CN114933283A - Production process of bromine from desalted concentrated seawater - Google Patents
Production process of bromine from desalted concentrated seawater Download PDFInfo
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 112
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 109
- 239000013535 sea water Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 55
- 238000004821 distillation Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 239000012267 brine Substances 0.000 claims abstract description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000007664 blowing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 54
- 239000000460 chlorine Substances 0.000 claims description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 17
- 230000020477 pH reduction Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000605 extraction Methods 0.000 abstract description 11
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010612 desalination reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a production process of bromine from desalinated concentrated seawater, which comprises the following steps: the method comprises the following steps: acidifying and oxidizing brine; step two: an air blowing step; step three: an absorption and enrichment step; step four: an oxidation distillation step; step five: and (5) tail gas recovery. The method of the invention provides a process technology for extracting bromine from concentrated seawater after seawater desalination for the first time, wherein dilute acid is adopted to adjust the pH value to 2.0-4.0, chlorine gas is added to carry out oxidation reaction in a pipeline reactor, and the addition amount of the chlorine gas is 1.05-1.35 times of the theoretical addition amount. The process flow is simple, the extraction rate of bromine is high, the utilization rate of elements is high, the cost is low, and the quality of industrial bromine of a product obtained by separating bromine water reaches the QB/T2021-1994 high-class product standard.
Description
Technical Field
The invention belongs to the technical field of bromine production processes, and particularly relates to a production process of bromine from desalted concentrated seawater.
Background
Bromine is an important basic chemical raw material, and downstream products of bromine are widely applied to the fields of petroleum, medicine, national defense and the like. With the rapid development of economy in China, the market demand is strongly increased. In nature, bromine is not stable and is mainly present in bromine salts. In China, bromine resources are distributed more intensively, and bromine salt mainly exists in underground brine and seawater. In recent ten years, the economy of China is rapidly developed, the industrial production is rapidly improved, the yield of bromine is rapidly improved, the history is new and high, and the consumption of bromine is greatly increased. The bromine can be produced by 15-16 million tons every year in China, and the world is the third bromine-producing big country following the United states and Israel, but China is also a big world using bromine, and the bromine needs to be imported by more than 5 million tons every year.
Since the 90 s of the last century, the total yield of bromine in China reaches more than 150 million tons, and the total exploitation amount exceeds more than 40 percent of the total reserve of underground brine bromine. The well depth for exploiting the underground brine is reduced to dozens of meters from the original several meters, and the water supply amount of a single well is also reduced from 15m 3 Reduction of the reaction time/h to 15m 3 And about/h. The bromine content of the underground brine is nearly 300g/m 3 Reduced to a minimum of only 90g/m 3 . The bromine content in offshore seawater is reduced at a rate of 5% per year, which causes the difficulty of the bromine extraction process to be increased, the total amount and the grade of bromine resources to be rapidly reduced, and the bromine extraction industry faces the dilemma that the traditional bromine resources are gradually exhausted. The shortage of bromine supply and demand caused by resource shortage becomes a normal state, the price of bromine in China runs high for a long time, and especially the price of bromine in this year creates a new history. Therefore, the development of the extraction of bromine from the seawater and the concentrated seawater after the seawater desalination becomes an important way for preparing bromine. The desalinated concentrated seawater has the advantages of stable source, large quantity, higher temperature and clean water quality, and can be used for extracting bromine, so that the current situation that the industry of extracting bromine in China mainly depends on underground brine is avoided, a novel bromine resource source is developed, the production scale is improved, the flexibility of factory building is increased, and the industrial gathering effect can be fully exerted.
Disclosure of Invention
In view of the above, the invention provides a production process of bromine from desalinated concentrated seawater, aiming at overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a production process of bromine from desalinated concentrated seawater comprises the following steps:
the method comprises the following steps: acidifying and oxidizing brine;
adding dilute acid into the concentrated seawater from a power plant to adjust the pH value of the concentrated seawater, introducing chlorine into a pipeline after the pH value of the concentrated seawater is adjusted, wherein the addition amount of the chlorine is 1.05-1.35 times of the theoretical addition amount, and the concentrated seawater generates free bromine through an acidification oxidation pipeline reactor;
step two: an air blowing step;
the concentrated seawater is delivered to a blow-off tower after full reaction, uniformly distributed from the top of the blow-off tower, flows through a packing layer from top to bottom, air is blown into the bottom of the blow-off tower for resolution, and the free bromine is blown out from the top of the blow-off tower and enters an absorption tower;
step three: an absorption and enrichment step;
the method comprises the following steps that (1) the blown-out gas containing free bromine from the top of a blowing-out tower enters an absorption tower from the top of the absorption tower, meanwhile, sulfur dioxide gas generated by a sulfur incinerator reaction and fresh water or circulating absorption liquid are added to the top of the absorption tower, when the bromine content in the absorption liquid reaches 40-80g/l, the absorption liquid is discharged to a finished liquid pool from the bottom of the absorption tower, tail gas of the absorption tower is pumped into an enrichment foam capturing tower, and hydrobromic acid liquid in the absorption tower is enriched, recovered and merged into the finished liquid pool;
step four: an oxidation distillation step;
pumping the finished liquid containing hydrobromic acid at the bottoms of the absorption tower and the enrichment foam capturing tower into a distillation tower through a pump, introducing the preheated finished liquid into the distillation tower from the top of the distillation tower after tail gas is absorbed by a tail gas recovery tower, spraying the finished liquid at the top of a bromine reaction section of the distillation tower, introducing steam and chlorine gas from the bottom of the distillation tower for countercurrent displacement, controlling the temperature of the top of the distillation tower to be 85-105 ℃ through adding steam, and obtaining bromine finished product after bromine-containing steam discharged from the distillation tower passes through a condenser, a separator and a rectifying tower;
step five: a tail gas recovery step;
and the recovery tower takes the preheated hydrobromic acid-containing finished liquid as an absorption liquid, and after excessive chlorine and uncondensed bromine discharged from the distillation tower, a condenser and a separator and a small amount of chlorine discharged from the condenser of the rectification tower are recovered, the absorption mother liquid enters the distillation tower to react and extract bromine, and unabsorbed inert tail gas is discharged from a blow-down pipe at the top of the recovery tower.
Preferably, a helical blade is arranged in the acidification and oxidation pipeline reactor in the brine acidification and oxidation step.
Preferably, a high-definition network camera is arranged outside the distillation tower in the oxidative distillation step.
Preferably, the concentrated seawater at the bottom of the blowout tower is discharged from the bottom of the tower through a liquid seal pipe and flows into a lower-level brine tank for salt production.
Preferably, the bottom acid liquid of the distillation tower enters a dilute acid liquid pool to be used as the acidizing liquid of the concentrated water.
Preferably, the blow-off tower, the absorption tower and the enrichment foam capturing tower adopt a three-tower connected structure.
Preferably, SO in the tail gas discharged from the enrichment froth capturing tower 2 The content is 10-100 ppm.
Compared with the prior art, the invention has the following advantages:
(1) the method provides a process technology for extracting bromine from concentrated seawater after seawater desalination for the first time, the pH value is adjusted to 2.0-4.0 by adopting dilute acid, chlorine gas is added into a pipeline reactor for oxidation reaction, and Br in brine is oxidized into Br 2 The addition amount of chlorine gas is 1.05-1.35 times of the theoretical addition amount. The bromine content in the mother liquor is about 40-80 g/l. The mother liquid of hydrobromic acid is oxidized into free bromine by chlorine gas, and is heated and evaporated by steam, and the temperature of the top of the distillation tower is controlled within the range of 85-105 ℃ by adding steam. And after the bromine-containing steam at the tower top is condensed, bromine water is separated to obtain the product industrial bromine, and the quality of the industrial bromine product reaches QB/T2021-.
(2) The method adopts an acidification oxidation pipeline reactor to ensure that chlorine gas and concentrated seawater are fully mixed and reacted,
(3) the waste acid generated by sulfur dioxide absorption and chlorine gas oxidative distillation in the method realizes cyclic utilization, and the part of waste acid enters a dilute acid liquid pool from the bottom of a distillation tower to be used as the acid adjustment of concentrated seawater.
(4) The method adopts a three-tower conjoined structure of a blow-out tower, an absorption tower and an enrichment foam-catching tower, and the tail gas from the enrichment foam-catching tower contains a small amount of SO 2 HBr and air enter the blow-off tower again after being pressurized by the draught fan, and enriched tail gas circulates after being pressurized by the draught fan, so that the element utilization rate is improved, and the tail gas emission is reduced.
(5) The method uses on-line detection to absorb the tail gas SO 2 Setting the relationship between the sulfur dioxide content and the spiral frequency of sulfur addition in DCS, and controlling SO in tail gas 2 The content of the bromine is within the range of 10-100ppm, the bromine extraction rate and the utilization rate of sulfur elements are accurately controlled, and the bromine extraction rate and the utilization rate of the sulfur elements are improved.
(6) According to the method, colors in the distillation tower are observed by using a high-definition network camera, accurate addition control of chlorine and steam is realized by measuring the colors of the upper and lower sight glasses of the distillation tower through effective data conversion, the extraction rate of the distillation tower can reach more than 99%, and the extraction rate of bromine is greatly improved.
(7) The method adopts the finished solution as tail gas absorption solution, the preheated finished solution containing hydrobromic acid is taken as absorption solution by a recovery tower, and after excessive chlorine gas and uncondensed bromine which are discharged from a bromine reaction distillation tower condenser and a separator and a small amount of chlorine gas which is discharged from a rectification tower condenser are recovered, the absorbed mother solution enters a bromine reaction distillation tower for reaction and bromine extraction. The unabsorbed inert tail gas is discharged from the vent pipe at the top of the recovery tower, so that the utilization rate of chlorine is improved to the maximum extent, and the consumption of raw materials is reduced.
Drawings
FIG. 1 is a schematic view of a process flow diagram of the present invention;
FIG. 2 is a schematic diagram of a distillation column in the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to the following examples.
The technological process of the present invention is shown in figure 1, concentrated sea water produced by sea water desalination by using power generation afterheat in a power plant is adjusted in pH value by dilute acid, chlorine gas is added to carry out oxidation reaction in a pipeline reactor, and Br in brine is added - By oxidation to Br 2 The circulating gas is analyzed and blown out by an absorption tower, and then is absorbed into hydrobromic acid mother liquor by sulfur dioxide and water, and the hydrobromic acid mother liquor is recycledOxidizing gas into free bromine, heating with steam to evaporate, condensing bromine-containing steam, and separating bromine water to obtain industrial bromine product. The whole process comprises the working procedures of brine acidification and oxidation, air blowing, sulfur dioxide absorption and enrichment, oxidation and distillation, tail gas recovery, sulfur dioxide preparation and the like. The specific procedures are as follows:
(1) acidifying and oxidizing bittern
The concentrated seawater from power plant has concentration of 4-6 Baume degree and bromine content of 60-100PPm, and diluted acid is added to adjust pH value of concentrated seawater to 2.0-4.0 to form acidic environment, so as to inhibit hydrolysis of bromine and chlorine, and improve utilization rate of chlorine and extraction rate of bromine.
After the pH value of the concentrated seawater is adjusted, chlorine gas is introduced into a pipeline (liquid chlorine from a liquid chlorine steel cylinder is vaporized by a chlorine gas vaporizer, so that the pressure of the chlorine gas is stably output from the pipeline, and then the chlorine gas is accurately metered by a rotor flowmeter), wherein the addition amount of the chlorine gas is 1.05-1.35 times of the theoretical addition amount. Oxidizing the bromide ions in the brine into free bromide molecules in a pipeline, reducing chlorine into chloride ions, dissolving the chloride ions in concentrated seawater, and generating free bromine by the concentrated seawater through an acidification oxidation pipeline reactor.
The chemical reaction formula of the process is as follows:
2Br - +Cl 2 →2Cl - +Br 2
the oxidation reaction in the process is the key of the whole production process, and if the oxidation reaction is insufficient, the bromine ion oxidation rate in the concentrated seawater is low, so that the extraction rate is low, and the bromine resource is wasted. Therefore, the invention adopts the acidification oxidation pipeline reactor, strictly controls the addition amount of the chlorine and the reaction residence time, and ensures that the chlorine and the concentrated seawater are fully mixed and reacted. The acidification and oxidation pipeline reactor does not need any external power, the spiral blade is arranged in the pipeline reactor, so that the dilute acid, the concentrated seawater and the chlorine impact the spiral blade when flowing in the pipeline reactor, the velocity gradient of the movement of the mixed liquid flow is increased or turbulent flow is formed, the separation-position movement-rejoining is formed during laminar flow, violent vortex flow can be generated in the section direction during turbulent flow, and strong shearing force acts on the mixed liquid to further separate and mix the mixed liquid, thereby ensuring the full mixing reaction of the chlorine and the concentrated seawater.
(2) Air blow out
The concentrated seawater is delivered to a blow-off tower after full reaction, uniformly distributed at the top of the blow-off tower, and flows through a packing layer from top to bottom, and free bromine in the concentrated seawater is blown in air from the bottom of the tower by a fan for analysis. The free bromine is blown out from the top of the tower and enters an absorption tower. The concentrated seawater blown out of the tower bottom is discharged from the tower bottom through a liquid seal pipe and flows into a lower-level brine pool for salt production.
(3) Absorption enrichment
The blow-off gas containing free bromine coming out of the top of the blow-off tower enters the absorption tower from the top of the absorption tower, and simultaneously, sulfur dioxide gas generated by the reaction of the sulfur incinerator and fresh water (or circulating absorption liquid) are added into the top of the absorption tower. Through oxidation-reduction reaction, gaseous bromine molecules are changed into HBr, and the HBr is absorbed by water to form hydrobromic acid, and sulfur dioxide is oxidized to form sulfuric acid. When the bromine content of the absorption liquid (finished liquid) containing hydrobromic acid and sulfuric acid reaches 40-80g/l, the absorption liquid is discharged to a finished liquid pool from the bottom of the absorption tower. Most of tail gas of the absorption tower is air and slightly excessive SO 2 And contains hydrobromic acid in certain atomized form. And pumping tail gas of the absorption tower into an enrichment foam capturing tower, enriching and recovering hydrobromic acid liquid in the absorption tower, and merging the hydrobromic acid liquid into a finished liquid pool.
The tail gas from the enrichment mist capturing tower contains a small amount of SO 2 HBr and air are pressurized by the draught fan, and then the tail gas enters the blow-off tower again. The blow-off tower, the absorption tower and the enrichment foam capturing tower adopt a three-tower connected structure, and the enrichment tail gas is pressurized by a fan and then circulated. Excess SO in the recycle 2 And a small amount of HBr is circularly absorbed by the brine. The chemical reaction formula of the process is as follows:
Br 2 +SO 2 +H 2 O→HBr+H 2 SO 4
it can be seen from the reaction equation that the amount of sulfur dioxide fed affects the bromine absorption. SO (SO) 2 If the addition amount is too small, the bromine is absorbed incompletely and cannot be reduced completely; if the addition amount is too much, sulfur dioxide can not be fully utilized, the bromine blowing rate in the blowing tower is reduced, the blowing cost is increased, and the resource waste is caused. Therefore, the invention uses on-line detection to absorb the tail gas SO 2 The content of (A) is adjusted in real time according to the content of the tail gasThe addition of sulfur realizes the optimization of the process.
(4) Oxidative distillation
Pumping the finished liquid containing hydrobromic acid at the bottoms of the absorption tower and the enrichment and foam-catching tower into a distillation tower by a pump, and preheating the finished liquid by using the waste distillation liquid. The preheated finishing liquid enters from the top of the distillation tower after absorbing tail gas by a tail gas recovery tower and is sprayed down from the top of the bromine reaction section (filling section). Introducing steam and chlorine gas from the bottom of the tower for countercurrent displacement, vaporizing the bromine molecules obtained by oxidation displacement, discharging the vaporized bromine molecules from the upper part of the tower together with water vapor, and adding the vaporized bromine molecules into the tower to control the temperature of the tower top to be 85-105 ℃. The bromine vapor discharged from the tower is mixed with water vapor and condensed into liquid bromine and bromine-containing water through a tubular condenser. The liquid bromine and bromine water have different densities and are automatically layered in a separator, the lower layer is liquid bromine with higher density and is discharged from the lower port of the separator, and then the industrial finished bromine is obtained by rectification; the upper layer is saturated bromine water with lower density, which is extracted from the middle part of the separator and returned to the reactive distillation tower. The uncondensed gas is discharged from the emptying port of the condenser and the top of the separator. The uncondensed gas contains partial excessive chlorine, uncondensed bromine and the like, and enters a tail gas recovery tower to preheat mother liquor to recover chlorine and bromine in the mother liquor. Bottom of distillation column (hydrochloric acid reduced from chlorine and absorption column SO) 2 Sulfuric acid generated by oxidation) acid liquor enters a dilute acid liquor pool to be used as the acidizing fluid of concentrated water.
The chemical reaction formula of the procedure is as follows:
2HBr+Cl 2 →2HCl+Br 2
the amount of chlorine and steam added is a key control point in the process. According to the invention, the color in the distillation tower is observed by using a high-definition network camera, the length of the reddish brown bromine vapor gas in the distillation tower is analyzed, the degree of chemical reaction is judged, and then the addition amount of chlorine and vapor is automatically controlled on line by combining multi-angle analysis of other factors. The amount of chlorine and steam added is a critical control point in the process. Bromine is generated after the chlorine gas reacts with the finished solution, the bromine is vaporized under the action of steam and is evaporated from the top of the tower, and the waste steam liquid is discharged from the bottom of the tower. In the process, an interface is formed, above which is reddish brown containing bromine, and at the next moment, colorless distilled waste liquid is formed. As shown in figure 2, the method provided by the invention has the advantages that the color in the distillation tower is observed by using a high-definition network camera, the position of the reddish brown bromine steam interface in the distillation tower is analyzed, the interface position is converted into a signal of 0-100% to judge the degree of chemical reaction, the pneumatic valve opening of chlorine and steam is controlled according to the signal, and finally, the addition amount of chlorine and steam is automatically controlled on line by correcting the temperature at the top of the tower.
(5) Tail gas recovery
And the recovery tower takes preheated hydrobromic acid-containing finishing liquid as absorption liquid, and after excessive chlorine and uncondensed bromine discharged from a bromine reaction distillation tower condenser and a separator and a small amount of chlorine discharged from a rectification tower condenser are recovered, the absorption mother liquid enters the bromine reaction distillation tower to react and extract bromine. The unabsorbed inert tail gas is discharged from the vent pipe at the top of the recovery tower.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (7)
1. A production process of bromine from desalinated concentrated seawater is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: acidifying and oxidizing brine;
adding dilute acid into the concentrated seawater from a power plant to adjust the pH value of the concentrated seawater, introducing chlorine into a pipeline after the pH value of the concentrated seawater is adjusted, wherein the addition amount of the chlorine is 1.05-1.35 times of the theoretical addition amount, and the concentrated seawater generates free bromine through an acidification oxidation pipeline reactor;
step two: an air blowing step;
the concentrated seawater is delivered to a blow-off tower after full reaction, uniformly distributed at the top of the blow-off tower, flows through a packing layer from top to bottom, air is blown in from the bottom of the tower for analysis, and the free bromine is blown out from the top of the tower and enters an absorption tower;
step three: an absorption and enrichment step;
the method comprises the following steps that a blow-out gas containing free bromine from the top of a blow-out tower enters an absorption tower from the top of the absorption tower, meanwhile, sulfur dioxide gas generated by a sulfur incinerator reaction and fresh water or circulating absorption liquid are added to the top of the absorption tower, when the bromine content in the absorption liquid reaches 40-80g/l, the absorption liquid is discharged to a finished liquid pool from the bottom of the absorption tower, tail gas of the absorption tower is pumped into an enrichment foam capturing tower, and hydrobromic acid liquid in the absorption tower is enriched, recovered and merged into the finished liquid pool;
step four: an oxidation distillation step;
pumping finished liquid containing hydrobromic acid at the bottoms of an absorption tower and an enrichment foam capturing tower into a distillation tower through a pump, allowing the preheated finished liquid to enter from the top of the distillation tower after tail gas is absorbed by a tail gas recovery tower, spraying the finished liquid down from the top of a bromine reaction section of the distillation tower, introducing steam and chlorine from the bottom of the distillation tower for countercurrent displacement, controlling the temperature of the top of the distillation tower to be 85-105 ℃ through adding steam, and allowing bromine-containing steam discharged from the distillation tower to pass through a condenser, a separator and a rectification tower to obtain a finished bromine product;
step five: a tail gas recovery step;
and the recovery tower takes preheated hydrobromic acid-containing finishing liquid as absorption liquid, and after excessive chlorine and uncondensed bromine discharged from the distillation tower, a condenser and a separator and a small amount of chlorine discharged from the condenser of the rectifying tower are recovered, the absorption mother liquor enters the distillation tower to react and extract bromine, and unabsorbed inert tail gas is discharged from a vent pipe at the top of the recovery tower.
2. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein the process comprises the following steps: and a helical blade is arranged in the acidification and oxidation pipeline reactor in the step of acidification and oxidation of the brine.
3. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein: and a high-definition network camera is arranged outside the distillation tower in the step of oxidizing distillation.
4. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein the process comprises the following steps: and the concentrated seawater blown out of the tower bottom is discharged from the tower bottom through a liquid seal pipe and flows into a lower-level brine pool for salt production.
5. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein: and the bottom acid liquid of the distillation tower enters a dilute acid liquid pool to be used as the acidizing liquid of the concentrated water.
6. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein: the blow-off tower, the absorption tower and the enrichment foam capturing tower adopt a three-tower connected structure.
7. The process for producing bromine from desalinated concentrated seawater according to claim 1, wherein: SO in tail gas from enrichment foam capturing tower 2 The content is 10-100 ppm.
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| CN116161622A (en) * | 2023-04-25 | 2023-05-26 | 天津长芦汉沽盐场有限责任公司 | Method for preparing bromine by using carnallite mother liquor |
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