A process system for concentrating bromine from seawater

Abstract

The application relates to a seawater concentration bromine extraction process system and belongs to the technical field of salt chemical industry and new energy. The patent adopts a variety of novel waste heat deep recovery process methods and special equipment, recovers the waste heat resources of all process sections of the plant including the waste heat of high-temperature waste liquid of a bromine extraction distillation section to the maximum extent and uses the waste heat for process heating, greatly reduces the load demand of an external heat source by 70%-90%, and supplies the heating steam of a bromine extraction distillation tower and the liquid chlorine gasification heat source demand through the following modes: a high-temperature SO2 flue gas waste heat boiler of a sulfur incinerator, a bromine steam discharged from the bromine extraction distillation tower is condensed by a high-temperature condensation waste heat pump, electric heating based on photovoltaic and wind power generation and the like, and boiler steam, so that the original boiler steam and fossil fuel consumption are completely replaced, the original boiler is changed into an emergency standby heat source, and energy operation cost is remarkably reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to a seawater concentration bromine extraction process system, belonging to the field of salt chemical industry and new energy technology. BACKGROUND

[0002] The patent aims to shut down the steam boiler in the seawater concentration bromine extraction production workshop, through greatly adjusting the energy production and use mode, building a new thermal process and using new energy power driving, etc., to realize a new energy supply and driving system.

[0003] The basic principles, process flow, energy production, distribution, use and discharge of seawater concentration bromine extraction are briefly introduced as follows.

[0004] Based on the salt chemical plant of seawater salt making, bromine, lithium and other substances can be extracted from seawater or concentrated bitter brine after salt making, and the basic principle of the commonly used "chlorine gas oxidation air blowing method for bromine production" is as follows.

[0005] Under acidic conditions, bromide ions (Br-) are oxidized to bromine molecules (Br2) using chlorine gas as an oxidizing agent, and the ionic reaction formula is as follows.

[0006] 2Br- + Cl2 = Br2 + 2 Cl-.

[0007] The free bromine is blown out with air, so it is called air blowing method.

[0008] Acidic bromine production uses sulfur dioxide as an absorbent, and fresh water spray is used to assist the absorption of air and bromine mixture, and the absorption completed liquid is called primary acid, and the chemical reaction formula is as follows.

[0009] Br2 + SO2 + 2H2O = 2HBr + H2SO4.

[0010] The primary acid is passed into chlorine gas for oxidation, and bromine is re- released, and hydrochloric acid is generated, and the chemical reaction formula is as follows.

[0011] 2HBr + Cl2 = 2HCl + Br2.

[0012] Finally, bromine is distilled out with water vapor, separated by condensation, and the finished product bromine is obtained.

[0013] The process flow is described as follows.

[0014] The seawater (brine) is pumped into the blowing tower, dilute acid and chlorine are added into the outlet pipe of the pump, the mixed acidified chlorinated brine is sprayed from the upper part of the blowing tower and falls down, the air is blown from the bottom of the tower by the air blower, when the brine contacts with the air, the free bromine in the brine is stripped and blown out. The blown waste liquid is discharged from the bottom of the blowing tower and is used for salt making. The mixed gas discharged from the top of the blowing tower is sent into the absorption tower and is mixed and absorbed by sulfur dioxide and water mist, the formed finished liquid is called primary acid, the air after purification by the air trap is blown by the air blower and enters the bottom of the blowing tower and is used in the system. The primary acid is added from the top of the distillation tower, water vapor and chlorine are introduced from the bottom, when the primary acid flows along the filler from top to bottom, it contacts with the chlorine and water vapor from bottom to top, and is continuously oxidized and distilled, the bromine and water vapor mixed gas is discharged from the top of the tower, is condensed and separated, and the liquid bromine is prepared, and the crude bromine water is returned to the absorption tower for continuous circulation.

[0015] The chlorine is usually prepared by gasification of liquid chlorine through a water bath tank, and the process is as follows: the liquid chlorine is sent into the water bath bottle, the bottle nozzle is connected with the chlorine clamp tightly, the water bath tank is filled with water, and the water in the tank is heated by steam, the temperature is controlled at 75-83℃ by the electromagnetic valve, the temperature range can realize the gasification of liquid chlorine and avoid the generation of explosive nitrogen trichloride, and the gasified chlorine is supplied.

[0016] The preparation process of SO2 gas is as follows: the sulfur is fed into the sulfur combustion furnace through the distributor, burns with the oxygen in the air blown in at high temperature to generate sulfur dioxide gas, is cooled by air and washed by circulating water, the temperature is controlled below 70℃, and then is introduced into the blowing and absorption tower for reduction and absorption to prepare the finished liquid for bromine production.

[0017] The distillation process for bromine extraction is as follows: the finished liquid is preheated by the recovered liquid, is introduced into the distillation tower and is oxidized by chlorine, and is distilled by water vapor at the same time, the bromine is distilled out, the temperature at the top of the tower is controlled at 80-90℃, and the crude bromine is prepared after condensation, the bromine distillation recovered liquid is cooled by brine heat exchange and then is introduced into the collection tank, and is then used for brine acidification.

[0018] There is obvious energy waste in the above-mentioned traditional seawater bromine extraction process, for example: the high-temperature flue gas (up to 600-700℃) generated when the sulfur combustion furnace prepares SO2 gas is usually not recovered due to its strong corrosiveness and small flue gas volume, but is directly introduced into the water washing tower for spraying and cooling to 50-60℃; the waste sulfuric acid liquid SH1 is usually not recovered due to its strong corrosiveness, small flow and low temperature grade, and is finally wasted; the steam bromine recovery liquid discharged from the bromine extraction distillation column is usually recovered by a special heat exchanger, but the original special heat exchanger has poor heat transfer performance and high cost, and the amount of recovered waste heat is relatively small, so that the discharge temperature of the steam bromine recovery liquid is usually still as high as 50-60℃ or above, the waste heat in the low-temperature section is still wasted, and the amount of water vapor added is relatively large, resulting in high energy consumption and operating cost. In summary, due to the strong corrosiveness and small flow of the flue gas and process water, a large proportion of waste heat resources is wasted, and it is necessary to recover and utilize the waste heat to achieve energy saving and consumption reduction. SUMMARY

[0019] The purpose and task of the present application is to fundamentally abandon the fossil energy-driven power system and transform into a new energy power system by adopting a new energy production, transportation and utilization method in view of the inherent technical limitations in the above-mentioned seawater bromine extraction process.

[0020] The specific description of the present application is: a seawater concentration bromine extraction process system, which is composed of a seawater concentration and air blowing method bromine extraction subsystem, a sulfur combustion furnace SO2 flue gas preparation subsystem, a liquid chlorine gasification subsystem, a bromine extraction distillation liquid bromine preparation subsystem, a combustion furnace high-temperature waste heat flash steam boiler subsystem, a bromine extraction distillation process waste heat deep recovery subsystem and connecting pipelines and components thereof, wherein the seawater concentration and air blowing method bromine extraction subsystem comprises a salt field 40, a bitter brine pump 41, an air blowing tower 42 and connecting pipelines and components thereof, the liquid chlorine gasification subsystem comprises a liquid chlorine gasification tank 50, a water bath tank 51 and connecting pipelines and components thereof, the sulfur combustion furnace SO2 flue gas preparation subsystem comprises a sulfur combustion furnace 1, an ash settling tank 2, a high-temperature SO2 flue 3, a water washing tower 4, a clean SO2 flue gas pipe 5, a Roots blower 6, a water washing pump 7, an absorption tower 9 and connecting pipelines and components thereof, and the bromine extraction distillation liquid bromine preparation subsystem comprises a bromine extraction distillation tower 31, a bromine vapor exhaust pipe 32, a bromine vapor condenser 33, a waste liquid pump 34, a waste liquid heat recovery device 35 and connecting pipelines and components thereof, characterized in that the combustion furnace high-temperature waste heat flash steam boiler subsystem comprises a heat exchange sleeve 20, a heat exchange pipe 26, a miniature high-temperature waste heat water boiler 10, a feed water pump 16, a flash tank 23, a blower 21, a compressed working medium storage tank 22, a mixed air door 19 and connecting pipelines and components thereof, and the bromine extraction distillation process waste heat deep recovery subsystem comprises a high-efficiency corrosion-resistant deep heat recovery device 36, a high-temperature heat pump steam device 37 and a new energy electric heating steam furnace 38 and connecting pipelines and components thereof; wherein the feed inlet of the upper part of the air blowing tower 42 is communicated with the water inlet pipe of sulfuric acid SH, the gas inlet pipe of chlorine gas CL and the outlet of the bitter brine pump 41 respectively, the inlet of the bitter brine pump 41 is connected with the bitter brine outlet of the salt field 40, the salt field 40 is provided with an inlet of seawater Ws and an outlet of coarse salt Na, the lower part of the air blowing tower 42 is provided with an inlet of ambient air A, the bottom is provided with a drainage outlet of acidic wastewater P, and the top is a bromine and air mixed gas BrA exhaust outlet connected with the bromine and air mixed gas BrA inlet of the lower part of the absorption tower 9; the chlorine gas CL inlet of the air blowing tower 42 is connected with the chlorine gas outlet of the liquid chlorine gasification tank 50, the lower part of the liquid chlorine gasification tank 50 is provided with a liquid chlorine CLy, and the liquid chlorine gasification tank 50 is arranged in the tank of the water bath tank 51, which is provided with an inlet of heat source steam / water H1 and an outlet of heat source return water H2; the upper part of the absorption tower 9 is provided with an inlet of absorption spraying water R, the bottom is provided with a liquid outlet of finished liquid BrH, and the top is provided with an inlet of clean SO2 flue gas S2.The air inlet of the sulfur combustion furnace 1 is provided with a sulfur S inlet and an air inlet, wherein the air inlet is communicated with the ambient air A through a Roots blower 6, the exhaust end of the sulfur combustion furnace 1 is provided with an outlet of high-temperature SO2 flue gas S1, and is connected with the inlet of the fly ash settling tank 2; the outlet of the fly ash settling tank 2 is connected with the inlet of the high-temperature SO2 flue 3; the connection between the high-temperature SO2 flue 3 and the water washing tower 4 is the cooling SO2 flue gas S3; the top exhaust port of the water washing tower 4 is connected with the top air inlet of the absorption tower 9 through a clean SO2 flue gas pipe 5; the bottom liquid outlet of the water washing tower 4 is connected with the inlet of the water washing pump 7; the outlet of the water washing pump 7 is connected with the circulating water inlet of the water washing tower 4, the water inlet pipe of the water supplement B and the waste sulfuric acid liquid SH1 drainage pipe respectively; the outer side of the high-temperature SO2 flue 3 is provided with a heat exchange sleeve 26, and the closed annular space between the two is a region for flow heat exchange of the heat exchange medium; the air inlet of the heat exchange sleeve 26 is arranged at one end of the cooling SO2 flue gas S3, and the air outlet of the heat exchange sleeve 26 is arranged at one end of the high-temperature SO2 flue gas S1 air inlet; the outer side of the sulfur combustion furnace 1 is provided with a heat exchange sleeve 20, and the closed annular space between the two is a region for flow heat exchange of the heat exchange medium; the air inlet of the heat exchange sleeve 20 is arranged at one end of the sulfur combustion furnace 1 exhaust port, and the air outlet of the heat exchange sleeve 20 is arranged at one end of the sulfur combustion furnace 1 air inlet; the air outlet of the heat exchange sleeve 20 is connected with the high-pressure inlet of the mixed air door 19 and the inlet of the inlet rectifying section 11 of the micro high-temperature waste heat boiler 10; the micro high-temperature waste heat boiler 10 further comprises an outer shell 12, an ultra-large temperature difference heat exchanger 13 and an outlet tapered section; the medium-temperature heat exchange medium outlet of the outlet tapered section is connected with the low-pressure outlet of the mixed air door 19, the inlet of the air blower 21 and the air outlet of the compressed medium storage tank 22; the air outlet of the air blower 21 is connected with the air inlet of the heat exchange sleeve 26; the air outlet of the heat exchange sleeve 26 is connected with the air inlet of the heat exchange sleeve 20; the water inlet of the ultra-large temperature difference heat exchanger 13 is connected with the outlet of the water supply pump 16; the water outlet of the ultra-large temperature difference heat exchanger 13 is connected with the high-temperature water inlet of the flash tank 23; the medium-temperature water outlet of the flash tank 23 is communicated with the inlet of the water supply pump 16 and the water supply pipe of the desalted water supplement Bc; the outlet of the secondary steam Q2 at the top of the flash tank 23 is connected with the inlet of the heat source steam / water H1 of the water bath tank 51, the inlet of the heating steam Q of the bromine distillation tower 31, the outlet of the primary steam Q1 of the new energy electric heating steam furnace 38 and the outlet of the third steam Q3 of the high-temperature heat pump steam device 37 respectively; the new energy electric heating steam furnace 38 is further provided with the inlet of the electric boiler water supplement W2; the inside of the new energy electric heating steam furnace 38 is provided with an electric heater 39; the two ends of the electric heater 39 are connected with the power supply line of the new energy power supply E respectively.The low-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device 36 is connected with the liquid outlet at the bottom of the absorption tower 9 through a liquid BrH supply pipe, the low-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device 36 is connected with the low-temperature side inlet of the original waste liquid heat recovery device 35, the low-temperature side outlet of the original waste liquid heat recovery device 35 is connected with the liquid inlet at the upper part of the bromine extraction distillation tower 31, the chlorine gas CL inlet at the lower part of the bromine extraction distillation tower 31 is connected with the chlorine gas outlet of the liquid chlorine gasification tank 50, the liquid outlet at the bottom of the bromine extraction distillation tower 31 is connected with the inlet of the waste liquid pump 34, the outlet of the waste liquid pump 34 is connected with the high-temperature side inlet of the original waste liquid heat recovery device 35, the high-temperature side outlet of the original waste liquid heat recovery device 35 is connected with the high-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device 36, and the high-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device 36 is communicated with the water return pipe of the bromine extraction waste liquid SH2; the top of the bromine extraction distillation tower 31 is a gathering area of bromine and water vapor mixed gas Br1, the top gas outlet is connected with the gas inlet at the upper part of the bromine vapor condenser 33 through a bromine vapor exhaust pipe 32, the liquid outlet at the lower part of the bromine vapor condenser 33 is communicated with the water outlet pipe of the liquid bromine Br, and the liquid outlet of the crude bromine water Br at the bottom of the bromine vapor condenser 33 is connected with the liquid inlet at the upper part of the bromine extraction distillation tower 31; the cooling water outlet of the bromine vapor condenser 33 is connected with the low-temperature heat source inlet of the high-temperature heat pump steam device 37 through a cooling water return pipe C2, the cooling water inlet of the bromine vapor condenser 33 is connected with the low-temperature heat source outlet of the high-temperature heat pump steam device 37 through a cooling water inlet pipe C1, the heating side inlet of the high-temperature heat pump steam device 37 is communicated with the water inlet pipe of the heat pump water supply W3, and the heating side outlet of the high-temperature heat pump steam device 37 is the outlet of the third steam Q3.

[0021] The water outlet pipe section of the super-large temperature difference heat exchanger 13 is provided with a safety valve group 14 and a water supply temperature sensor 15, the flue gas outlet pipe section of the sulfur combustion furnace 1 is provided with a combustion furnace flue gas temperature sensor 17, the outlet pipe section of the air blower 21 is provided with a mixed smoke temperature sensor 18, and the connection between the high-temperature SO2 flue 3 and the water washing tower 4 is provided with a medium-temperature flue gas sensor 27; wherein the operation temperature of the water supply temperature sensor 15 is controlled by the opening degree of the electric regulating valve at the outlet of the water supply pump 16, and the low-limit temperature of the mixed smoke temperature sensor 18 is controlled by the opening degree of the mixed air door 19; the low-limit temperature of the combustion furnace flue gas temperature sensor 17 and the low-limit temperature of the medium-temperature flue gas sensor 27 are both controlled by the flow rate of the air blower 21 adjusted by a frequency converter or an air inlet guide vane.

[0022] The working medium in the compressed working medium storage tank 22 is high-pressure nitrogen or compressed air.

[0023] The material of the heat exchange sleeve 20 is carbon steel or boiler steel, and an insulation layer is arranged or not arranged outside; the material of the heat exchange sleeve 26 is carbon steel or boiler steel, and an insulation layer is arranged outside.

[0024] The super large temperature difference heat exchanger 13 adopts a serpentine coil structure, a transverse or longitudinal tube bundle structure, a plate structure or a tube-plate structure; when the transverse or longitudinal tube bundle structure is adopted, the heat exchange pipe adopts a light pipe or finned pipe structure; and the heat exchange material of the super large temperature difference heat exchanger 13 adopts carbon steel, ND steel, stainless steel 304 or stainless steel 316L.

[0025] The material of the feed water pump 16 adopts a high-temperature cast iron pump or a stainless steel water pump.

[0026] The high-efficiency corrosion-resistant deep heat recovery device 36 adopts a high-efficiency graphene plastic pipe heat exchanger; and the original waste liquid heat recovery device 35 adopts a silicon carbide heat exchanger, a glass heat exchanger and / or a fluoroplastic heat exchanger.

[0027] The heat pump host of the high-temperature heat pump steam device 37 adopts a single-stage voltage compression type high-temperature heat pump type, and a series electric heater generates water vapor.

[0028] The innovation points and beneficial effects of the present application are as follows.

[0029] (1) A new energy production, transportation, use and distribution method is adopted to realize the process energy and power driving of seawater concentration and bromine extraction, including greatly adjusting the energy production, transportation, use and distribution process flow in the process production, greatly reducing the energy consumption through energy-saving measures, and fundamentally abandoning the power system driven by fossil energy through the use of waste heat steam, heat pump steam, new energy power generation and electric heat steam.

[0030] (2) In view of the strong corrosive nature of high-temperature SO2 flue gas, the present patent is based on the acid dew point control method, which ensures that the temperature of the inner wall of the sulfur combustion furnace shell and the flue gas exhaust pipe in contact with the flue gas is always maintained above the acid dew point, so as to ensure that there is no acid dew point corrosion, and to ensure that the original equipment system in the waste heat recovery process will not have corrosion problems.

[0031] (3) The present patent adopts the method of setting a sleeve outside the sulfur combustion furnace shell and the high-temperature flue gas pipe thereafter, and exchanging heat through the annular area, and the heat exchange medium is nitrogen or air, which has no corrosive nature, so that common boiler steel, such as carbon steel, ND steel, stainless steel 304 or stainless steel 316L, can be used as the heat exchange pipe material, thereby greatly reducing the processing difficulty and cost of the heat exchanger and the entire waste heat boiler, and solving the problem of sulfur combustion furnace flue gas waste heat recovery.

[0032] (4) The waste heat boiler can produce high-parameter waste heat water, and can also produce 0.1-0.6 MPa level saturated wet steam through a flash tank, which is more convenient for recycling in process production.

[0033] (5) By precisely controlling the most critical boiler water supply temperature to meet the parameter needs of external heat source; control the sleeve inlet temperature and the combustion furnace exhaust temperature to avoid serious corrosion problems, ensure the safe, stable and reliable operation of the equipment, improve the service life, and significantly reduce the whole cycle operation cost. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is the system schematic diagram of the conventional production process of seawater concentration and bromine extraction, Figure 2 is the system schematic diagram of the present application.

[0035] Figure 1 , 2 The numbers and names of the components in the figure are as follows.

[0036] Sulfur combustion furnace 1, fly ash settling tank 2, high-temperature SO2 flue 3, water washing tower 4, clean SO2 flue gas pipe 5, Roots blower 6, water washing pump 7, original heat exchanger 8, absorption tower 9, miniature high-temperature waste heat hot water boiler 10, import rectifier section 11, shell 12, super large temperature difference heat exchanger 13, safety valve group 14, water supply temperature sensor 15, water supply pump 16, combustion furnace exhaust temperature sensor 17, mixed smoke temperature sensor 18, combustion furnace exhaust temperature sensor 17, mixed smoke temperature sensor 18, mixed air door 19, heat exchange sleeve 20, air blower 21, compressed working medium gas storage tank 22, flash tank 23, heat exchange sleeve 26, medium-temperature flue gas sensor 27, bromine extraction distillation tower 31, bromine vapor exhaust pipe 32, bromine vapor condenser 33, waste liquid pump 34, original waste liquid heat recovery device 35, high-efficiency corrosion-resistant deep heat recovery device 36, high-temperature heat pump steam device 37, new energy electric heating steam furnace 38, electric heater 39, salt field 40, bitter brine pump 41, air blowing tower 42, chlorine gas tank 50, water bath 51, coal or gas-fired boiler 60, air blower 61, environmental air A, water supplement B, desalted water supplement Bc, liquid bromine Br, bromine and water vapor mixture Br1, crude bromine water Br2, bromine and air mixture BrA, finished liquid BrH, cooling incoming water C1, cooling outgoing water C2, chlorine gas CL, liquid chlorine CLy, new energy source E, heat source steam / water H1, heat source outgoing water H2, crude salt Na, heating steam Q, new steam Q0, primary steam Q1, secondary steam Q2, third steam Q3, spray water R, sulfur S, high-temperature SO2 flue gas S1, clean SO2 flue gas S2, cooling SO2 flue gas S3, sulfuric acid SH, waste sulfuric acid liquid SH1, bromine extraction waste liquid SH2, boiler feed water W1, electric boiler water supplement W2, heat pump feed water W3, seawater Ws. DETAILED DESCRIPTION

[0037] Figure 1 is the system schematic diagram and embodiment of the conventional production process of seawater concentration and bromine extraction, Figure 2 is the system schematic diagram and embodiment of the present application.

[0038] The system diagram and embodiment of the conventional production process of seawater concentration and bromine extraction are shown in Figure 1 The system is composed of the original seawater concentration and air blowing method bromine extraction subsystem, the original sulfur combustion furnace SO2 flue gas preparation subsystem, the original liquid chlorine gasification subsystem, the original bromine extraction distillation liquid bromine preparation subsystem, the steam boiler subsystem and their connecting pipelines and components. The original seawater concentration and air blowing method bromine extraction subsystem includes the salt field 40, the brine pump 41, the air blowing tower 42 and their connecting pipelines and components. The original liquid chlorine gasification subsystem includes the liquid chlorine gasification tank 50, the water bath tank 51 and their connecting pipelines and components. The original sulfur combustion furnace SO2 flue gas preparation subsystem includes the sulfur combustion furnace 1, the fly ash settling tank 2, the high-temperature SO2 flue 3, the water washing tower 4, the clean SO2 flue gas pipe 5, the Roots blower 6, the water washing pump 7, the absorption tower 9 and their connecting pipelines and components. The original bromine extraction distillation liquid bromine preparation subsystem includes the bromine extraction distillation tower 31, the bromine vapor exhaust pipe 32, the bromine vapor condenser 33, the waste liquid pump 34, the original waste liquid heat recovery device 35 and their connecting pipelines and components. The steam boiler subsystem includes the coal or gas boiler 60, the air blower 61 and their connecting pipelines and components. The outlet of the new steam Q0 of the coal or gas boiler 60 is connected with the inlet of the heat source steam / water H1 of the water bath tank 51 and the inlet of the heating steam Q of the bromine extraction distillation tower 31 respectively. The coal or gas boiler 60 is also provided with the inlet of the boiler feed water W1. The combustion-supporting air inlet of the coal or gas boiler 60 is connected with the air outlet of the air blower 61. The air inlet of the air blower 61 is communicated with the ambient air (A).

[0039] The specific embodiments of the present application are as follows, which are shown in Figure 2The specific description of the application is: a seawater concentration bromine extraction process system, which is composed of a seawater concentration and air blowing method bromine extraction subsystem, a sulfur combustion furnace SO2 flue gas preparation subsystem, a liquid chlorine gasification subsystem, a bromine extraction distillation liquid bromine preparation subsystem, a combustion furnace high-temperature waste heat flash steam boiler subsystem, a bromine extraction distillation process waste heat deep recovery subsystem and connecting pipelines and components thereof. The seawater concentration and air blowing method bromine extraction subsystem includes a salt field 40, a bitter brine pump 41, an air blowing tower 42 and connecting pipelines and components thereof. The liquid chlorine gasification subsystem includes a liquid chlorine gasification tank 50, a water bath tank 51 and connecting pipelines and components thereof. The sulfur combustion furnace SO2 flue gas preparation subsystem includes a sulfur combustion furnace 1, an ash settling tank 2, a high-temperature SO2 flue 3, a water washing tower 4, a clean SO2 flue gas pipe 5, a Roots blower 6, a water washing pump 7, an absorption tower 9 and connecting pipelines and components thereof. The bromine extraction distillation liquid bromine preparation subsystem includes a bromine extraction distillation tower 31, a bromine vapor exhaust pipe 32, a bromine vapor condenser 33, a waste liquid pump 34, a waste liquid heat recovery device 35 and connecting pipelines and components thereof. The combustion furnace high-temperature waste heat flash steam boiler subsystem includes a heat exchange sleeve 20, a heat exchange pipe 26, a miniature high-temperature waste heat water boiler 10, a feed water pump 16, a flash tank 23, a blower 21, a compressed working medium storage tank 22, a mixed air door 19 and connecting pipelines and components thereof. The bromine extraction distillation process waste heat deep recovery subsystem includes a high-efficiency corrosion-resistant deep heat recovery device 36, a high-temperature heat pump steam device 37 and a new energy electric heating steam furnace 38 and connecting pipelines and components thereof. The air blowing tower 42 upper inlet is communicated with the sulfuric acid SH water inlet pipe, the chlorine gas CL gas inlet pipe and the bitter brine pump 41 outlet respectively. The bitter brine pump 41 inlet is connected with the bitter brine outlet of the salt field 40. The salt field 40 is provided with a seawater Ws inlet and a coarse salt Na outlet. The air blowing tower 42 lower part is provided with an ambient air A inlet. The bottom is provided with an acidic wastewater P drain port. The top is a bromine and air mixture BrA exhaust port, which is connected with the bromine and air mixture BrA inlet of the lower part of the absorption tower 9. The chlorine gas CL gas inlet of the air blowing tower 42 is connected with the chlorine gas outlet of the liquid chlorine gasification tank 50. The lower part of the liquid chlorine gasification tank 50 is provided with a liquid chlorine CLy. The liquid chlorine gasification tank 50 is arranged in the tank of the water bath tank 51. The water bath tank 51 is provided with a heat source steam / water H1 inlet and a heat source return water H2 outlet. The upper part of the absorption tower 9 is provided with an absorption spray water R inlet. The bottom is provided with a completed liquid BrH drain port. The top is provided with a clean SO2 flue gas S2 inlet.The air inlet of the sulfur combustion furnace 1 is provided with a sulfur S inlet and an air inlet, wherein the air inlet is communicated with the ambient air A through a Roots blower 6, the exhaust end of the sulfur combustion furnace 1 is provided with an outlet of high-temperature SO2 flue gas S1, and is connected with the inlet of the fly ash settling tank 2; the outlet of the fly ash settling tank 2 is connected with the inlet of the high-temperature SO2 flue 3; the connection between the high-temperature SO2 flue 3 and the water washing tower 4 is the cooling SO2 flue gas S3; the top exhaust port of the water washing tower 4 is connected with the top air inlet of the absorption tower 9 through a clean SO2 flue gas pipe 5; the bottom liquid outlet of the water washing tower 4 is connected with the inlet of the water washing pump 7; the outlet of the water washing pump 7 is connected with the circulating water inlet of the water washing tower 4, the water inlet pipe of the water supplement B and the waste sulfuric acid liquid SH1 drainage pipe respectively; the outer side of the high-temperature SO2 flue 3 is provided with a heat exchange sleeve 26, and the closed annular space between the two is a region for flow heat exchange of the heat exchange medium; the air inlet of the heat exchange sleeve 26 is arranged at one end of the cooling SO2 flue gas S3, and the air outlet of the heat exchange sleeve 26 is arranged at one end of the high-temperature SO2 flue gas S1 air inlet; the outer side of the sulfur combustion furnace 1 is provided with a heat exchange sleeve 20, and the closed annular space between the two is a region for flow heat exchange of the heat exchange medium; the air inlet of the heat exchange sleeve 20 is arranged at one end of the sulfur combustion furnace 1 exhaust port, and the air outlet of the heat exchange sleeve 20 is arranged at one end of the sulfur combustion furnace 1 air inlet; the air outlet of the heat exchange sleeve 20 is connected with the high-pressure inlet of the mixed air door 19 and the inlet of the inlet rectifying section 11 of the micro high-temperature waste heat boiler 10; the micro high-temperature waste heat boiler 10 further comprises an outer shell 12, an ultra-large temperature difference heat exchanger 13 and an outlet tapered section; the medium-temperature heat exchange medium outlet of the outlet tapered section is connected with the low-pressure outlet of the mixed air door 19, the inlet of the air blower 21 and the air outlet of the compressed medium storage tank 22; the air outlet of the air blower 21 is connected with the air inlet of the heat exchange sleeve 26; the air outlet of the heat exchange sleeve 26 is connected with the air inlet of the heat exchange sleeve 20; the water inlet of the ultra-large temperature difference heat exchanger 13 is connected with the outlet of the water supply pump 16; the water outlet of the ultra-large temperature difference heat exchanger 13 is connected with the high-temperature water inlet of the flash tank 23; the medium-temperature water outlet of the flash tank 23 is communicated with the inlet of the water supply pump 16 and the water supply pipe of the desalted water supplement Bc; the outlet of the secondary steam Q2 at the top of the flash tank 23 is connected with the inlet of the heat source steam / water H1 of the water bath tank 51, the inlet of the heating steam Q of the bromine distillation tower 31, the outlet of the primary steam Q1 of the new energy electric heating steam furnace 38 and the outlet of the third steam Q3 of the high-temperature heat pump steam device 37 respectively; the new energy electric heating steam furnace 38 is further provided with the inlet of the electric boiler water supplement W2; the inside of the new energy electric heating steam furnace 38 is provided with an electric heater 39; the two ends of the electric heater 39 are connected with the power supply line of the new energy power supply E respectively.The low-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device 36 is connected with the liquid outlet at the bottom of the absorption tower 9 through a liquid BrH supply pipe, the low-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device 36 is connected with the low-temperature side inlet of the original waste liquid heat recovery device 35, the low-temperature side outlet of the original waste liquid heat recovery device 35 is connected with the liquid inlet at the upper part of the bromine extraction distillation tower 31, the chlorine gas CL inlet at the lower part of the bromine extraction distillation tower 31 is connected with the chlorine gas outlet of the liquid chlorine gasification tank 50, the liquid outlet at the bottom of the bromine extraction distillation tower 31 is connected with the inlet of the waste liquid pump 34, the outlet of the waste liquid pump 34 is connected with the high-temperature side inlet of the original waste liquid heat recovery device 35, the high-temperature side outlet of the original waste liquid heat recovery device 35 is connected with the high-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device 36, and the high-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device 36 is communicated with the water return pipe of the bromine extraction waste liquid SH2; the top of the bromine extraction distillation tower 31 is a gathering area of bromine and water vapor mixed gas Br1, the top gas outlet is connected with the gas inlet at the upper part of the bromine vapor condenser 33 through a bromine vapor exhaust pipe 32, the liquid outlet at the lower part of the bromine vapor condenser 33 is communicated with the water outlet pipe of the liquid bromine Br, and the liquid outlet of the crude bromine water Br at the bottom of the bromine vapor condenser 33 is connected with the liquid inlet at the upper part of the bromine extraction distillation tower 31; the cooling water outlet of the bromine vapor condenser 33 is connected with the low-temperature heat source inlet of the high-temperature heat pump steam device 37 through a cooling water return pipe C2, the cooling water inlet of the bromine vapor condenser 33 is connected with the low-temperature heat source outlet of the high-temperature heat pump steam device 37 through a cooling water inlet pipe C1, the heating side inlet of the high-temperature heat pump steam device 37 is communicated with the water inlet pipe of the heat pump water supply W3, and the heating side outlet of the high-temperature heat pump steam device 37 is the outlet of the third steam Q3.

[0040] The water outlet pipe section of the super-large temperature difference heat exchanger 13 is provided with a safety valve group 14 and a water supply temperature sensor 15, the flue gas outlet pipe section of the sulfur combustion furnace 1 is provided with a combustion furnace flue gas temperature sensor 17, the outlet pipe section of the air blower 21 is provided with a mixed smoke temperature sensor 18, and the connection between the high-temperature SO2 flue 3 and the water washing tower 4 is provided with a medium-temperature flue gas sensor 27; wherein the operation temperature of the water supply temperature sensor 15 is controlled by the opening degree of the electric regulating valve at the outlet of the water supply pump 16, and the low-limit temperature of the mixed smoke temperature sensor 18 is controlled by the opening degree of the mixed air door 19; the low-limit temperature of the combustion furnace flue gas temperature sensor 17 and the low-limit temperature of the medium-temperature flue gas sensor 27 are both controlled by the flow rate of the air blower 21 adjusted by a frequency converter or an air inlet guide vane.

[0041] The working medium in the compressed working medium storage tank 22 is high-pressure nitrogen or compressed air.

[0042] The material of the heat exchange sleeve 20 is carbon steel or boiler steel, and an insulation layer is arranged or not arranged outside; the material of the heat exchange sleeve 26 is carbon steel or boiler steel, and an insulation layer is arranged outside.

[0043] The super large temperature difference heat exchanger 13 adopts a serpentine coil structure, a transverse or longitudinal tube bundle structure, a plate structure or a tube-plate structure; when the transverse or longitudinal tube bundle structure is adopted, the heat exchange pipe adopts a light pipe or a finned pipe structure; and the heat exchange material of the super large temperature difference heat exchanger 13 adopts carbon steel, ND steel, stainless steel 304 or stainless steel 316L.

[0044] The material of the feed water pump 16 adopts a high-temperature cast iron pump or a stainless steel water pump.

[0045] The high-efficiency corrosion-resistant deep heat recovery device 36 adopts a high-efficiency graphene plastic pipe heat exchanger; and the original waste liquid heat recovery device 35 adopts a silicon carbide heat exchanger, a glass heat exchanger and / or a fluoroplastic heat exchanger.

[0046] The heat pump main machine of the high-temperature heat pump steam device 37 adopts a single-stage voltage compression type high-temperature heat pump type, and a series electric heater generates water vapor.

[0047] It should be noted that the present application constructs a brand new energy power system for seawater concentration and bromine extraction, and different specific implementation measures and specific implementation devices with different structures can be adopted according to the solution, and the above specific implementation mode is only one implementation type, and any other similar simple transformation mode, such as simple increase, reduction, transformation and change of relative position of internal components and interfaces, simple combination and adjustment of external pipelines and components, etc., all fall within the protection scope of the present application.

Claims

1. A seawater concentration bromine extraction process system, which is composed of a seawater concentration and air blowing method bromine extraction subsystem, a sulfur combustion furnace SO2 flue gas subsystem, a liquid chlorine gasification subsystem, a bromine extraction distillation liquid bromine subsystem, a combustion furnace high-temperature waste heat flash steam boiler subsystem, a bromine extraction distillation process waste heat deep recovery subsystem, and connecting pipelines and components thereof, wherein the seawater concentration and air blowing method bromine extraction subsystem includes a salt field (40), a brine pump (41), an air blowing tower (42), and connecting pipelines and components thereof, the liquid chlorine gasification subsystem includes a liquid chlorine gasification tank (50), a water bath tank (51), and connecting pipelines and components thereof, the sulfur combustion furnace SO2 flue gas subsystem includes a sulfur combustion furnace (1), an ash settling tank (2), a high-temperature SO2 flue (3), a water washing tower (4), a clean SO2 flue gas pipe (5), a Roots blower (6), a water washing pump (7), an absorption tower (9), and connecting pipelines and components thereof, the bromine extraction distillation liquid bromine subsystem includes a bromine extraction distillation tower (31), a bromine vapor exhaust pipe (32), a bromine vapor condenser (33), a waste liquid pump (34), a waste liquid heat recovery device (35), and connecting pipelines and components thereof, and the characteristic is that, The high-temperature waste heat flash steam boiler subsystem of the combustion furnace comprises a heat exchange sleeve (20), a heat exchange pipe (26), a micro high-temperature waste heat water boiler (10), a feed water pump (16), a flash tank (23), a blower (21), a compressed working medium storage tank (22), a mixed air door (19) and connecting pipelines and components thereof, the deep waste heat recovery subsystem of the bromine extraction distillation process comprises a high-efficiency corrosion-resistant deep heat recovery device (36), a high-temperature heat pump steam device (37), a new energy electric heating steam furnace (38) and connecting pipelines and components thereof, the air blowing tower (42) is provided with a feed inlet at the upper portion thereof, which is communicated with a water inlet pipe of sulfuric acid, an air inlet pipe of chlorine and an outlet of a bitter brine pump (41), the bitter brine pump (41) is connected with a bitter brine outlet of a salt field (40), the salt field (40) is provided with a seawater inlet and a coarse salt outlet, the air blowing tower (42) is provided with an ambient air inlet at the lower portion thereof, an acidic wastewater outlet at the bottom and a bromine and air mixture outlet at the top, and the bromine and air mixture outlet is connected with an air mixture inlet of a lower portion of an absorption tower (9), a chlorine inlet of the air blowing tower (42) is connected with a chlorine outlet of a liquid chlorine gasification tank (50), the lower portion of the liquid chlorine gasification tank (50) is provided with a liquid inlet of liquid chlorine, the liquid chlorine gasification tank (50) is arranged in a water bath tank (51), and the water bath tank (51) is provided with a heat source steam / water inlet and a heat source outlet; the upper portion of the absorption tower (9) is provided with an absorption spray water inlet, the bottom is provided with a complete liquid outlet, and the top is provided with a clean SO2 flue gas inlet; the air inlet pipe of the sulfur combustion furnace (1) is provided with a sulfur inlet and an air inlet, the air inlet is communicated with ambient air through a Roots blower (6), the flue gas outlet of the sulfur combustion furnace (1) is connected with an inlet of an ash settling tank (2), the outlet of the ash settling tank (2) is connected with an inlet of a high-temperature SO2 flue (3), the connection between the high-temperature SO2 flue (3) and the water washing tower (4) is a cooling SO2 flue gas, the top exhaust outlet of the water washing tower (4) is connected with the top inlet of the absorption tower (9) through a clean SO2 flue gas pipe (5), the bottom liquid outlet of the water washing tower (4) is connected with the inlet of a water washing pump (7), and the outlet of the water washing pump (7) is connected with the circulating water inlet of the water washing tower (4), a water inlet pipe of water supplement and a wastewater pipe of waste sulfuric acid liquid; a heat exchange pipe (26) is arranged outside the high-temperature SO2 flue (3), and a closed annular space between the heat exchange pipe (26) and the high-temperature SO2 flue (3) is a heat exchange area for a heat exchange medium, the air inlet of the heat exchange pipe (26) is arranged at one end of the cooling SO2 flue gas, and the air outlet of the heat exchange pipe (26) is arranged at one end of the high-temperature SO2 flue gas.The shell of the sulfur combustion furnace (1) is provided with a heat exchange sleeve (20), and the closed annular space between the two is a region for flow heat exchange of the heat exchange medium, wherein the gas inlet of the heat exchange sleeve (20) is arranged at one end of the smoke outlet of the sulfur combustion furnace (1), and the gas outlet of the heat exchange sleeve (20) is arranged at one end of the air inlet of the sulfur combustion furnace (1); the gas outlet of the heat exchange sleeve (20) is connected with the high-pressure inlet of the mixed air door (19) and the inlet of the inlet rectifying section (11) of the micro high-temperature waste heat boiler (10), the micro high-temperature waste heat boiler (10) further comprises a shell (12), an ultra-large temperature difference heat exchanger (13) and an outlet tapered section, the medium outlet of the outlet tapered section is connected with the low-pressure outlet of the mixed air door (19), the inlet of the air blower (21) and the gas outlet of the compressed medium storage tank (22), the gas outlet of the air blower (21) is connected with the gas inlet of the heat exchange sleeve (26), and the gas outlet of the heat exchange sleeve (26) is connected with the gas inlet of the heat exchange sleeve (20); wherein the water inlet of the ultra-large temperature difference heat exchanger (13) is connected with the outlet of the water supply pump (16), the water outlet of the ultra-large temperature difference heat exchanger (13) is connected with the high-temperature water inlet of the flash tank (23), the medium-temperature water outlet of the flash tank (23) is communicated with the inlet of the water supply pump (16) and the water supply pipe of the desalted water supply, the outlet of the secondary steam at the top of the flash tank (23) is connected with the heat source steam / water inlet of the water bath tank (51), the heating steam inlet of the bromine extraction distillation tower (31), the primary steam outlet of the new energy electric heating steam furnace (38) and the third steam outlet of the high-temperature heat pump steam device (37) respectively; wherein the new energy electric heating steam furnace (38) is further provided with an electric boiler water supply inlet, and the electric heater (39) is arranged in the new energy electric heating steam furnace (38), and the two ends of the electric heater (39) are connected with the power supply lines of the new energy power supply respectively; the low-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device (36) is connected with the liquid discharge port at the bottom of the absorption tower (9) through the liquid supply pipe of the complete liquid, the low-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device (36) is connected with the low-temperature side inlet of the original waste liquid heat recovery device (35), the low-temperature side outlet of the original waste liquid heat recovery device (35) is connected with the liquid inlet of the bromine extraction distillation tower (31) at the upper portion, the chlorine gas inlet of the bromine extraction distillation tower (31) at the lower portion is connected with the chlorine gas outlet of the liquid chlorine gasification tank (50), the bottom liquid outlet of the bromine extraction distillation tower (31) is connected with the inlet of the waste liquid pump (34), the outlet of the waste liquid pump (34) is connected with the high-temperature side inlet of the original waste liquid heat recovery device (35), the high-temperature side outlet of the original waste liquid heat recovery device (35) is connected with the high-temperature side inlet of the high-efficiency anti-corrosion deep heat recovery device (36), and the high-temperature side outlet of the high-efficiency anti-corrosion deep heat recovery device (36) is communicated with the waste water pipe of the bromine extraction waste liquid.The top of the bromine distillation column (31) is the collection area of bromine and water vapor mixture, the top gas outlet is connected with the gas inlet of the upper part of the bromine vapor condenser (33) through the bromine vapor exhaust pipe (32), the liquid outlet of the lower part of the bromine vapor condenser (33) is communicated with the water outlet pipe of the liquid bromine, the liquid outlet of the crude bromine water at the bottom of the bromine vapor condenser (33) is connected with the liquid inlet of the upper part of the bromine distillation column (31); the cooling water outlet of the bromine vapor condenser (33) is connected with the low-temperature heat source inlet of the high-temperature heat pump steam device (37) through the cooling water return pipe, the cooling water inlet of the bromine vapor condenser (33) is connected with the low-temperature heat source outlet of the high-temperature heat pump steam device (37) through the cooling water inlet pipe, the heating side inlet of the high-temperature heat pump steam device (37) is communicated with the water inlet pipe of the heat pump water supply, and the heating side outlet of the high-temperature heat pump steam device (37) is the outlet of the third steam; the working medium in the compression working medium storage tank (22) is high-pressure nitrogen or compressed air, and the material of the water supply pump (16) is high-temperature cast iron pump or stainless steel water pump.

2. A process system for concentrating and bromine extraction from seawater as claimed in claim 1, wherein The water outlet pipe section of the super large temperature difference heat exchanger (13) is provided with a safety valve group (14) and a water supply temperature sensor (15), the flue gas outlet pipe section of the sulfur combustion furnace (1) is provided with a combustion furnace flue gas temperature sensor (17), the outlet pipe section of the air blower (21) is provided with a mixed smoke temperature sensor (18), and the high-temperature SO2 flue (3) is provided with a medium-temperature flue gas sensor (27) at the connection with the water washing tower (4); the running temperature of the water supply temperature sensor (15) is controlled by the opening degree of the electric regulating valve at the outlet of the water supply pump (16), and the low limit temperature of the mixed smoke temperature sensor (18) is controlled by the opening degree of the mixed air door (19); the low limit temperature of the combustion furnace flue gas temperature sensor (17) and the low limit temperature of the medium-temperature flue gas sensor (27) are both controlled by the flow rate of the air blower (21) adjusted by the frequency converter or the air inlet guide vane.

3. A process system for concentrating and bromine extraction from seawater as claimed in claim 1, wherein The material of the heat exchange sleeve (20) is carbon steel, and an external heat preservation layer is arranged or not arranged; the material of the heat exchange sleeve pipe (26) is carbon steel, and an external heat preservation layer is arranged.

4. A process system for concentrating and recovering bromine from seawater as claimed in claim 1, wherein The super large temperature difference heat exchanger (13) adopts a serpentine coil structure, a horizontal or vertical tube bundle structure, a plate structure or a tube-plate structure; when the horizontal or vertical tube bundle structure is adopted, the heat exchange pipe adopts a light pipe or finned pipe structure; the heat exchange material of the super large temperature difference heat exchanger (13) is carbon steel, ND steel, stainless steel 304 or stainless steel 316L.

5. A process system for concentrating and bromine extraction from seawater as claimed in claim 1 wherein The high-efficiency corrosion-resistant deep heat recovery device (36) adopts a high-efficiency graphene plastic pipe heat exchanger; the original waste liquid heat recovery device (35) adopts a silicon carbide heat exchanger, a glass heat exchanger and / or a fluoroplastic heat exchanger.

6. A process system for concentrating and bromine extraction from seawater as claimed in claim 1, wherein The heat pump main machine of the high-temperature heat pump steam generating device (37) adopts a single-stage voltage compression type high-temperature heat pump type, and a series electric heater is used to generate water vapor.

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