CN115636395A - Method and equipment for producing bromine - Google Patents
Method and equipment for producing bromine Download PDFInfo
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- CN115636395A CN115636395A CN202211297719.7A CN202211297719A CN115636395A CN 115636395 A CN115636395 A CN 115636395A CN 202211297719 A CN202211297719 A CN 202211297719A CN 115636395 A CN115636395 A CN 115636395A
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- bromine
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 122
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title abstract description 13
- 239000012267 brine Substances 0.000 claims abstract description 96
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 96
- 239000000460 chlorine Substances 0.000 claims abstract description 75
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 71
- 238000004821 distillation Methods 0.000 claims abstract description 63
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 238000005070 sampling Methods 0.000 claims abstract description 21
- 230000005674 electromagnetic induction Effects 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 230000020477 pH reduction Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 48
- 239000006200 vaporizer Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 28
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 23
- 239000003595 mist Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 10
- BSKZDJXVMPWPRA-UHFFFAOYSA-N O.[Br] Chemical compound O.[Br] BSKZDJXVMPWPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000013505 freshwater Substances 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 241001131796 Botaurus stellaris Species 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 abstract description 7
- 238000009834 vaporization Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000004801 process automation Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SISAYUDTHCIGLM-UHFFFAOYSA-N bromine dioxide Inorganic materials O=Br=O SISAYUDTHCIGLM-UHFFFAOYSA-N 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Classifications
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a method and equipment for producing bromine, belonging to the technical field of bromine production, wherein the method for producing bromine comprises brine acidification, liquid chlorine vaporization, brine oxidation, resolution, absorption and distillation; the equipment for producing bromine comprises: the system comprises a distillation tower, an electromagnetic induction heating unit, an outlet heat exchanger, an inlet heat exchanger and an automatic sampling detection system; the system automatically finishes the real-time data of brine bromine content, chlorine and acid preparation, waste discharge bromine content and sulfur dioxide content and automatically transmits the data to the DCS control system through the online detection system, finishes automatic valve adjustment through process optimization design, achieves material-free input material balance, realizes process automation control, obviously improves the product precision and quality, obviously improves the production efficiency and greatly reduces the production cost.
Description
Technical Field
The invention relates to the technical field of bromine production, in particular to a method and equipment for producing bromine.
Background
Bromine as an important chemical raw material has wide application in various fields of industrial production, scientific research and life, so the method has important practical significance for the development and utilization of bromine resources. The application field of the method is rapidly widened along with the deep development of terminal products, and the method is mainly applied to the following fields at present: the compounds are widely applied to the fields of medicines, medical intermediates, pesticides, pesticide intermediates, dyes, dye intermediates, brominated flame retardants, fire extinguishing agents, refrigerants and other inorganic brominated products.
The bromine resources in China are mainly distributed in the east coastal areas, the main producing areas are Shandong, tianjin, hebei, jiangsu, liaoning and the like, and the bromine yield is extremely limited before 1987 due to the influence of process technology, raw materials, climate and the like. After 1987, shandong increased the strength of salt chemical development, established multiple sets of devices for extracting bromine by using underground brine in sequence, and made the bromine industry in China develop rapidly, the bromine production capacity of Shandong accounted for 85-90% of the nation, and the bromine production capacity of Weifang area accounted for 70% of the nation, which became the biggest bromine production base in the nation.
However, the following problems exist in the current production of bromine: the existing production system usually generates a large amount of waste heat in the process of producing bromine, so that resource waste is caused, and the production cost is overhigh; in key processes of bromine production, such as oxidation, absorption, distillation and other processes, the accuracy of detection results is affected by adopting manual sampling and testing or depending on the experience of operators for key process indexes such as brine bromine content detection, chlorine preparation and acid preparation amount, residual sulfur dioxide content, chlorine pressure, waste liquid bromine content and the like, the labor cost is high, certain harm is generated to the safety of workers, and certain pollution is caused to the environment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method and equipment for producing bromine, which automatically complete the real-time data of brine containing bromine, chlorine and acid preparation, waste discharge containing bromine and sulfur dioxide and automatically transmit the data to a DCS control system through an online detection system, complete automatic valve adjustment through process optimization design, achieve material-free input material balance, realize process automation control, obviously improve the precision and quality of products, obviously improve the production efficiency and greatly reduce the production cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing bromine includes acidifying bittern, gasifying liquid chlorine, oxidizing bittern, analyzing, absorbing and distilling.
Acidifying the brine, namely introducing the brine into a buffer tank along an open channel, pressurizing the brine in the buffer tank by a pump, conveying the brine to a blow-out tower, adding dilute sulfuric acid into the brine on a conveying pipeline for acidifying treatment, adjusting the pH value of the brine to be 2.5-4.5, and obtaining the acidified brine after the acidifying treatment is finished;
the bromine content of the brine is 100-400mg/L;
the mass fraction of the sulfuric acid in the dilute sulfuric acid is 15-18%;
each 1 ton of bromine is produced and consumed by 8300-8500m 3 And (3) brine.
The liquid chlorine is vaporized, the liquid chlorine is introduced into a vaporizer, the vaporizer is heated by warm water, the water temperature of the warm water is controlled to be 40-60 ℃, the liquid chlorine in the vaporizer is vaporized into chlorine, and the pressure in the vaporizer is controlled to be 0.25-0.35MPa by adjusting the flow and the water temperature of the liquid chlorine to supply the chlorine;
consuming 1-1.2t of chlorine gas for each 1 ton of bromine produced.
And (3) oxidizing the brine, introducing chlorine into the acidified brine, wherein the chlorine preparation rate is 105-145%, free bromine is generated, the oxidation rate reaches 88-92%, and the oxidized brine is obtained after the brine is oxidized.
And (3) analyzing, namely introducing the oxidized brine into a filler blowing-out tower, communicating the filler blowing-out tower with an absorption tower through an air passage to form a closed circulation system, introducing air into the bottom of the filler blowing-out tower, and controlling the introduction speed of the air to be 120000-140000m 3 H, the water is in countercurrent contact with the oxidized brine sprayed from top to bottom, and free bromine gas dissolved in the brine is in full contact with air and is blown out by the air to obtain bromine-containing air;
the spraying speed of the oxidized brine is 1100-1300m 3 /h；
The filler is a stepped ring with the diameter of 75-80mm.
The absorption comprises the steps that bromine-containing gas blown out from the top of the tower reacts with sulfur dioxide and mist fresh water added into an air duct at the top to generate hydrobromic acid and sulfuric acid, small droplets containing the hydrobromic acid and the sulfuric acid are enriched by an absorption tower mist eliminator and condensed into finished liquid, the finished liquid flows into a finished liquid storage tank from the bottom of the tower, gas separated from the finished liquid in the absorption tower enters a blower through a blower inlet, the gas is pressurized and then sent into a blow-off tower, and the gas circulates in a closed manner among the blow-off tower, the absorption tower, the mist eliminator and the blower;
the introduction speed of the bromine-containing gas is 2000-2200m 3 /h；
The introduction speed of the sulfur dioxide is 5000-5300m 3 /h；
The introducing speed of the mist fresh water is 3000-3400m 3 /h。
The distillation is carried out, the completion liquid is added from the top of a distillation tower by a pump, saturated water vapor and chlorine are added from the bottom of the distillation tower, the completion liquid is in countercurrent contact with the water vapor and the chlorine in the tower, hydrogen bromide is subjected to chlorine oxidation to generate elemental bromine and hydrogen chloride, the elemental bromine and part of the water vapor are discharged from the top of the distillation tower, the temperature is reduced to 30-40 ℃ by a heat exchanger and a cooler through condensation, the bromine enters a bromine-water separation bottle, a mixture of crude bromine and bromine water is obtained from the separation bottle, and the crude bromine is treated to remove redundant chlorine to obtain finished bromine which flows into a storage tank; mixing the bromine water mixture with the finished solution, sending the mixture back to the distillation tower for the next distillation process, recycling the acid-containing waste liquid at the bottom of the distillation tower, flowing into an acid preparation pool, and sending the acid-containing waste liquid to an outlet pipe of a brine pump for acidifying brine;
the adding speed of the finishing liquid is 1500-1800m 3 /h；
The introducing speed of the saturated steam is 3000-3200m 3 /h；
The introduction speed of the chlorine gas is 500-530m 3 /h；
2-2.3t of water vapor and 0.45-0.5t of chlorine are consumed for each 1 ton of bromine produced.
An apparatus for the production of bromine comprising: the system comprises a distillation tower, an electromagnetic induction heating unit, an outlet heat exchanger and an inlet heat exchanger;
an inlet heat exchanger is arranged at a feed inlet of the distillation tower, an outlet heat exchanger is arranged at a discharge outlet, an electromagnetic induction heating unit is arranged at an acid liquor inlet, one end of the electromagnetic induction heating unit is connected with an acid liquor tower, and the electromagnetic induction heating unit heats the acid liquor tower to enter the acid liquor temperature of the electromagnetic induction heating unit through DCS constant temperature control;
the outlet heat exchanger is connected with a pipeline between the material liquid tower and the distillation tower and is used for heating the material liquid in the pipeline between the material liquid tower and the distillation tower;
the distillation tower is connected with a chlorine vaporizer through a pipeline, a chlorine heater is arranged between the distillation tower and the chlorine vaporizer, and the chlorine heater is used for heating vaporized chlorine;
the chlorine vaporizer is connected with a hot water tank which provides energy for the chlorine vaporizer to vaporize chlorine. An electric heater and a temperature sensor are arranged in the hot water tank;
the pipeline between the distillation tower and the acid liquor tower is connected with a metal float flowmeter and an electric control valve, the pipeline between the distillation tower and the chlorine gas vaporizer is connected with a metal float flowmeter and an electric control valve, the metal float flowmeter and the electric control valve are electrically connected with an automatic control cabinet, and the automatic control cabinet is provided with a control main board and a touch screen.
The equipment for producing bromine further comprises an automatic sampling detection system; the automatic sampling detection system comprises a reaction kettle, automatic sampling equipment and an automatic analyzer, wherein the automatic sampling equipment and the automatic analyzer are connected with the reaction kettle;
the automatic sampling equipment is connected with the automatic analyzer, the automatic analyzer is connected with the industrial personal computer in a wireless network mode, the industrial personal computer is connected with the alarm, the industrial personal computer is also connected with the DCS system, the DCS system is connected with the electromagnetic control valve, and the DCS system can control the electromagnetic control valve to control the chlorine tower and the hydrochloric acid tower;
automatic sampling equipment includes sample pipeline and relief pressure valve, sample pipeline and reation kettle intercommunication, and the relief pressure valve is located sample pipeline, and the clean water tank of upper portion pipe connection of sample pipeline is equipped with the control valve on the pipeline of clean water tank and sample pipeline connection, and the lower part of sample pipeline is equipped with the air pump.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for producing bromine can effectively improve the purity of the finished bromine, and the prepared finished bromine has bromine content of more than or equal to 99.5 percent and Cl - Less than or equal to 0.05 percent, less than or equal to 0.001 percent of iodine (I), less than or equal to 0.002 percent of chlorine, less than or equal to 0.002 percent of sulfate, less than or equal to 0.00005 percent of iron (Fe) and less than or equal to 0.00005 percent of heavy metal (calculated by Pb);
(2) The method for producing bromine can improve the production efficiency by 5 percent and reduce the energy consumption of unit output value by 5 percent;
(3) The method for producing bromine can reduce the consumption of raw materials by 2 percent and save the production cost by 2.3 percent per ton of products.
Drawings
FIG. 1 is a flow chart for the production of bromine;
FIG. 2 is a diagram of an apparatus for producing bromine;
FIG. 3 is an automatic sampling inspection system.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
As shown in fig. 1, a method for producing bromine specifically comprises:
1. acidifying brine: and (2) introducing the brine into a buffer tank along an open channel, pressurizing and conveying the brine in the buffer tank to a blow-out tower by a pump, adding dilute sulfuric acid into the brine on a conveying pipeline for acidification treatment, adjusting the pH value of the brine to be 2.5, and obtaining the acidified brine after the acidification treatment is finished.
The bromine content of the brine is 100mg/L;
the mass fraction of sulfuric acid in the dilute sulfuric acid is 15 percent;
each 1 ton of bromine produced consumes 8300m 3 And (3) brine.
2. Liquid chlorine vaporization: introducing liquid chlorine into a vaporizer, heating the vaporizer by warm water, controlling the water temperature of the warm water to be 40 ℃, vaporizing the liquid chlorine in the vaporizer into chlorine, and controlling the pressure in the vaporizer to be 0.25MPa by adjusting the flow and the water temperature of the liquid chlorine to supply the chlorine;
every 1 ton of bromine produced, 1 ton of chlorine gas was consumed.
3. Brine oxidation: and (3) introducing chlorine gas into the acidified brine, wherein the chlorine preparation rate is 105%, free bromine is generated, the oxidation rate reaches 88%, and the oxidized brine is obtained after the brine is oxidized.
4. And (3) analysis: introducing oxidized bittern into a filler blow-off tower, communicating the filler blow-off tower with an absorption tower through an air passage to form a closed circulation system, introducing air into the bottom of the filler blow-off tower, and controlling the air introduction speed to be 120000m 3 H, the water is in countercurrent contact with the oxidized brine sprayed from top to bottom, and free bromine gas dissolved in the brine is in full contact with air and is blown out by the air to obtain bromine-containing air;
the spraying speed of the oxidized brine is 1100m 3 /h；
The packing is a stepped ring with a diameter of 75mm.
5. Absorption: the bromine-containing gas blown out from the top of the tower reacts with sulfur dioxide and atomized fresh water added into an air duct at the top of the tower to generate hydrobromic acid and sulfuric acid, small droplets containing the hydrobromic acid and the sulfuric acid are enriched by an absorber and condensed into finished liquid, the finished liquid flows into a finished liquid storage tank from the bottom of the tower, the gas separated from the finished liquid in the absorber enters a blower through an inlet of the blower, is pressurized and then is sent into a blowing tower, and the gas circulates in a closed manner among the blowing tower, the absorber, the mist eliminator and the blower.
The introduction speed of the bromine-containing gas is 2000m 3 /h；
The introduction speed of the sulfur dioxide is 5000m 3 /h；
The introducing speed of the mist fresh water is 3000m 3 /h；
6. And (3) distillation: adding the finished solution from the top of a distillation tower by using a pump, adding saturated water vapor and chlorine from the bottom of the distillation tower, enabling the finished solution to be in countercurrent contact with the water vapor and the chlorine in the tower, carrying out chlorine oxidation on hydrogen bromide to generate elemental bromine and hydrogen chloride, discharging the elemental bromine and part of the water vapor from the top of the distillation tower, condensing and cooling to 30 ℃ by using a heat exchanger and a cooler, feeding the cooled elemental bromine and the hydrogen chloride into a bromine-water separation bottle, separating the mixture of crude bromine and bromine-water obtained in the bottle, and treating the crude bromine to remove redundant chlorine to obtain finished bromine which flows into a storage tank; mixing the bromine water mixture with the finished solution, sending the mixture back to the distillation tower for the next distillation process, recycling the acid-containing waste liquid at the bottom of the distillation tower, flowing into an acid preparation pool, and sending the acid-containing waste liquid to an outlet pipe of a brine pump for acidifying brine;
the addition speed of the completion liquid is 1500m 3 /h；
The introducing speed of the saturated steam is 3000m 3 /h；
The introduction speed of the chlorine gas is 500m 3 /h；
For every 1 ton of bromine produced, 2t of water vapor and 0.45t of chlorine gas were consumed.
The bromine content in the prepared finished bromine is more than or equal to 99.5 percent, and Cl is contained - Less than or equal to 0.05 percent, less than or equal to 0.001 percent of iodine (I), less than or equal to 0.002 percent of chlorine, less than or equal to 0.002 percent of sulfate, less than or equal to 0.00005 percent of iron (Fe) and less than or equal to 0.00005 percent of heavy metal (calculated by Pb).
Example 2
As shown in fig. 1, a method for producing bromine specifically comprises:
1. acidifying brine: and (2) introducing the brine into a buffer tank along an open channel, pressurizing and conveying the brine in the buffer tank to a blow-out tower by a pump, adding dilute sulfuric acid into the brine on a conveying pipeline for acidification treatment, adjusting the pH value of the brine to 3.5, and obtaining the acidified brine after the acidification treatment is finished.
The bromine content of the brine is 300mg/L;
the mass fraction of sulfuric acid in the dilute sulfuric acid is 16%;
8400m is consumed for each 1 ton of bromine produced 3 And (3) brine.
2. Liquid chlorine vaporization: introducing liquid chlorine into a vaporizer, heating the vaporizer by warm water, controlling the water temperature of the warm water to be 50 ℃, vaporizing the liquid chlorine in the vaporizer into chlorine, and controlling the pressure in the vaporizer to be 0.30MPa by adjusting the flow and the water temperature of the liquid chlorine to supply the chlorine;
1.1t of chlorine gas is consumed for each 1 ton of bromine produced.
3. Brine oxidation: and (3) introducing chlorine gas into the acidified brine, wherein the chlorine preparation rate is 120%, free bromine is generated, the oxidation rate reaches 90%, and the oxidized brine is obtained after the brine is oxidized.
4. And (3) analysis: introducing the oxidized brine into a filler blow-off tower, communicating the filler blow-off tower with an absorption tower through an air passage to form a closed circulation system, and introducing the oxidized brine into the filler blow-off towerIntroducing air into the bottom of the material blowing tower, and controlling the air introduction speed to be 130000m 3 H, the water is in countercurrent contact with the oxidized brine sprayed from top to bottom, and free bromine gas dissolved in the brine is in full contact with air and is blown out by the air to obtain bromine-containing air;
the spraying speed of the oxidized brine is 1200m 3 /h；
The packing is a stepped ring with a diameter of 78mm.
5. Absorption: the bromine-containing gas blown out from the top of the tower reacts with sulfur dioxide and mist fresh water added into the top air channel to generate hydrobromic acid and sulfuric acid, small droplets containing the hydrobromic acid and the sulfuric acid are enriched by an absorption tower mist eliminator and condensed into finished liquid, the finished liquid flows into a finished liquid storage tank from the bottom of the tower, the gas separated from the finished liquid in the absorption tower enters a blower through a blower inlet, the gas is pressurized and then sent into a blowing-out tower, and the gas is circulated in a closed manner among the blowing-out tower, the absorption tower, the mist eliminator and the blower.
The introduction speed of the bromine-containing gas is 2100m 3 /h；
The introduction speed of the sulfur dioxide is 5200m 3 /h；
The introducing speed of the mist fresh water is 3200m 3 /h；
6. And (3) distillation: adding the finished solution from the top of a distillation tower by using a pump, adding saturated water vapor and chlorine from the bottom of the distillation tower, enabling the finished solution to be in countercurrent contact with the water vapor and the chlorine in the tower, carrying out chlorine oxidation on hydrogen bromide to generate elemental bromine and hydrogen chloride, discharging the elemental bromine and part of the water vapor from the top of the distillation tower, condensing and cooling to 35 ℃ by using a heat exchanger and a cooler, feeding the mixture into a bromine-water separation bottle, separating the mixture of crude bromine and bromine-water obtained in the bottle, and treating the crude bromine to remove redundant chlorine to obtain finished bromine which flows into a storage tank; mixing the bromine water mixture with the finished solution, sending the mixture back to the distillation tower for the next distillation process, recycling the acid-containing waste liquid at the bottom of the distillation tower, flowing into an acid preparation pool, and sending the acid-containing waste liquid to an outlet pipe of a brine pump for acidifying brine;
the adding speed of the finishing liquid is 1600m 3 /h；
The introduction speed of the saturated steam is 3100m 3 /h；
The introduction speed of the chlorine gas is 510m 3 /h；
For every 1 ton of bromine produced, 2.1t of water vapor and 0.47t of chlorine gas were consumed.
The bromine content in the prepared bromine product is more than or equal to 99.5 percent, and Cl is contained in the bromine product - Less than or equal to 0.05 percent, less than or equal to 0.001 percent of iodine (I), less than or equal to 0.002 percent of chlorine, less than or equal to 0.002 percent of sulfate, less than or equal to 0.00005 percent of iron (Fe) and less than or equal to 0.00005 percent of heavy metal (calculated by Pb).
Example 3
As shown in fig. 1, a method for producing bromine specifically comprises:
1. acidifying brine: and (2) introducing the brine into a buffer tank along an open channel, pressurizing and conveying the brine in the buffer tank to a blow-out tower by a pump, adding dilute sulfuric acid into the brine on a conveying pipeline for acidification treatment, adjusting the pH value of the brine to 4.5, and obtaining the acidified brine after the acidification treatment is finished.
The bromine content of the brine is 400mg/L;
the mass fraction of sulfuric acid in the dilute sulfuric acid is 18 percent;
consuming 8500m per 1 ton bromine produced 3 And (3) brine.
2. Liquid chlorine vaporization: introducing liquid chlorine into a vaporizer, heating the vaporizer by warm water, controlling the water temperature of the warm water to be 60 ℃, vaporizing the liquid chlorine in the vaporizer into chlorine, and controlling the pressure in the vaporizer to be 0.35MPa by adjusting the flow and the water temperature of the liquid chlorine to supply the chlorine;
1.2t of chlorine gas is consumed for each 1 ton of bromine produced.
3. Brine oxidation: and (3) introducing chlorine gas into the acidified brine, wherein the chlorine preparation rate is 145%, free bromine is generated, the oxidation rate reaches 92%, and the oxidized brine is obtained after the brine is oxidized.
4. And (3) analysis: introducing oxidized bittern into a filler blowing-out tower, communicating the filler blowing-out tower with an absorption tower through an air passage to form a closed circulation system, introducing air into the bottom of the filler blowing-out tower, and controlling the introduction speed of the air to be 140000m 3 H, the water is in countercurrent contact with the oxidized brine sprayed from top to bottom, and free bromine gas dissolved in the brine is in full contact with air and is blown out by the air to obtain bromine-containing air;
the spraying speed of the oxidized brine is 1300m 3 /h；
The filler is a stepped ring with the diameter of 80mm.
5. Absorption: the bromine-containing gas blown out from the top of the tower reacts with sulfur dioxide and mist fresh water added into the top air channel to generate hydrobromic acid and sulfuric acid, small droplets containing the hydrobromic acid and the sulfuric acid are enriched by an absorption tower mist eliminator and condensed into finished liquid, the finished liquid flows into a finished liquid storage tank from the bottom of the tower, the gas separated from the finished liquid in the absorption tower enters a blower through a blower inlet, the gas is pressurized and then sent into a blowing-out tower, and the gas is circulated in a closed manner among the blowing-out tower, the absorption tower, the mist eliminator and the blower.
The introduction speed of the bromine-containing gas is 2200m 3 /h；
The introduction speed of the sulfur dioxide is 5300m 3 /h；
The introducing speed of the mist fresh water is 3400m 3 /h；
6. And (3) distillation: adding the finished solution from the top of a distillation tower by using a pump, adding saturated water vapor and chlorine from the bottom of the distillation tower, enabling the finished solution to be in countercurrent contact with the water vapor and the chlorine in the tower, carrying out chlorine oxidation on hydrogen bromide to generate elemental bromine and hydrogen chloride, discharging the elemental bromine and part of the water vapor from the top of the distillation tower, condensing and cooling to 40 ℃ by using a heat exchanger and a cooler, feeding the cooled elemental bromine and the hydrogen chloride into a bromine-water separation bottle, separating the mixture of crude bromine and bromine-water obtained in the bottle, and treating the crude bromine to remove redundant chlorine to obtain finished bromine which flows into a storage tank; mixing the bromine water mixture with the finished solution, sending the mixture back to the distillation tower for the next distillation process, recycling the acid-containing waste liquid at the bottom of the distillation tower, flowing into an acid preparation pool, and sending the acid-containing waste liquid to an outlet pipe of a brine pump for acidifying brine;
the addition speed of the completion liquid is 1800m 3 /h；
The introducing speed of the saturated water vapor is 3200m 3 /h；
The introduction speed of the chlorine gas is 530m 3 /h；
For every 1 ton of bromine produced, 2.3t of water vapor and 0.5t of chlorine gas were consumed.
The bromine content in the prepared bromine product is more than or equal to 99.5 percent, and Cl is contained in the bromine product - Less than or equal to 0.05 percent, less than or equal to 0.001 percent of iodine (I), less than or equal to 0.002 percent of chlorine, less than or equal to 0.002 percent of sulfate, less than or equal to 0.00005 percent of iron (Fe),the heavy metal (calculated by Pb) is less than or equal to 0.00005 percent.
Example 4
As shown in fig. 2, an apparatus for producing bromine, comprising: the device comprises a distillation tower, an electromagnetic induction heating unit, an outlet heat exchanger and an inlet heat exchanger.
An inlet heat exchanger is arranged at a feed inlet of the distillation tower, an outlet heat exchanger is arranged at a discharge outlet, an electromagnetic induction heating unit is arranged at an acid liquor inlet, one end of the electromagnetic induction heating unit is connected with an acid liquor tower, and the electromagnetic induction heating unit heats the acid liquor tower to enter the acid liquor temperature of the electromagnetic induction heating unit through DCS constant temperature control.
The outlet heat exchanger is connected with a pipeline between the material liquid tower and the distillation tower, and the outlet heat exchanger is used for heating material liquid in the pipeline between the material liquid tower and the distillation tower.
The distillation tower is connected with a chlorine vaporizer through a pipeline, a chlorine heater is arranged between the distillation tower and the chlorine vaporizer, and the chlorine heater is used for heating the vaporized chlorine.
The chlorine vaporizer is connected with a hot water tank which provides energy for the chlorine vaporizer to vaporize chlorine. An electric heater and a temperature sensor are arranged in the hot water tank.
A metal float flowmeter and an electric regulating valve are connected to a pipeline between the distillation tower and the acid liquor tower, a metal float flowmeter and an electric regulating valve are connected to a pipeline between the distillation tower and the chlorine vaporizer, the metal float flowmeter and the electric regulating valve are electrically connected with an automatic control cabinet, and the automatic control cabinet is provided with a control main board and a touch screen;
the equipment for producing bromine further comprises an automatic sampling detection system; as shown in fig. 3, the automatic sampling and detecting system comprises a reaction kettle, an automatic sampling device and an automatic analyzer, wherein the automatic sampling device and the automatic analyzer are connected with the reaction kettle, electromagnetic control valves are arranged on an air pipe and an acid pipe on the side wall of the lower part of the reaction kettle, the air pipe is connected with a chlorine tower, and the acid pipe is connected with a hydrochloric acid tower.
The automatic sampling equipment is connected with the automatic analyzer, the automatic analyzer is in wireless network connection with the industrial personal computer, the industrial personal computer is connected with the alarm, the industrial personal computer is further connected with the DCS system, the DCS system is connected with the electromagnetic control valve, and the DCS system can control the electromagnetic control valve to control the chlorine tower and the hydrochloric acid tower.
Automatic sampling equipment includes sample pipeline and relief pressure valve, sample pipeline and reation kettle intercommunication, and the relief pressure valve is located sample pipeline, and the clean water tank of upper portion pipe connection of sample pipeline is equipped with the control valve on the pipeline of clean water tank and sample pipeline connection, and the lower part of sample pipeline is equipped with the air pump.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A process for preparing bromine includes acidifying bittern, gasifying liquid chlorine, oxidizing bittern, analyzing, absorbing and distilling.
2. The method for producing bromine according to claim 1, wherein the brine is acidified, the brine is introduced into a buffer tank along an open channel, the brine in the buffer tank is pressurized by a pump and sent to a blow-off tower, dilute sulfuric acid is added into the brine on a conveying pipeline for acidification treatment, the pH value of the brine is adjusted to be 2.5-4.5, and the acidified brine is obtained after the acidification treatment;
the bromine content of the brine is 100-400mg/L;
the mass fraction of the sulfuric acid in the dilute sulfuric acid is 15-18%;
each 1 ton of bromine is produced and consumed by 8300-8500m 3 And (3) brine.
3. The method for producing bromine according to claim 1, wherein the liquid chlorine is vaporized, the liquid chlorine is introduced into a vaporizer, the vaporizer is heated with warm water, the temperature of the warm water is controlled to be 40 to 60 ℃, the liquid chlorine in the vaporizer is vaporized to chlorine gas, and the pressure in the vaporizer is controlled to be 0.25 to 0.35MPa by adjusting the flow rate and the temperature of the liquid chlorine to supply the chlorine gas;
1-1.2t of chlorine gas is consumed for each 1 ton of bromine produced.
4. The method for producing bromine according to claim 1, wherein the brine is oxidized, chlorine gas is introduced into the acidified brine, the chlorine preparation rate is 105-145%, free bromine is generated, the oxidation rate is 88-92%, and the oxidized brine is obtained after the brine is oxidized.
5. The method for producing bromine according to claim 1, wherein the desorption comprises introducing the oxidized brine into a packing blowing-out tower, communicating the packing blowing-out tower with an absorption tower through an air passage to form a closed circulation system, and introducing air into the bottom of the packing blowing-out tower at a speed of 120000-140000m 3 H, the water is in countercurrent contact with the oxidized brine sprayed from top to bottom, and free bromine gas dissolved in the brine is in full contact with air and is blown out by the air to obtain bromine-containing air;
the spraying speed of the oxidized brine is 1100-1300m 3 /h；
The packing is a stepped ring with the diameter of 75-80mm.
6. The method for producing bromine according to claim 1, wherein in the absorption, bromine-containing gas blown from the top of the tower reacts with sulfur dioxide and mist fresh water added in a top air duct to generate hydrobromic acid and sulfuric acid, small droplets of the hydrobromic acid and the sulfuric acid are enriched by an absorber mist eliminator and condensed into a finished liquid, the finished liquid flows from the bottom of the tower into a finished liquid storage tank, gas separated from the finished liquid in the absorber enters a blower through a blower inlet, the gas is pressurized and then sent to a blow-off tower, and the gas is circulated in a closed manner among the blow-off tower, the absorber, the mist eliminator and the blower;
of said bromine-containing gasThe feeding speed is 2000-2200m 3 /h；
The introduction speed of the sulfur dioxide is 5000-5300m 3 /h；
The introducing speed of the mist fresh water is 3000-3400m 3 /h。
7. The method for producing bromine according to claim 1, wherein the distillation is carried out by adding the completion liquid from the top of a distillation tower by a pump, adding saturated water vapor and chlorine gas from the bottom of the distillation tower, carrying out countercurrent contact between the completion liquid and the water vapor and between the completion liquid and the chlorine gas in the distillation tower, carrying out chlorine oxidation on hydrogen bromide to generate elemental bromine and hydrogen chloride, discharging the elemental bromine and part of the water vapor from the top of the distillation tower, condensing and cooling to 30-40 ℃ by a heat exchanger and a cooler, feeding the elemental bromine and the part of the water vapor into a bromine-water separation bottle, separating the crude bromine into a crude bromine-water mixture obtained by the bottle, treating the crude bromine to remove excessive chlorine to obtain a finished bromine, and feeding the finished bromine into a storage tank; after being mixed with the finished solution, the bromine-water mixture is sent back to the distillation tower for the next distillation process, acid-containing waste liquid at the bottom of the distillation tower is recycled, flows into an acid preparation pool and is sent to an outlet pipe of a brine pump to acidify brine;
the adding speed of the finishing liquid is 1500-1800m 3 /h；
The introducing speed of the saturated steam is 3000-3200m 3 /h；
The introduction speed of the chlorine gas is 500-530m 3 /h；
2-2.3t of water vapor and 0.45-0.5t of chlorine are consumed for each 1 ton of bromine produced.
8. An apparatus for producing bromine, comprising: the system comprises a distillation tower, an electromagnetic induction heating unit, an outlet heat exchanger and an inlet heat exchanger;
an inlet heat exchanger is arranged at a feed inlet of the distillation tower, an outlet heat exchanger is arranged at a discharge outlet, an electromagnetic induction heating unit is arranged at an acid liquor inlet, one end of the electromagnetic induction heating unit is connected with an acid liquor tower, and the electromagnetic induction heating unit heats the acid liquor tower to enter the acid liquor temperature of the electromagnetic induction heating unit through DCS constant temperature control;
the outlet heat exchanger is connected with a pipeline between the material liquid tower and the distillation tower and is used for heating the material liquid in the pipeline between the material liquid tower and the distillation tower;
the distillation tower is connected with a chlorine vaporizer through a pipeline, a chlorine heater is arranged between the distillation tower and the chlorine vaporizer, and the chlorine heater is used for heating vaporized chlorine;
the chlorine vaporizer is connected with a hot water tank which provides energy for the chlorine vaporizer to vaporize chlorine; an electric heater and a temperature sensor are arranged in the hot water tank;
the pipeline between the distillation tower and the acid liquor tower is connected with a metal float flowmeter and an electric control valve, the pipeline between the distillation tower and the chlorine gas vaporizer is connected with a metal float flowmeter and an electric control valve, the metal float flowmeter and the electric control valve are electrically connected with an automatic control cabinet, and the automatic control cabinet is provided with a control main board and a touch screen.
9. The apparatus for producing bromine of claim 8 further comprising an automatic sampling detection system; the automatic sampling detection system comprises a reaction kettle, automatic sampling equipment and an automatic analyzer, wherein the automatic sampling equipment and the automatic analyzer are connected with the reaction kettle;
the automatic sampling equipment is connected with the automatic analyzer, the automatic analyzer is connected with the industrial personal computer in a wireless network manner, the industrial personal computer is connected with the alarm, the industrial personal computer is also connected with the DCS system, the DCS system is connected with the electromagnetic control valve, and the DCS system can control the electromagnetic control valve to control the chlorine tower and the hydrochloric acid tower;
automatic sampling equipment includes sample pipeline and relief pressure valve, sample pipeline and reation kettle intercommunication, and the relief pressure valve is located sample pipeline, and the clean water tank of upper portion pipe connection of sample pipeline is equipped with the control valve on the pipeline of clean water tank and sample pipeline connection, and the lower part of sample pipeline is equipped with the air pump.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117430089A (en) * | 2023-12-20 | 2024-01-23 | 山东菜央子盐场有限公司 | Method for extracting bromine from brine by gaseous membrane method |
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