrosion.The present invention includes the concentrated seawater basin (1) that can be passed through concentrated seawater, described concentrated seawater storage tank (1) connects conversion basin (3) by circulating pump (2), convert basin and have bromine simple substance transforming agent tank (4) by the connection of medicament pipe, convert basin and have stripping tower (6) by stripping liquid feeding pump (5) connection, stripping tower is connected by stripping pipeline (7) absorption tower (8), upper end, absorption tower is by closed loop pipeline (9), the bottom of stripping blower fan (10) connection stripping tower, and stripping tower, absorption tower connect bromine simple substance abstraction pool (12) by transfer pipeline (11).
Description
Technical field
The present invention relates to a kind of concentrated seawater processing 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 pesticide, medicine, oil, fuel, be to produce fire retardant, extinguishing chemical and the basic chemical raw materials of sensitive material, it the miscellaneous inorganic bromide being derived, 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 sea water, and in sea water, brominated about 65mg/L, belongs to the trace element that abundance is bigger.Supply falls short of demand for existing domestic old-fashioned production bromine, and therefore to carry bromine the most urgent for sea water.The bromine resource of China is mainly distributed on the coastal region in east China, and sea water carries bromine production raw material and typically takes from the concentrated seawater produced in the concentrated seawater during 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, circulating seawer is heated by its Lowlevel thermal energy waste heat produced during utilizing soda manufacture carbonation process, after be concentrated to give dense salt through multistage evaporation, then dense salt being carried bromine, the dense salt after finally carrying bromine is evaporated brine；Multistage evaporation be four to Pyatyi evaporate；Dense salt is 14～15.The dense salt of Be.But the bromine purity that this method proposes is the highest, and yield is relatively low, and easily causes environmental pollution, and equipment corrosion is the most 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 that mainly solution sea water method for extracting bromine existing for prior art proposes is the highest, yield is relatively low, and easily causes environmental pollution, the most serious technical problem waited of equipment corrosion.
The above-mentioned technical problem of the present invention is mainly addressed by following technical proposals:
A kind of concentrated seawater of the present invention carries bromine closed loop blow-removing system, including the concentrated seawater basin that can be passed through concentrated seawater, described concentrated seawater storage tank connects conversion basin by circulating pump, convert basin and have bromine simple substance transforming agent tank by the connection of medicament pipe, convert basin and have stripping tower by the connection of stripping liquid feeding pump, stripping tower is connected by stripping pipeline absorption tower, upper end, absorption tower is by closed loop pipeline, the bottom of stripping blower fan connection stripping tower, and stripping tower, absorption tower connect bromine simple substance abstraction pool by transfer pipeline.
Stripping tower, absorption tower are the nucleus equipments in whole set process method, basic functional principle: in stripping tower, gas-liquid two-phase is during counter current contacting, and solute constantly will be transferred to gas phase by liquid phase, thus reaches the purpose of separation and concentration, and carrier gas used is air；Absorption tower absorption process contrast, solute is transferred in the middle of liquid phase from gas phase, absorbs and assembles, and absorbing liquid typically uses carbon tetrachloride or tetrabromoethane etc..
Solvent-extracted ultimate principle is the similar intermiscibility according to solute to solvent, and bromine dissolubility in organic solvent is big, and bromine enters the extract and separate such as organic solvent gathering and water.
As preferably, described stripping tower passes through pipeline connection with the bottom on absorption tower, this pipeline connects and has circulating pump, stripping to adjust liquid pump.
As preferably, described bromine simple substance abstraction pool connects carbon tetrachloride by pipeline and adds tank.
As preferably, described conversion basin, bromine simple substance transforming agent tank, stripping tower, absorption tower are all that fiberglass is made.Bromine is strong oxidizer, the strong skin ambustion of energy, has aggressive to metal, and present device uses glass steel material processing 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 includes:
A. the concentrated seawater in be produced is passed in conversion basin and carries out acidifying oxidation, bromine simple substance transforming agent tank is passed through bromine simple substance transforming agent, make the brominated scope control of concentrated seawater at Br: 50-350mg/L, add the acid waste water after hydrochloric acid and extract and separate and carry out concentrated seawater acidifying, adding oxychloride according to concentrated seawater amount, pH value controls at 2-5.5, and joining chlorine rate is 100%-150% simultaneously, in concentrated seawater, bromide ion oxidation generates free bromine, and bromine conversion ratio is 80%-95%；
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower through pipeline by stripping liquid feeding pump, utilizes high atomization shower nozzle to carry out atomizing spray；Stripping tower inside subject component is provided with from top to bottom: demister, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 1-4 set according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to bromine dissociating power in water, kinetic energy consumption, thermal energy consumption, and stripping temperature is 0 DEG C-80 DEG C；Stripping gas liquid ratio causes system pressure drop to increase impact according to running cost and gas liquid ratio increase, and gas 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, air through stripping blower fan, free bromine accelerates dissociation release, bromine enters absorption tower with air through demister, absorption tower inside subject component is from top to bottom: demister, extractant atomizer, absorption tower filler, packing support, redistributor etc., stripping tower filler, packing support and redistributor are according to extractant spray flux, bromine rate of dissolution is set to 1-3 set, extractant spray flux is 1-5 times of bromine, the water smoke formed in the steam partly carried secretly in demister air-isolation and stripping, bromine water amount is made to significantly reduce, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing；
D. entering bottom, absorption tower containing bromine stripping air through stripping pipeline, the spray of counter current contacting extractant from bottom to top from absorption tower, solvent is in extractant, and bromine dissolution rate in extractant reaches more than 98%；
E. the extractant dissolving bromine bottom absorption tower enters bromine simple substance abstraction pool, by standing, be layered, separating, acid waste water is delivered to recycle in concentrated seawater acidification technique with circulating pump, and the extract after separation carries out separating, refining again, obtains the product bromine of high-quality.
The present invention utilizes concentrated seawater air stripping, organic solvent spray-absorption, extract, refined, tail gas closed loop cycle bromine technology, including being acidified oxidation, air stripping, organic solvent spray-absorption, extraction, five steps of tail gas closed loop cycle.
1. must first calculate before oxidation during concentrated seawater carries bromine, add hydrochloric acid or sulphuric acid, the waste water after extract and separate of the present invention is acidity, is acidified concentrated seawater as raw material, recycles, energy-conserving and environment-protective；
2. the liquid fine particle that tradition atomizer is formed, because of factor impacts such as spray angle, gravity, inertia, sprays uneven, uses Dynawave nozzle principle to solve in design；
3. stripping fan delivery is big, wind speed anxious, and air rises uneven in tower, and design air distributor solves；
4. during temperature difference fluctuation or stripping run, temperature rises in tower, and free bromine blowout rate fluctuates, and designs and automatic temperature-controlled is combined with stripping liquid feeding pump, control liquid inlet volume；
5. using fiberglass two dimension winding technology, equipment integral one-step molding, intensity is big, more resistant to pressure, anticorrosion；
As preferably, in described step a, the brominated scope control of concentrated seawater is at Br: 100-250mg/L, and 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 gas liquid ratio is 100-120:1, and stripping tower filler, packing support and redistributor are set to 1-2 set.
As preferably, in described step c, stripping tower filler, packing support are set to 1-2 set with redistributor, and extractant spray flux is 1.5-3 times of bromine.
Therefore, concentration and separation that the present invention uses in stripping tower, absorption tower, assemble separation method, cost is greatly reduced, obtain making full use of of resource, the closed loop cycle of tail gas utilizes, it is to avoid the environmental pollution in production technology, and considers the strong oxidizing property of bromine, the aggressive to hardware in lectotype selection, use fiberglass equipment without exception, solve the equipment corrosion problem in production.
Accompanying drawing explanation
Accompanying drawing 1 is a kind of structural representation of the present invention.
Parts, position and numbering in figure: concentrated seawater basin 1, circulating 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 pipeline 11, bromine simple substance abstraction pool 12, circulating pump 13, stripping adjust liquid pump 14, carbon tetrachloride to add tank 15.
Detailed description of the invention
Below by embodiment, and combine accompanying drawing, technical scheme is described in further detail.
Embodiment: a kind of concentrated seawater of this example carries bromine closed loop blow-removing system, such as Fig. 1, including the concentrated seawater basin 1 that can be passed through concentrated seawater, concentrated seawater storage tank connects conversion basin 3 by circulating pump 2, convert basin and have bromine simple substance transforming agent tank 4 by the connection of medicament pipe, convert basin and have stripping tower 6 by stripping liquid feeding pump 5 connection, stripping tower is connected by stripping pipeline 7 absorption tower 8, upper end, absorption tower connects 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 pipeline 11.Stripping tower passes through pipeline connection with the bottom on absorption tower, this pipeline connects and has circulating pump 13, stripping to adjust liquid pump 14.Bromine simple substance abstraction pool connects carbon tetrachloride by pipeline and adds tank 15.Conversion basin, bromine simple substance transforming agent tank, stripping tower, absorption tower are all that fiberglass 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 in conversion basin 3 and carries out acidifying oxidation, bromine simple substance transforming agent tank 4 is passed through bromine simple substance transforming agent, make the brominated scope control of concentrated seawater at Br: 150mg/L, add the acid waste water after hydrochloric acid and extract and separate and carry out concentrated seawater acidifying, adding oxychloride according to concentrated seawater amount, pH value controls 3, and joining chlorine rate is 120% simultaneously, in concentrated seawater, bromide ion oxidation generates free bromine, and bromine conversion ratio is 80%-95%；
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower 6 through pipeline by stripping liquid feeding pump 5, utilizes high atomization shower nozzle to carry out atomizing spray；Stripping tower inside subject component is provided with from top to bottom: demister, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 2 sets according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to bromine dissociating power in water, kinetic energy consumption, thermal energy consumption, and stripping temperature is 30 DEG C；Stripping gas liquid ratio causes system pressure drop to increase impact according to running cost and gas liquid ratio increase, and gas 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, air through stripping blower fan 10, free bromine accelerates dissociation release, bromine enters absorption tower 8 with air through demister, absorption tower inside subject component is from top to bottom: demister, extractant atomizer, absorption tower filler, packing support, redistributor etc., stripping tower filler, packing support and redistributor are according to extractant spray flux, bromine rate of dissolution is set to 2 sets, extractant spray flux is 2 times of bromine, the water smoke formed in the steam partly carried secretly in demister air-isolation and stripping, bromine water amount is made to significantly reduce, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing；
D. entering bottom, absorption tower 8 through stripping pipeline 7 containing bromine stripping air, the spray of counter current contacting extractant from bottom to top from absorption tower, solvent is in extractant, and bromine dissolution rate in extractant reaches more than 98%；
E. the extractant dissolving bromine bottom absorption tower 8 enters bromine simple substance abstraction pool 12, by standing, be layered, separating, acid waste water is delivered to recycle in concentrated seawater acidification technique with circulating pump 13, and the extract after separation carries out separating, refining again, obtains the product bromine of high-quality.
The foregoing is only the specific embodiment of the present invention, but the architectural feature of the present invention is not limited thereto, any those skilled in the art is in the field of the invention, and change or the modification made all are contained among the scope of the claims of the present invention.
Claims (5)
1. a concentrated seawater carries bromine closed loop blow-removing system, including the concentrated seawater basin (1) that can be passed through concentrated seawater, it is characterized in that described concentrated seawater storage tank (1) is connected by circulating pump (2) and convert basin (3), convert basin and have bromine simple substance transforming agent tank (4) by the connection of medicament pipe, convert basin and have stripping tower (6) by stripping liquid feeding pump (5) connection, stripping tower is connected by stripping pipeline (7) absorption tower (8), closed loop pipeline (9) is passed through in upper end, absorption tower, the bottom of stripping blower fan (10) connection stripping tower, stripping tower, absorption tower connects bromine simple substance abstraction pool (12) by transfer pipeline (11), stripping tower (6) passes through pipeline connection with the bottom on absorption tower (8), connect on this pipeline and have circulating pump (13), stripping adjusts liquid pump (14)；The bromine closed loop stripping method that carries utilizing concentrated seawater to carry bromine closed loop blow-removing system includes:
A. the concentrated seawater in be produced is passed in conversion basin (3) and carries out acidifying oxidation, bromine simple substance transforming agent tank (4) is passed through bromine simple substance transforming agent, make the brominated scope control of concentrated seawater at Br: 50-350mg/L, add the acid waste water after hydrochloric acid and extract and separate and carry out concentrated seawater acidifying, add oxychloride according to concentrated seawater amount simultaneously
PH value controls at 2-5.5, and joining chlorine rate is 100%-150%, and in concentrated seawater, bromide ion oxidation generates free bromine, and bromine conversion ratio is 80%-95%；
B. the concentrated seawater after acidifying oxidation is delivered to the top of stripping tower (6) through pipeline by stripping liquid feeding pump (5), utilizes high atomization shower nozzle to carry out atomizing spray；Stripping tower inside subject component is provided with from top to bottom: demister, stripping tower filler, packing support, redistributor, stripping tower filler, packing support and redistributor are set to 1-4 set according to the vapor liquid equilibrium of stripping, gas-liquid stripping ratio, amount of filler, vapor liquid equilibrium is according to bromine dissociating power in water, kinetic energy consumption, thermal energy consumption, stripping temperature is 20 DEG C-40, and the automatic temperature-controlled of stripping is combined with stripping liquid feeding pump；Stripping gas liquid ratio causes system pressure drop to increase impact according to running cost and gas liquid ratio increase, and gas liquid ratio is 100-120:1, free bromine blowout rate more than 90%；
C. concentrated seawater atomized fine particle is in the interval of stripping tower filler, air through stripping blower fan (10), free bromine accelerates dissociation release, bromine enters absorption tower (8) with air through demister, absorption tower inside subject component is from top to bottom: demister, extractant atomizer, absorption tower filler, packing support, redistributor, absorption tower filler, packing support and redistributor are according to extractant spray flux, bromine rate of dissolution is set to 1-3 set, extractant spray flux is 1-5 times of bromine, the water smoke formed in the steam partly carried secretly in demister air-isolation and stripping, bromine water amount is made to significantly reduce, concentrated seawater after separation is discharged outside tower, postorder salt manufacturing；
D. entering absorption tower (8) bottom containing bromine stripping air through stripping pipeline (7), the spray of counter current contacting extractant from bottom to top from absorption tower, solvent is in extractant, and bromine dissolution rate in extractant reaches more than 98%；
E. the extractant of absorption tower (8) bottom dissolving bromine enters bromine simple substance abstraction pool (12), by standing, be layered, separating, acid waste water is delivered to recycle in concentrated seawater acidification technique with circulating pump (13), and the extract after separation carries out separating, refining again, obtains the product bromine of high-quality.
A kind of concentrated seawater the most according to claim 1 carries bromine closed loop blow-removing system, it is characterised in that described bromine simple substance abstraction pool (12) connects carbon tetrachloride by pipeline and adds tank (15).
A kind of concentrated seawater the most according to claim 1 and 2 carries bromine closed loop blow-removing system, it is characterised in that described conversion basin (3), bromine simple substance transforming agent tank (4), stripping tower (6), absorption tower (8) are all that fiberglass is made.
A kind of concentrated seawater the most according to claim 1 and 2 carries bromine closed loop blow-removing system, it is characterised in that in described step a, the brominated scope control of concentrated seawater is at Br: 100-250mg/L, and pH value controls at 2.5-4.0, and joining chlorine rate is 110-130%.
A kind of concentrated seawater the most according to claim 1 and 2 carries bromine closed loop blow-removing system, it is characterised in that in described step c, absorption tower filler, packing support are set to 1-2 set with redistributor, and extractant spray flux is 1.5-3 times of bromine.
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040067192A1 (en) * | 2002-10-07 | 2004-04-08 | The Procter & Gamble Company | Conversion of sodium bromide to anhydrous hydrobromic acid and sodium bisulfate |
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- 2014-06-05 CN CN201410246456.6A patent/CN104250040B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2663092A (en) * | 1991-09-16 | 1993-04-27 | Catalytica, Inc. | Process and catalyst for producing bromine |
| 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 |
| CN101913564A (en) * | 2010-07-30 | 2010-12-15 | 天津长芦海晶集团有限公司 | Method for preparing bromine from brine |
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| CN202594778U (en) * | 2012-06-18 | 2012-12-12 | 山东裕源集团有限公司 | Bromine production system |
| CN103754823A (en) * | 2014-01-08 | 2014-04-30 | 清华大学 | Reaction-extraction coupling method for extracting molecular bromine or iodine |
| 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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