CN114074970A - Method and system for recycling acid and bromine simple substance from electrolysis reverse osmosis concentrated water - Google Patents

Method and system for recycling acid and bromine simple substance from electrolysis reverse osmosis concentrated water Download PDF

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CN114074970A
CN114074970A CN202010843851.8A CN202010843851A CN114074970A CN 114074970 A CN114074970 A CN 114074970A CN 202010843851 A CN202010843851 A CN 202010843851A CN 114074970 A CN114074970 A CN 114074970A
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absorption tower
gas
bromine
reverse osmosis
water
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CN114074970B (en
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司艳晓
徐孝轩
胡长朝
党伟
唐志伟
丁鹏元
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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China Petroleum and Chemical Corp
Sinopec Exploration and Production Research Institute
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1406—Multiple stage absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1418—Recovery of products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/096—Bromine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
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    • C02F2201/4614—Current
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4616—Power supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4619—Supplying gas to the electrolyte

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Abstract

The invention belongs to the field of wastewater treatment, and discloses a method and a system for recycling acid and bromine simple substances from electrolysis reverse osmosis concentrated water. The system comprises an electrolytic cell, a gas collecting pipeline system, a primary absorption tower, a secondary absorption tower and a distillation condensing device. The method comprises the following steps: cl produced by anodic oxidation2、Br2Making the gas escape under the action of hot air, introducing gas components into the lower end of a primary absorption tower by using a gas collecting system, contacting spray water to obtain primary absorbed liquid and unabsorbed gas, allowing the unabsorbed gas to enter the lower end of a secondary absorption tower, allowing the primary absorbed liquid to enter the upper end of the secondary absorption tower, and allowing the liquid to pass through Cl2And HBr in two absorption towersThe reaction was carried out and the bromine was further concentrated. And finally, purifying in a distillation and condensation device to obtain the finished bromine. The absorption liquid generated by the secondary absorption tower can be recycled as acid liquor. The method does not need to add an oxidant, and can realize bromine extraction and acid liquor recovery.

Description

Method and system for recycling acid and bromine simple substance from electrolysis reverse osmosis concentrated water
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method and a system for recycling acid and bromine simple substances from concentrated water by electrolysis and reverse osmosis.
Background
The pollutants in the water extracted from the shale gas mainly comprise heavy metals, grease, soluble organic matters and high-concentration salts, the anions mainly comprise chloride ions and bromide ions, and the concentration of the bromide ions can reach more than 100mg/L in some areas of the Fuling gas field. In order to meet the treatment requirement of discharge, the current treatment scheme of the shale gas produced water mainly comprises pretreatment for removing organic matters and ultrafiltration reverse osmosis membrane for removing salinity. For the concentrated water treatment after reverse osmosis, at present, the salt in the wastewater is continuously concentrated by mainly adopting a distillation method, and finally, the salt is directly changed into solid miscellaneous salt in a dry state. However, the concentrated water contains a large amount of bromine, and the direct drying and concentration can cause the waste of bromine resources.
The current method for recovering bromine from bromine-containing wastewater comprises the following steps: CN109399571A adopts bromine-containing waste water to react with chlorine to generate crude bromine, and then the crude bromine enters a rectifying tower and is washed by sulfuric acid to obtain the finished bromine. CN103407965A proposes that after wastewater is acidified and oxidized, a polytetrafluoroethylene or polytetrafluoroethylene-like gaseous membrane component is adopted to carry out bromine extraction. Both of the above patents involve the consumption of large amounts of oxidizing agent, and are in need of further improvement.
CN102556972A proposes that bromine ions are oxidized into elemental bromine by using an electrochemical oxidation anode, and bromine is obtained by removing the solution in the anode chamber and performing air blowing, condensation and gas-liquid separation. CN109371416A proposes to treat bromine-containing wastewater by electrolysis, and contact an extractant with the electrolyzed solution to recover elemental bromine from the extract phase. However, in the concentrated water obtained by the reverse osmosis treatment of the shale gas produced water, the content of chloride ions and bromide ions is high, and the content of chloride ions is dozens of times of that of bromide ions, so a large amount of chlorine gas is also generated in the electrolysis process, and the two patents do not provide a corresponding method.
Disclosure of Invention
The invention aims to provide a method and a system for recycling acid and bromine simple substances from concentrated water by electrolysis reverse osmosis aiming at the defects of the prior art. By utilizing the system and the method, bromine in the wastewater can be extracted, and meanwhile, the acid solution is recovered.
In order to achieve the above object, one aspect of the present invention provides a system for recovering acid and elemental bromine from concentrated water by electrolysis of reverse osmosis, the system comprising an electrolysis bath, a gas collection pipeline system, a primary absorption tower, a secondary absorption tower and a distillation and condensation device; wherein the content of the first and second substances,
the electrolytic cell comprises a closed shell, an anode, a cathode, an inlet, an outlet and an aeration pipe;
the first-stage absorption tower comprises a first lower end air inlet, a second lower end air inlet, an upper end air outlet pipe, a first packing area and a first water outlet pipe, and the first water outlet pipe is arranged at the lower part of the first-stage absorption tower;
the second-stage absorption tower comprises a third lower-end air inlet, an upper-end water inlet, a second packing area and a second water outlet pipe, and the second water outlet pipe is arranged at the lower part of the second-stage absorption tower;
one end of the gas collecting pipeline system is hermetically connected with an outlet of the electrolytic cell; the other end of the gas collecting pipeline is hermetically connected with a first lower end gas inlet of the primary absorption tower; an air outlet pipe at the upper end of the primary absorption tower is hermetically connected with an air inlet at the second lower end of the secondary absorption tower; the first-stage absorption tower is connected with a water inlet at the upper end of the second-stage absorption tower through a first water outlet pipe; the secondary absorption tower is connected with the distillation condensing device through a second water outlet pipe;
the gas collecting pipeline system is provided with a suction fan.
The invention also provides a method for recovering acid and bromine simple substances from the electrolyzed reverse osmosis concentrated water, which adopts the system for recovering acid and bromine simple substances from the electrolyzed reverse osmosis concentrated water and comprises the following steps:
(1) the reverse osmosis concentrated water enters the electrolytic tank and is subjected to electrochemical oxidation treatment under the action of hot air introduced through an aeration pipe to obtain gas components containing gaseous chlorine and gaseous bromine;
(2) the gas component containing gaseous chlorine and gaseous bromine enters the lower end of the primary absorption tower through the gas collecting pipeline system and is introduced with SO from a second lower end gas inlet2The gas enters a first packing area of the primary absorption tower together and contacts spray water from the upper end of the primary absorption tower to obtain primary absorbed liquid and unabsorbed gas;
(3) the liquid after the primary absorption enters the upper end of the secondary absorption tower and is used as spraying liquid of the secondary absorption tower, and the unabsorbed gas enters the lower end of the secondary absorption tower and contacts the spraying liquid in a second packing area of the secondary absorption tower to obtain liquid after the secondary absorption;
(4) and introducing the liquid after the secondary absorption into the distillation and condensation device for distillation and condensation to obtain a finished bromine product and recover acid.
The technical scheme of the invention has the following beneficial effects:
the method can extract bromine in the reverse osmosis concentrated water without adding an oxidant, thereby saving bromine resources. While recovering the acid solution. The purity of bromine can reach more than 90%, and the recovered acid solution can be used for adjusting the pH value in wastewater treatment.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic diagram of a system for recovering acid and elemental bromine from concentrated water by electrolytic reverse osmosis provided in accordance with various embodiments of the present invention.
Wherein, 1-no diaphragm plate frame type electrolytic cell; 2-a power supply; 3-a first-stage absorption tower; 4-a secondary absorption tower; 5-a distillation condensing unit; 6-gas collection piping system; 7-a first lower end air inlet; 8-a second lower end air inlet; 9-an air outlet pipe at the upper end; 10-a first packing region; 11-a first water outlet pipe; 12-a second packing region; 13-second water outlet pipe.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention provides a system for recycling acid and bromine simple substances from electrolytic reverse osmosis concentrated water, which comprises an electrolytic bath, a gas collecting pipeline system, a primary absorption tower, a secondary absorption tower and a distillation condensing device, wherein the electrolytic bath is arranged in the electrolytic reverse osmosis concentrated water; wherein the content of the first and second substances,
the electrolytic cell comprises a closed shell, an anode, a cathode, an inlet, an outlet and an aeration pipe;
the first-stage absorption tower comprises a first lower end air inlet, a second lower end air inlet, an upper end air outlet pipe, a first packing area and a first water outlet pipe, and the first water outlet pipe is arranged at the lower part of the first-stage absorption tower;
the second-stage absorption tower comprises a third lower-end air inlet, an upper-end water inlet, a second packing area and a second water outlet pipe, and the second water outlet pipe is arranged at the lower part of the second-stage absorption tower;
one end of the gas collecting pipeline system is hermetically connected with an outlet of the electrolytic cell; the other end of the gas collecting pipeline is hermetically connected with a first lower end gas inlet of the primary absorption tower; an air outlet pipe at the upper end of the primary absorption tower is hermetically connected with an air inlet at the second lower end of the secondary absorption tower; the first-stage absorption tower is connected with a water inlet at the upper end of the second-stage absorption tower through a first water outlet pipe; and the secondary absorption tower is connected with the distillation condensing device through a second water outlet pipe.
The gas collecting pipeline system is provided with a suction fan.
According to the present invention, preferably, the electrolytic cell is a diaphragm-free plate and frame type electrolytic cell.
According to the invention, preferably, the anode is a chlorine evolution active electrode which is a ruthenium iridium titanium or ruthenium iridium tin titanium electrode; the cathode is an iron electrode, a copper electrode, an aluminum electrode or a graphite electrode.
According to the invention, the packing of the first packing region and the second packing region is preferably random pall ring packing. The loose pall ring packing is made of ceramic or plastic.
In the invention, the aerator pipe adopts a high-temperature-resistant and water vapor-resistant aerator.
In the invention, because of the adoption of the sealing connection, the gas collecting pipeline system does not release the gas generated by electrolysis into the air.
The invention also provides a method for recovering acid and bromine simple substances from the electrolyzed reverse osmosis concentrated water, which adopts the system for recovering acid and bromine simple substances from the electrolyzed reverse osmosis concentrated water and comprises the following steps:
(1) the reverse osmosis concentrated water enters the electrolytic tank and is subjected to electrochemical oxidation treatment under the action of hot air introduced through an aeration pipe to obtain gas components containing gaseous chlorine and gaseous bromine;
(2) the gas component containing gaseous chlorine and gaseous bromine enters the lower end of the primary absorption tower through the gas collecting pipeline system and SO introduced from the lower end of the primary absorption tower2The gas enters a first packing area of the first-stage absorption tower together and contacts spray water from the upper end of the first-stage absorption tower to obtain first-stage absorbed liquidBulk and unabsorbed gases;
(3) the liquid after the primary absorption enters the upper end of the secondary absorption tower and is used as spraying liquid of the secondary absorption tower, and the unabsorbed gas enters the lower end of the secondary absorption tower and contacts the spraying liquid in a second packing area of the secondary absorption tower to obtain liquid after the secondary absorption;
(4) and introducing the liquid after the secondary absorption into the distillation and condensation device for distillation and condensation to obtain a finished bromine product and recover acid.
Preferably, the method comprises the following steps:
(1) the reverse osmosis concentrated water enters the diaphragm-free plate frame type electrolytic tank through the inlet, and is subjected to electrochemical oxidation treatment under the action of hot air introduced from the aeration pipe to obtain gas components containing gaseous chlorine and gaseous bromine;
(2) the gas component containing gaseous chlorine and gaseous bromine enters a first lower end gas inlet at the lower end of the primary absorption tower through the gas collecting pipeline system and SO is introduced from a second lower end gas inlet at the lower end of the primary absorption tower2The gas enters a first packing area of the primary absorption tower together and contacts spray water from the upper end of the primary absorption tower to obtain primary absorbed liquid and unabsorbed gas;
(3) the liquid after the primary absorption enters an upper end water inlet at the upper end of the secondary absorption tower through the first water outlet pipe and is used as spraying liquid of the secondary absorption tower, the unabsorbed gas enters a third lower end air inlet at the lower end of the secondary absorption tower through an upper end air outlet pipe and contacts with the spraying liquid in a second packing area of the secondary absorption tower, and secondary absorption liquid is obtained;
(4) and introducing the liquid after the secondary absorption into the distillation and condensation device through a second water outlet pipe for distillation and condensation to obtain a finished bromine product and recover acid.
In the invention, after the reverse osmosis concentrated water is subjected to electrochemical oxidation treatment, chlorine ions and bromine ions can be oxidized into Cl at the anode2、Br2Bromine ion may also be generated as Cl2By oxidation to Br2. To electricityIntroducing hot air into the solution, wherein Cl is contained2、Br2Under the action of hot air, the gas escapes in a gaseous state. Collecting gas by using the gas collecting pipeline system, introducing the collected gas into the lower end of the primary absorption tower, and synchronously introducing SO into the lower end of the primary absorption tower2Spraying water at the upper end to obtain H at the bottom of the first-stage absorption tower2SO4And dilute HBr and HCl solution. And (3) continuously introducing the solution into a secondary absorption tower, continuously introducing gas which is not absorbed by the primary absorption tower and escapes from the electrolytic cell at the lower end of the secondary absorption tower, and continuously reacting chlorine and HBr to obtain bromine. Distilling and heating the solution to obtain bromine, and then obtaining the finished bromine by a condensing device. The purpose of setting up the two-stage absorption tower is to concentrate the bromine simple substance. The remaining solution is H2SO4Acid solution of HCl and the remaining H2SO4And HCl, and the recovered acid is used for pH adjustment of wastewater treatment. The reaction equation for the above reaction is as follows:
2Br-→Br2+2e-，E0＝1.09VvsSHEformula 1
2Cl-→Cl2+2e-，E0＝1.36VvsSHEFormula 2
Cl2+2Br-→Br2+2Cl-Formula 3
In the invention, the gas in the electrolytic bath is collected by using the gas collecting pipeline system and is introduced into the first lower end gas inlet of the primary absorption tower, and simultaneously SO is introduced into the second lower end gas inlet of the primary absorption tower2And spray water is arranged at the upper end of the primary absorption tower.
As a preferred scheme, the spray water arranged at the upper end of the primary absorption tower is deionized water.
According to the invention, preferably, the temperature of the hot air is 45-50 ℃, and the gas quantity of the hot air is 0.05-0.15L/min; the power supply used for the electrochemical oxidation treatment is a constant-current stabilized power supply, and the current density of the electrochemical oxidation treatment is 5-40mA/cm2。
According to the invention, preferably, saidThe liquid-gas ratio of the water amount of the spray water in the primary absorption tower to the gas amount of the gas in the primary absorption tower is controlled to be 5-8L/m3(ii) a The liquid-gas ratio of the liquid amount of the spray liquid in the secondary absorption tower to the gas amount of the gas in the secondary absorption tower is controlled to be 1-5L/m3。
In the invention, the gas of the primary absorption tower comprises: the gaseous component comprising gaseous chlorine and gaseous bromine and SO2. The gas in the secondary absorption tower is gas which is not absorbed in the primary absorption tower.
The method is particularly suitable for high-chlorine and high-bromine reverse osmosis concentrated water, and preferably, the concentration of chloride ions in the reverse osmosis concentrated water is more than 5g/L, and the concentration of bromide ions in the reverse osmosis concentrated water is more than 0.5 g/L.
The method and system for recovering acid and bromine from concentrated water by reverse osmosis electrolysis will be described in detail with reference to fig. 1.
In each of the following examples:
anodes were purchased from blue star (beijing) chemical machinery ltd;
cathodes were purchased from Baojirongsheng nonferrous metals, Inc.;
detecting the concentration of bromide ions in the reverse osmosis concentrated water by adopting an ion chromatography, and please refer to the reference of research on a determination method of bromide ions in an aqueous solution for details;
detecting the concentration of a bromine simple substance generated by the two-stage absorption tower and the purity of a finished bromine product obtained in the step (4) by adopting a spectrophotometry, wherein the details are shown in a reference of measuring free bromine in hydrobromic acid by using a spectrophotometry;
the volume of the electrolytic cell is 2L;
the volumes of the primary absorption tower and the secondary absorption tower are both 10L; the heights of the first filler area and the second filler area are both 20 cm; the distance from the bottom of the first packing area to the bottom of the first-stage absorption tower is 10 cm; the distance from the bottom of the second packing area to the bottom of the secondary absorption tower is 10 cm.
Example 1
As shown in fig. 1, the present embodiment provides a system for recovering acid and elemental bromine from concentrated water by reverse osmosis electrolysis, which comprises a diaphragm-free plate-and-frame type electrolytic cell 1, a gas collecting pipeline system 6, a primary absorption tower 3, a secondary absorption tower 4 and a distillation and condensation device 5; wherein the content of the first and second substances,
the diaphragm-free plate frame type electrolytic cell 1 comprises a closed shell, a ruthenium iridium titanium electrode, an iron electrode, an inlet, an outlet and an aeration pipe;
the primary absorption tower 3 comprises a first lower end air inlet 7, a second lower end air inlet 8, an upper end air outlet pipe 9, a first packing area 10 and a first water outlet pipe 11, and the first water outlet pipe 11 is arranged at the lower end of the primary absorption tower 3;
the secondary absorption tower 4 comprises a third lower end air inlet, an upper end water inlet, a second packing area 12 and a second water outlet pipe 13, and the second water outlet pipe 13 is arranged at the lower end of the secondary absorption tower 4;
one end of the gas collecting pipeline system 6 is hermetically connected with an outlet of the diaphragm-free plate frame type electrolytic cell 1; the other end of the gas collecting pipeline is hermetically connected with a first lower end gas inlet 7 of the primary absorption tower 3; an air outlet pipe 9 at the upper end of the primary absorption tower 3 is hermetically connected with an air inlet 8 at the second lower end of the secondary absorption tower 4; a first water outlet pipe 11 of the primary absorption tower 3 is connected with a water inlet at the upper end of the secondary absorption tower 4; the secondary absorption tower 4 is connected with the distillation condensing device 5 through a second water outlet pipe 13.
The gas collection line system 6 is also provided with a suction fan (not shown).
The fillers of the first filler area 10 and the second filler area 12 are random pall ring fillers, and the materials of the random pall ring fillers are ceramics.
The aerator pipe adopts a high-temperature resistant and water vapor resistant aerator.
Example 2
The embodiment provides a method for recovering acid and bromine from concentrated water by electrolysis and reverse osmosis, which adopts the system for recovering acid and bromine from concentrated water by electrolysis and reverse osmosis described in embodiment 1, and comprises the following steps:
(1) the reverse osmosis concentrated water enters the diaphragm-free plate-frame type electrolytic tank 1 through the inlet, and is subjected to electrochemical oxidation treatment under the action of hot air introduced through the aeration pipe to obtain gas components containing gaseous chlorine and gaseous bromine;
(2) the gas component containing gaseous chlorine and gaseous bromine enters a first lower end gas inlet 7 at the lower end of the primary absorption tower 3 through the gas collecting pipeline system 6, and SO is introduced from a second lower end gas inlet 8 at the lower end of the primary absorption tower 32The gas enters a first packing area 10 of the first-stage absorption tower 3 together, and contacts spray water from the upper end of the first-stage absorption tower 3 to obtain first-stage absorbed liquid and unabsorbed gas;
(3) the primary absorbed liquid enters an upper end water inlet at the upper end of the secondary absorption tower 4 through the first water outlet pipe 11 and is used as spraying liquid of the secondary absorption tower 4, the unabsorbed gas enters a third lower end air inlet at the lower end of the secondary absorption tower 4 through an upper end air outlet pipe 9 and contacts with the spraying liquid in a second packing area 12 of the secondary absorption tower 4, and secondary absorbed liquid is obtained;
(4) and introducing the liquid after the secondary absorption into the distillation and condensation device 5 through a second water outlet pipe 13 for distillation and condensation to obtain a finished bromine product and recover acid.
The concentration of chloride ions in the reverse osmosis concentrated water is 15g/L, and the concentration of bromide ions is 1 g/L. The aerator pipe adopts a high-temperature resistant and water vapor resistant aerator.
The temperature of the hot air is 50 ℃, and the gas quantity of the hot air is 0.1L/min; the power supply 2 used for the electrochemical oxidation treatment is a constant-current stabilized power supply, and the current density of the electrochemical oxidation treatment is 40mA/cm2The effective area of the electrode is 400cm2(ii) a The gas quantity of gaseous chlorine and gaseous bromine generated by the electrochemical oxidation treatment is 0.22L/min;
the gas amount of the gas component containing gaseous chlorine and gaseous bromine entering the primary absorption tower 3 was 0.32L/min, and the SO was2The introduction amount of the water is 0.1L/min, and the water amount of the spray water is 2.5 mL/min; the liquid amount of the spray liquid of the secondary absorption tower 4 is 1mL/min, and the introduction amount of the gas introduced into the secondary absorption tower 4 is 0.21L/min; the amount of spray water in the primary absorption tower 3 and the amount of spray water in the primary absorption tower 3The gas content of the gas had a liquid-gas ratio of 5.95L/m3(ii) a The liquid-gas ratio of the liquid amount of the spray liquid in the secondary absorption tower 4 to the gas amount of the gas in the secondary absorption tower 4 is 4.76L/m3。
The liquid generated by the two-stage absorption tower contains bromine simple substance, chloride ions and sulfate radicals, wherein the content of the bromine simple substance is 20g/L, the liquid is finally introduced into a distillation condensing device 5, and the purity of the obtained bromine is 90%. The remaining solution is H2SO4Acid solution of HCl and the remaining H2SO4And HCl, and the recovered acid is used for pH adjustment of wastewater treatment.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. A system for recycling acid and bromine simple substances from concentrated water by electrolysis and reverse osmosis is characterized by comprising an electrolytic bath, a gas collecting pipeline system, a primary absorption tower, a secondary absorption tower and a distillation condensing device; wherein the content of the first and second substances,
the electrolytic cell comprises a closed shell, an anode, a cathode, an inlet, an outlet and an aeration pipe;
the first-stage absorption tower comprises a first lower end air inlet, a second lower end air inlet, an upper end air outlet pipe, a first packing area and a first water outlet pipe, and the first water outlet pipe is arranged at the lower part of the first-stage absorption tower;
the second-stage absorption tower comprises a third lower-end air inlet, an upper-end water inlet, a second packing area and a second water outlet pipe, and the second water outlet pipe is arranged at the lower part of the second-stage absorption tower;
one end of the gas collecting pipeline system is hermetically connected with an outlet of the electrolytic cell; the other end of the gas collecting pipeline is hermetically connected with a first lower end gas inlet of the primary absorption tower; an air outlet pipe at the upper end of the primary absorption tower is hermetically connected with an air inlet at the second lower end of the secondary absorption tower; the first-stage absorption tower is connected with a water inlet at the upper end of the second-stage absorption tower through a first water outlet pipe; the secondary absorption tower is connected with the distillation condensing device through a second water outlet pipe;
the gas collecting pipeline system is provided with a suction fan.
2. An electrolytic reverse osmosis concentrated water recovery system for acid and elemental bromine according to claim 1, wherein the electrolyzer is a diaphragm-free plate and frame electrolyzer.
3. An electrolytic reverse osmosis concentrated water recovery system for acid and elemental bromine according to claim 1, wherein the anode is a chlorine evolution active electrode; the cathode is an iron electrode, a copper electrode, an aluminum electrode or a graphite electrode.
4. The system for recovering acid and elemental bromine from concentrated water by electrolysis and reverse osmosis according to claim 3, wherein the chlorine evolution high-activity electrode is a ruthenium iridium titanium or ruthenium iridium tin titanium electrode.
5. The system for concentrated water electrolytic reverse osmosis acid and elemental bromine recovery according to claim 1, wherein the packing of the first and second packing zones is random pall ring packing.
6. The system for concentrated water by electrolysis and reverse osmosis to recover acid and bromine according to claim 5, wherein the random pall ring packing is made of ceramic or plastic.
7. A method for recovering acid and bromine from concentrated water by electrolytic reverse osmosis, which is characterized in that the method adopts the system for recovering acid and bromine from concentrated water by electrolytic reverse osmosis as claimed in any one of claims 1 to 6, and comprises the following steps:
(1) the reverse osmosis concentrated water enters the electrolytic tank and is subjected to electrochemical oxidation treatment under the action of hot air introduced through an aeration pipe to obtain gas components containing gaseous chlorine and gaseous bromine;
(2) the gas component containing gaseous chlorine and gaseous bromine enters the lower end of the primary absorption tower through the gas collecting pipeline system and is introduced with SO from a second lower end gas inlet2The gas enters a first packing area of the primary absorption tower together and contacts spray water from the upper end of the primary absorption tower to obtain primary absorbed liquid and unabsorbed gas;
(3) the liquid after the primary absorption enters the upper end of the secondary absorption tower and is used as spraying liquid of the secondary absorption tower, and the unabsorbed gas enters the lower end of the secondary absorption tower and contacts the spraying liquid in a second packing area of the secondary absorption tower to obtain liquid after the secondary absorption;
(4) and introducing the liquid after the secondary absorption into the distillation and condensation device for distillation and condensation to obtain a finished bromine product and recover acid.
8. A method for recovering acid and bromine from concentrated water by electrolysis and reverse osmosis according to claim 7, wherein the temperature of the hot air is 45-55 ℃, and the gas quantity of the hot air is 0.05-0.15L/min; the power supply used for the electrochemical oxidation treatment is a constant-current stabilized power supply, and the current density of the electrochemical oxidation treatment is 5-40mA/cm2。
9. The method for recovering acid and bromine from concentrated water by electrolysis and reverse osmosis according to claim 7, wherein the liquid-gas ratio of the water amount of the spray water in the primary absorption tower to the gas amount of the gas in the primary absorption tower is controlled to be 5-8L/m3(ii) a The liquid-gas ratio of the liquid amount of the spray liquid in the secondary absorption tower to the gas amount of the gas in the secondary absorption tower is controlled to be 1-5L/m3。
10. A method of electrolyzing reverse osmosis concentrated water to recover acid and elemental bromine according to claim 7, wherein the concentration of chloride ions in the reverse osmosis concentrated water is >5g/L and the concentration of bromide ions is >0.5 g/L.
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US2950180A (en) * 1957-03-22 1960-08-23 Basf Ag Chemical reactor tower
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