CN116835834B - Bromine-containing wastewater treatment device and bromine-containing wastewater recycling process - Google Patents
Bromine-containing wastewater treatment device and bromine-containing wastewater recycling process Download PDFInfo
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- CN116835834B CN116835834B CN202311074190.7A CN202311074190A CN116835834B CN 116835834 B CN116835834 B CN 116835834B CN 202311074190 A CN202311074190 A CN 202311074190A CN 116835834 B CN116835834 B CN 116835834B
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- acidification
- bromine
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 76
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002351 wastewater Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 14
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 92
- 230000020477 pH reduction Effects 0.000 claims abstract description 73
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000007888 film coating Substances 0.000 claims abstract description 33
- 238000009501 film coating Methods 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 21
- 238000010030 laminating Methods 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 241000252254 Catostomidae Species 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 52
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 48
- 230000003647 oxidation Effects 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- -1 iron ions Chemical class 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 210000002489 tectorial membrane Anatomy 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000003842 bromide salts Chemical class 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 230000003311 flocculating effect Effects 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229940006460 bromide ion Drugs 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000001649 bromium compounds Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000001960 triggered effect Effects 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910001503 inorganic bromide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2025—Chlorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a bromine-containing wastewater treatment device and a bromine-containing wastewater recycling process, comprising an acidification adsorption device and a rack for fixing the acidification adsorption device; a lifting plate is arranged in the acidification adsorption device, and a porous membrane is coated on the surface of the lifting plate; the acidification adsorption device is provided with a film covering unit for covering films and recovering porous films; the film laminating unit comprises a film laminating frame, a shovel blade and a plurality of suckers arranged on the film laminating frame, and a film roll matched with the suckers is arranged on one side of the acidification adsorption device; the film coating frame is arranged above the acidification adsorption device in a sliding way, and the acid regulating pipe is provided with a guide sliding rod matched with the film coating frame; the film coating frame is provided with a guide groove matched with the shovel blade; the invention utilizes an electrochemical method to realize the extraction of bromide ions in the sewage and the reduction of COD in the sewage; the porous membrane is adopted in the acidification adsorption device to adsorb and collect flocculate, so that impurities in bromine-containing industrial wastewater after acid adjustment are reduced, and the acid adjustment efficiency is improved.
Description
Technical Field
The invention relates to the technical field of water treatment devices, in particular to a bromine-containing wastewater treatment device and a bromine-containing wastewater recycling process.
Background
Bromine is one of the important chemical raw materials, and a wide variety of inorganic bromides, bromates and organic compounds containing bromine derived from the bromine have special value in national economy and technological development. The aromatic organic bromide has wide application in various aspects such as pharmacy, pesticide, dye and the like, and when the aromatic organic bromide is prepared by bromination reaction, the utilization rate of bromine is only 50 percent, so industrial wastewater rich in bromide ions and organic bromide can be generated, and the wastewater also contains more metal ions such as iron ions or aluminum ions. The bromine ions have great interference on COD measurement, so that the COD content in water is larger than the actual value, and the bromine ions and the organic bromides inhibit the normal metabolism of engineering bacteria in a biochemical system, when the bromine content exceeds 2000mg/L, the efficiency of the biochemical system is reduced by 70 percent, and if bromine in industrial wastewater rich in the bromine ions and the organic bromides is prepared into a sodium bromide product, the wastewater treatment cost is greatly reduced, and considerable economic benefit is generated.
At present, in China, a product scheme obtained by extracting bromine from industrial wastewater containing rich bromide ions and organic bromides mainly contains bromine, bromine is used as a dangerous chemical, storage cost and transportation cost are high, and sodium bromide is used as an inorganic salt, so that the storage and transportation are convenient. And when bromide ions and organic bromides exist, oxidation resources can be robbed, and when advanced oxidation technology is applied to treat wastewater, oxidation resources can be robbed, so that oxidation efficiency is reduced, and COD (chemical oxygen demand) reduction is not obvious.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bromine-containing wastewater treatment device and a bromine-containing wastewater recycling process.
In order to solve the technical problems, the invention is solved by the following technical scheme: a bromine-containing wastewater treatment device comprises an acidification adsorption device and a rack for fixing the acidification adsorption device.
In the above scheme, preferably, a lifting plate is arranged in the acidification adsorption device, and a porous membrane is coated on the surface of the lifting plate;
the acidification adsorption device is provided with a film covering unit for covering films and recovering porous films;
the film laminating unit comprises a film laminating frame, a shovel blade and a plurality of suckers arranged on the film laminating frame, and a film roll matched with the suckers is arranged on one side of the acidification adsorption device;
the film coating frame is arranged above the acidification adsorption device in a sliding way, and the acidification adsorption device is provided with a guide sliding rod matched with the film coating frame;
the film coating frame is provided with a guide groove matched with the shovel blade;
when the lifting plate is lifted to the top of the acidification adsorption device, the film coating frame slides to shovel the porous film on the lifting plate into the guide groove, and a new porous film adsorbed by the sucker is coated on the surface of the lifting plate.
In the above scheme, preferably, the film coating frame is provided with a supporting plate, and the supporting plate is connected with the bottom of the guiding groove and is used for providing support for the porous film shoveled into the guiding groove.
In the above scheme, preferably, the acidification adsorption device is provided with a side plate, a first spring is arranged between the film covering frame and the side plate, and the first spring is a tension spring.
In the above scheme, preferably, the lifting plate outer fringe is equipped with the heating wire that is used for fusing porous membrane, be equipped with on the acidizing adsorption equipment with slide back tectorial membrane frame matched with first button, first button is connected with the heating wire electricity.
In the above scheme, preferably, the lifting plate is provided with a lifting screw sleeve, the frame is provided with a driving screw rod in threaded fit with the lifting screw sleeve, the driving screw rod is provided with a first gear, the frame is provided with a driving motor, and the driving motor is provided with a second gear meshed with the first gear.
In the above scheme, preferably, the acidification adsorption device is provided with a locking unit for locking the tectorial membrane frame, the locking unit comprises a lock pin, a first electromagnet and a second spring, the tectorial membrane frame is provided with a pin hole matched with the lock pin, the lock pin is provided with a limiting plate, the second spring is arranged between the limiting plate and the acidification adsorption device, and the first electromagnet is fixedly arranged on the acidification adsorption device.
In the above scheme, preferably, the end part of the lifting screw sleeve is provided with a mounting plate, the bottom of the acidification adsorption device is provided with a second button matched with the mounting plate after lifting, and the second button is connected with the first electromagnetic iron.
In the above scheme, preferably, the mounting plate is provided with a second electromagnet, the bottom of the acidification adsorption device is provided with an adsorption plate adsorbed by the lifted second electromagnet, and the adsorption plate is connected with the film coating frame through a pull rope.
In the above scheme, preferably, the acidification adsorption device is provided with a plurality of guide pulleys matched with the porous membrane for guiding the acidification adsorption device.
In the above scheme, preferably, a resource utilization process of a bromine-containing wastewater treatment device comprises the following steps:
s1: acidifying adsorption, namely introducing industrial wastewater rich in bromide ions and organic bromides (the content of the bromide ions is 20mg/L-10 g/L) into an acidifying adsorption device, and regulating the pH value of the industrial wastewater to 2-4 by using 98% sulfuric acid to obtain acidified bromine-containing industrial wastewater;
simultaneously, sulfuric acid reacts with metal ions such as iron ions in the wastewater to generate ferric salt, so that organic matters in the wastewater generate flocculent precipitate, then the lifting plate is lifted upwards to adhere the flocculent precipitate to the porous membrane, after the lifting plate is lifted to the top, the locking unit is unlocked, the porous membrane adhered with the flocculent is shoveled into the supporting plate by the membrane covering frame under the action of the tensile force of the first spring, and meanwhile, a sucker adsorbs the new porous membrane to cover the surface of the lifting plate and is fused by the heating wire to cover the surface of the lifting plate;
s2: LAT advanced oxidation, namely introducing the acidified bromine-containing industrial wastewater into an LAT advanced oxidation tank for LAT advanced catalytic oxidation, and oxidizing bromide ions in the acidified liquid on an anode to generate bromine molecules after the LAT advanced oxidation tank is electrified, wherein the acidified liquid in the LAT advanced oxidation tank is changed into oxidizing liquid;
s3: LAT catalyst activation: introducing the oxidation solution into a buffer tank, and adding a LAT catalyst into the buffer tank to activate bromide ions, organic bromides and bromine molecules to obtain an activated oxidation solution;
s4: blowing off: introducing activated oxidation liquid into a stripping tower, spraying the activated oxidation liquid from the top of the stripping tower, blowing out bromine molecules in the activated oxidation liquid along with air, and finally enabling industrial wastewater to flow out of air containing the bromine molecules from the bottom of the stripping tower to enter a washing tower from the top of the stripping tower;
s5: washing: the bromine-containing air enters a washing tower for washing, and other gas impurities such as carbon dioxide, chlorine and the like in the bromine-containing air are washed and removed to obtain purer bromine-containing air;
s6: in the absorption tower, bromine molecules flow from top to bottom along with air pushed by a Roots blower, are absorbed by 20% sodium sulfide solution sprayed from the top in the absorption tower to generate sodium bromide and sulfur, and finally mixed liquid of the sodium bromide and the sulfur is obtained;
s7: and (3) filtering: removing sulfur in the mixed solution of sodium bromide and sulfur in a filtering mode to obtain a 45% sodium bromide liquid product;
s8: and (5) crystallization and drying: and (3) drying 45% of liquid sodium bromide crystals to obtain sodium bromide solids which are more than or equal to 98.5%.
The beneficial effects of the invention are as follows:
1. the electrochemical method is utilized to realize the extraction of bromine ions in the sewage and the reduction of COD in the sewage;
2. the cost of wastewater treatment is reduced, and considerable economic benefits are generated;
3. the LAT advanced oxidation reaction is typically performed at lower temperature and pressure conditions than conventional chemical treatment methods, without the use of high temperature or high pressure thermochemical reactions. This can reduce energy consumption and reduce adverse effects on the environment;
4. the LAT advanced oxidation reaction can achieve sustained use by regenerating and recycling the electrode material. This is beneficial to resource conservation and sustainable development;
5. the LAT advanced oxidation reaction has certain selectivity, can selectively oxidize bromide ions in the sewage without generating obvious influence on other harmless components or pollutants, and is beneficial to realizing effective extraction and separation of bromine;
6. the porous membrane is adopted in the acidification adsorption device to adsorb and collect flocculate, so that impurities in bromine-containing industrial wastewater after acid adjustment are reduced, and the acid adjustment efficiency is improved.
Drawings
Fig. 1 is a schematic diagram of a front view structure of the present invention.
Fig. 2 is a schematic view of a partial enlarged structure of the present invention at a.
FIG. 3 is a schematic view of the three-dimensional structure of the film frame of the present invention.
Fig. 4 is a schematic perspective view of a lifting plate and a lifting screw sleeve according to the present invention.
Fig. 5 is a schematic perspective view of a driving screw and a first gear according to the present invention.
FIG. 6 is a flow chart of the bromine-containing wastewater recycling process.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and detailed description: see fig. 1-6.
Example 1: the utility model provides a bromine-containing wastewater treatment device, includes acidizing adsorption equipment 1 and is used for fixing the frame 2 of this acidizing adsorption equipment 1, be equipped with on the frame 2 with the stand that acidizing adsorption equipment 1 bottom is fixed mutually, during the use, with bromine-containing waste water adding in the acidizing adsorption equipment 1, add concentrated sulfuric acid again and carry out the acid regulation, after the acid regulation is accomplished, discharge through the valve of acidizing adsorption equipment 1 bottom.
When concentrated sulfuric acid is added into the acidification adsorption device 1, the concentrated sulfuric acid reacts with metal ions such as iron ions in bromine-containing wastewater to generate ferric salt, and flocculation is generated after the ferric salt reacts with organic matters, so that flocculent precipitate is generated in the solution during acid adjustment, and the quality of subsequent processes is affected when the acidified wastewater is discharged into the next oxidation process simultaneously, and therefore, flocculation needs to be cleaned during acid adjustment.
In order to achieve a better flocculation cleaning effect, the lifting plate 3 capable of lifting is slidably arranged in the acidification adsorption device 1, the acidification adsorption device 1 is preferably a rectangular tank, the lifting plate 3 is preferably a rectangular plate with the outer edge attached to the inner wall of the tank body, as shown in fig. 4, the lifting plate 3 is a screen plate, a plurality of through holes are formed in the screen plate, the porous membrane 4 is covered on the upper surface of the lifting plate 3, the lifting plate 3 is arranged at the bottom of the acidification adsorption device 1 initially, after a period of acidification, the lifting plate 3 ascends, flocculation suspended in a solution of the acidification adsorption device 1 is adhered to the porous membrane 4, and other bromine-containing wastewater is filtered to the lower side of the lifting plate 3, so that collection adsorption on flocculation is achieved.
The lifting plate 3 is provided with a porous membrane 4 on the upper end surface, the lower end surface is fixedly provided with a lifting screw sleeve 21, the lower end of the lifting screw sleeve 21 is penetrated with the bottom of the acidification adsorption device 1, a sealing ring is arranged between the outer wall of the lifting screw sleeve 21 and the wall body at the bottom of the acidification adsorption device 1, the sealing ring can be preferably a Y-shaped sealing ring, multiple layers of O-shaped sealing rings can also be adopted, the frame 1 is provided with a driving screw 22 in threaded fit with the lifting screw sleeve 21, the driving screw 22 is rotationally arranged at the bottom of the frame 2, and the driving screw 22 can only rotate on the frame 2 and can not relatively slide, when the driving screw 22 rotates, the lifting screw sleeve 21 can be driven to longitudinally slide from the bottom to the inside of the acidification adsorption device 1.
The lower end of the driving screw 22 is fixedly provided with a first gear 23, the frame 2 is provided with a driving motor 24, the driving motor 24 is provided with a second gear 25 meshed with the first gear 23, and when the driving motor 24 is electrified, the driving screw 22 can be rotated through the cooperation of the second gear 25 and the first gear 23, and then the lifting or the lowering of the lifting screw sleeve 21 is further realized.
The acidification adsorption device 1 is provided with a film covering unit for covering films and recovering porous films 4, the film covering unit comprises a film covering frame 5, a scraper knife 6 and a plurality of suckers 7 arranged on the film covering frame 5, the scraper knife 6 is fixedly arranged at the lower end of the left side of the film covering frame 5, the film covering frame 5 is slidably arranged above the acidification adsorption device 1, specifically, as shown in fig. 1, the left side of the acidification adsorption device 1 is fixedly provided with a side plate 12, the right end surface of the side plate 12 is provided with a guide sliding rod 9 extending rightward, the guide sliding rod 9 is preferably a hexagonal rod, a plurality of groups of guide sliding rods can be arranged, the film covering frame 5 is slidably arranged on the guide sliding rod 9, and hexagonal holes matched with the shapes of the sliding rods are formed in the guide sliding rod, namely, the film covering frame 5 is slidably arranged above the acidification adsorption device 1 through the guide sliding rod 9.
A first spring 13 is arranged between the film coating frame 5 and the side plate 12, the first spring 13 is preferably a tension spring, the first spring 13 is sleeved on the guide slide rod 9, and two ends of the first spring are fixedly connected with the side plate 12 and the left end face of the film coating frame 5; at the beginning, the film coating frame 5 is locked on the right side of the acidification adsorption device 1, at the moment, the first spring 13 is in a stretched state, when the film coating frame 5 is unlocked, the film coating frame can slide leftwards under the action of the tensile force of the first spring 13, and at the moment, if the lifting plate 3 is positioned on the top of the acidification adsorption device 1, the shovel blade 6 also slides leftwards along with the film coating frame 5 to shovel out the porous film 4 with flocculate on the surface of the lifting plate 3 on the path.
The film coating frame 5 is provided with a guide groove 10 matched with the scraper knife 6, as shown in fig. 3, the bottom of the guide groove 10 extends to a side far away from the scraper knife 6 to be provided with a supporting plate 11, preferably, the scraper knife 6 and the supporting plate 11 are integrally formed with the film coating frame 5, the material of the film coating frame 5 can be preferably engineering plastics, and can also be supported by adopting wear-resistant materials such as wear-resistant alloy, when the scraper knife 6 slides leftwards along with the film coating frame 5 to scoop out the porous film 4 on the lifting plate 3, one scooped end of the porous film 4 enters the guide groove 10 and then is placed on the supporting plate 11, preferably, the porous film 4 is a hard flexible film, namely the film can be coiled but also has a certain bending rigidity.
As shown in fig. 3, the suction cup 7 is disposed on one side of the scraper knife 6 near the supporting plate 11, a film roll 8 matched with the suction cup 7 is disposed on one side of the acidification adsorption device 1, the film roll 8 is a porous film roll, specifically as shown in fig. 2, the film roll 8 is rotatably disposed on a right side wall body of the acidification adsorption device 1, a plurality of guide pulleys 46 for guiding the porous film 4 are disposed on the left side of the film roll 8, one end of the film roll 8 extends leftwards and is disposed on the guide pulleys 46, when the film coating frame 5 is locked on the right side of the acidification adsorption device 1, the suction cup 7 is in a state of being adsorbed with the porous film 4 on the guide pulleys 46, and when the lifting plate 3 is lifted to the top of the acidification adsorption device 1, the film coating frame 5 slides to scoop the porous film 4 on the lifting plate 3 into the guide grooves 10, and covers a new porous film 4 adsorbed by the suction cup 7 on the surface of the lifting plate 3.
As shown in fig. 4, the outer edge of the lifting plate 3 is provided with an electric heating wire 14 for fusing the porous membrane 4, the left end surface of the acidification adsorption device 1 is provided with a first button 15 matched with the sliding film coating frame 5, that is, when the film coating frame 5 is stretched to the leftmost side by the stretching force of the first spring 13, the film coating frame 5 can trigger the first button 15, the first button 15 is electrically connected with the electric heating wire 14, when the first button 15 is triggered, the electric heating wire 14 can be electrified and heated, that is, after the sucking disc 7 covers the adsorbed new porous membrane 4 on the surface of the lifting plate 3 from right to left, the first button 15 is triggered, so that the new porous membrane 4 on the surface of the lifting plate 3 is fused, and the porous membrane 4 is adsorbed by residual water stains on the surface of the lifting plate 3.
The acidification adsorption device 1 is provided with a locking unit for locking the tectorial membrane frame 5, the locking unit comprises a lock pin 31, a first electromagnet 32 and a second spring 33, the lock pin 31 is longitudinally arranged on the right side of the acidification adsorption device 1 in a sliding mode, the tectorial membrane frame 5 is provided with a pin hole 34 matched with the lock pin 31, the pin hole 34 is arranged on the lower end face of the shovel blade 6, the lock pin 31 is provided with a limiting plate 35, the second spring 33 is arranged between the limiting plate 35 and the acidification adsorption device 1, the second spring 33 is sleeved on a rod body at the lower end of the lock pin 31, two ends of the second spring 33 are respectively propped against the limiting plate 35 and the wall body of the acidification adsorption device 1, the first electromagnet 32 is fixedly arranged on the wall body of the acidification adsorption device 1, the first electromagnet 32 is in a power-off state initially, the lock pin 31 is matched with the pin hole 34 to enable the tectorial membrane frame 5 to be fixed on the right side of the acidification adsorption device 1, at the moment, the first electromagnet 32 is in a stretching state, after the first electromagnet 32 is electrified, the limiting plate 35 is adsorbed by the first electromagnet 32 and compresses the second spring 33, and the lock pin 31 is enabled to be separated from the lock pin 31 from the matched with the pin hole 34, and the lock pin 31 is in a stretching state freely to be in a stretching state by the first electromagnet 13.
The lower end of the lifting screw sleeve 21 extends to the left side and fixedly provided with a mounting plate 41, the upper end surface of the mounting plate 41 is fixedly provided with a second electromagnet 43, the bottom of the acidification adsorption device 1 is provided with a second button 42 matched with the mounting plate 41 after lifting, namely, when the lifting screw sleeve 21 slides upwards to a limit position, the mounting plate 41 triggers the second button 42, the second button 42 is electrically connected with the first electromagnet 32, namely, when the lifting plate 3 slides upwards to the topmost position along with the lifting screw sleeve 21, the first electromagnet 32 is triggered to enable the lock pin 31 to unlock, at the moment, the film coating frame 5 slides leftwards to scoop up a waste film on the lifting plate 3, and a new film adsorbed by the suction cup 7 is coated.
The bottom of the acidification adsorption device 1 is provided with an adsorption plate 44 adsorbed by a lifted second electromagnet 43, the adsorption plate 44 is connected with the film coating frame 5 through a pull rope 45, after the lifting screw sleeve 21 is lifted to the uppermost limit position, the second electromagnet 43 is adsorbed by the adsorption plate 44, at the moment, acid-regulating and filtered liquid in the acidification adsorption device 1 is discharged, new bromine-containing wastewater and concentrated sulfuric acid are added for next acid-regulating, then the lifting screw sleeve 21 slides downwards under the action of the driving motor 24 to reset, the second electromagnet 43 is adsorbed by the adsorption plate 44, the adsorption plate 44 pulls the film coating frame 5 through the pull rope 45 to slide rightwards to reset, then the locking pin 31 is locked with the pin hole 34 in a matching way, and the sucker 7 continues to adsorb a new porous film 4 on the guide pulley 46.
In this embodiment, the electrical apparatus or the electronic component may be automatically controlled by connection of a PLC controller, so as to improve the acid-adjusting efficiency.
A recycling process of a bromine-containing wastewater treatment device comprises the following steps:
s1: acidifying adsorption, namely introducing industrial wastewater rich in bromide ions and organic bromides (the content of the bromide ions is 20mg/L-10 g/L) into an acidifying adsorption device, and regulating the pH value of the industrial wastewater to 2-4 by using 98% sulfuric acid to obtain acidified bromine-containing industrial wastewater;
simultaneously, sulfuric acid reacts with metal ions such as iron ions in the wastewater to generate ferric salt, so that organic matters in the wastewater generate flocculent precipitate, then the lifting plate 3 is lifted upwards to adhere the flocculent precipitate to the porous membrane 4, after being lifted to the top, the locking unit is unlocked, the membrane covering frame 5 shovels the porous membrane 4 adhered with flocculate onto the supporting plate 11 under the tensile force of the first spring 13, and simultaneously, the sucker 7 adsorbs the new porous membrane 4 to cover the surface of the lifting plate 3, and the new porous membrane is fused by the heating wire 14 to cover the surface of the lifting plate 3.
S2: LAT advanced oxidation, namely introducing the acidified bromine-containing industrial wastewater into an LAT advanced oxidation tank for LAT advanced catalytic oxidation, and oxidizing bromide ions in the acidified liquid on an anode to generate bromine molecules after the LAT advanced oxidation tank is electrified, wherein the acidified liquid in the LAT advanced oxidation tank is changed into oxidizing liquid;
s3: LAT catalyst activation: introducing the oxidation solution into a buffer tank, and adding a LAT catalyst into the buffer tank to activate bromide ions, organic bromides and bromine molecules to obtain an activated oxidation solution;
s4: blowing off: introducing activated oxidation liquid into a stripping tower, spraying the activated oxidation liquid from the top of the stripping tower, blowing out bromine molecules in the activated oxidation liquid along with air, and finally enabling industrial wastewater to flow out of air containing the bromine molecules from the bottom of the stripping tower to enter a washing tower from the top of the stripping tower;
s5: washing: the bromine-containing air enters a washing tower for washing, and other gas impurities such as carbon dioxide, chlorine and the like in the bromine-containing air are washed and removed to obtain purer bromine-containing air;
s6: in the absorption tower, bromine molecules flow from top to bottom along with air pushed by a Roots blower, are absorbed by 20% sodium sulfide solution sprayed from the top in the absorption tower to generate sodium bromide and sulfur, and finally mixed liquid of the sodium bromide and the sulfur is obtained;
s7: and (3) filtering: removing sulfur in the mixed solution of sodium bromide and sulfur in a filtering mode to obtain a 45% sodium bromide liquid product;
s8: and (5) crystallization and drying: and (3) drying 45% of liquid sodium bromide crystals to obtain sodium bromide solids which are more than or equal to 98.5%.
Embodiment one:
influence of pH value on COD and bromide ion removal rate during acidification;
taking 5 beakers, numbering 1, 2, 3, 4 and 5, respectively adding 500ml of PTA production wastewater into the 5 beakers, respectively adjusting the pH values to 1, 2, 3, 4 and 5, respectively corresponding the pH values to the beaker numbers one by one, respectively putting the wastewater from the 5 beakers into a LAT advanced oxidation tank for oxidation for 15 minutes, then adding 0.03g of LAT catalyst, stirring for 15 minutes for activation, introducing the activated water into a stripping tower, and measuring the COD and bromide ion content of the stripped water. The data results are given in the following table:
| raw water | Adjust ph=1 | Adjusting ph=2 | Adjusting ph=3 | Adjust ph=4 | Adjust ph=5 | |
| COD（mg/L） | 150 | 30.1 | 32.3 | 35.4 | 53.2 | 80.4 |
| Bromide ion (mg/L) | 400 | 26.1 | 26.6 | 28.9 | 120.9 | 208.5 |
| COD removal Rate (%) | 79.93 | 78.47 | 76.4 | 64.53 | 46.4 | |
| Bromine ion removal Rate (%) | 93.48 | 93.35 | 92.78 | 69.78 | 47.88 |
The lower the pH value during acidification, the better the removal rate of COD and bromide ions is, and the pH value during acidification is adjusted to 2-3 properly in consideration of economic benefits.
Embodiment two:
influence of oxidation time of LAT advanced oxidation tank on COD and bromide ion removal rate;
taking 5 beakers, numbering 1, 2, 3, 4 and 5, respectively adding 500ml of PTA production wastewater into the 5 beakers, regulating the pH value to 2.5, respectively putting the wastewater from the 5 beakers into LAT advanced tanks for oxidization for 5, 10, 15, 20 and 25 minutes, then adding 0.03g of LAT catalyst, stirring for 15 minutes for activation, introducing the activated water into a stripping tower, and measuring the COD and bromide ion content of the stripped water. The data results are given in the following table:
| raw water | Oxidizing for 5 min | Oxidizing for 10 min | Oxidizing for 15 min | Oxidizing for 20 min | Oxidizing for 25 min | |
| COD（mg/L） | 150 | 100.9 | 72.3 | 35.6 | 34.7 | 24.6 |
| Bromide ion (mg/L) | 400 | 150.7 | 83.6 | 64.3 | 44.8 | 38.9 |
| COD removal Rate (%) | 32.73 | 51.8 | 76.27 | 76.86 | 83.6 | |
| Bromine ion removal Rate (%) | 62.33 | 79.1 | 83.93 | 88.8 | 90.27 |
From the above data, it was found that the longer the oxidation time of the LAT advanced oxidation tank, the better the removal rate of COD and bromide ion, and the oxidation time was preferably selected to 15 minutes in view of economic efficiency.
Embodiment III:
the effect of LAT catalyst addition COD and bromide removal rate;
taking 5 beakers, numbering 1, 2, 3, 4 and 5, respectively adding 500ml of PTA production wastewater into the 5 beakers, regulating the pH value to 2.5, respectively putting the wastewater from the 5 beakers into a LAT advanced oxidation tank for oxidation for 15 minutes, respectively adding 0.01g, 0.02g, 0.03g, 0.04g and 0.05g of LAT catalyst, stirring for 15 minutes, activating, introducing the activated water into a stripping tower, and measuring the COD and bromide ion content of the stripped water. The data results are given in the following table:
| raw water | 0.01g | 0.02g | 0.03g | 0.04g | 0.05g | |
| COD（mg/L） | 150 | 118.5 | 83.1 | 37.8 | 34.8 | 33 |
| Bromide ion (mg/L) | 400 | 334.7 | 206.8 | 50.6 | 39.7 | 32.4 |
| COD removal Rate (%) | 21 | 44.6 | 74.8 | 76.8 | 78 | |
| Bromine ion removal Rate (%) | 94.75 | 48.3 | 87.35 | 90.1 | 91.9 |
From the above data, it was found that the removal rate of COD and bromide ions increased rapidly to 0.03g as the amount of LAT catalyst added increased, and the rate of increase became slower, and that the amount of LAT catalyst added was preferably 0.03g in view of economic efficiency.
Embodiment four:
influence of residence time of LAT catalyst in water on COD and bromide removal rate;
taking 5 beakers, numbering 1, 2, 3, 4 and 5, respectively adding 500ml of PTA production wastewater into the 5 beakers, regulating the pH value to 2.5, respectively putting the wastewater from the 5 beakers into a LAT advanced oxidation tank for oxidation for 15 minutes, then adding 0.03g of LAT catalyst, respectively stirring for 5 minutes, 10 minutes, 15 minutes, 20 minutes and 25 minutes for activation, introducing the activated water into a stripping tower, and measuring the COD and bromide ion content of the stripped water. The data results are given in the following table:
| raw water | 5min | 10min | 15min | 20min | 25min | |
| COD（mg/L） | 150 | 118.5 | 83.1 | 37.8 | 34.8 | 33 |
| Bromide ion (mg/L) | 400 | 334.7 | 206.8 | 50.6 | 39.7 | 32.4 |
| COD removal Rate (%) | 21 | 44.6 | 74.8 | 76.8 | 78 | |
| Bromine ion removal Rate (%) | 94.75 | 48.3 | 87.35 | 90.1 | 91.9 |
Fifth embodiment:
the influence of the gas-liquid ratio on COD and bromide ion removal rate during stripping;
taking 5 beakers, numbering 1, 2, 3, 4 and 5, respectively adding 500ml of PTA production wastewater into the 5 beakers, regulating the pH values to 2.5, respectively putting the wastewater from the 5 beakers into an electrolytic tank LAT-LEC for oxidization for 15 minutes, then adding 0.03g of LAT-BAB-1 catalyst, respectively stirring for 15 minutes for activation, introducing the activated water into a stripping tower, and respectively regulating the gas-liquid ratio during stripping to be 50: 1. 100: 1. 150: 1. 200: 1. 250:1, measuring the content of COD and bromide ions in the water after stripping. The data results are given in the following table:
| raw water | 50：1 | 100：1 | 150：1 | 290：1 | 250：1 | |
| COD（mg/L） | 150 | 118.5 | 83.1 | 37.8 | 34.8 | 33 |
| Bromide ion (mg/L) | 400 | 334.7 | 206.8 | 50.6 | 39.7 | 32.4 |
| COD removal Rate (%) | 21 | 44.6 | 74.8 | 76.8 | 78 | |
| Bromine ion removal Rate (%) | 94.75 | 48.3 | 87.35 | 90.1 | 91.9 |
The embodiment of the invention provides a method for treating PTA production wastewater, which comprises the following steps:
PTA production wastewater in laboratory contains 4000mg/L bromine and 1500mg/L COD
Acidifying: 1000ml of PTA production wastewater is taken, 98% concentrated sulfuric acid is added into the PTA production wastewater, and the pH value of the wastewater is adjusted to 2.5 under stirring.
LAT advanced oxidation tank electrooxidation: and (3) introducing the activated PTA production wastewater into an electrolytic tank for electrolysis, wherein the voltage during electrolysis is 3.6V, the current is 5A, and the electrolysis is carried out for 15 minutes, and oxidizing bromine ions and organic bromides into bromine simple substances.
LAT catalyst activation: after acidification, 0.05g LAT catalyst is added into the PTA production wastewater, and the mixture is stirred for 15 minutes to activate bromide ions and organic bromides.
Blowing off: introducing oxidized PTA production wastewater into a stripping tower, blowing out bromine simple substance along with air, and flowing out the stripped industrial wastewater from the bottom of the tower, wherein the COD (chemical oxygen demand) of the wastewater is measured to be 30mg/l.
Absorption: absorbing bromine simple substance of bromine-containing air by using an absorbent (20% sodium sulfide aqueous solution) to obtain mixed liquid of sodium bromide and sulfur, and ending the absorption process when the pH value of the absorption liquid is 5.5-6.5. The absorbent selected is sodium sulfide.
And (3) filtering: and (3) separating sulfur from sodium bromide liquid by using a filter to obtain a 45% sodium bromide liquid product. Evaporating and crystallizing to obtain sodium bromide solid crystals.
The bromine content is reduced from 4000mg/L to 10mg/L in the whole process, and the COD is reduced from 1500mg/L to 30mg/L.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The utility model provides a bromine-containing wastewater treatment device, includes acidizing adsorption equipment (1) and is used for fixed frame (2) of this acidizing adsorption equipment (1), its characterized in that: a lifting plate (3) is arranged in the acidification adsorption device (1), and a porous membrane (4) is coated on the surface of the lifting plate (3);
a film coating unit for coating and recovering the porous film (4) is arranged on the acidification adsorption device (1);
the film laminating unit comprises a film laminating frame (5), a shovel blade (6) and a plurality of suckers (7) arranged on the film laminating frame (5), and a film roll (8) matched with the suckers (7) is arranged on one side of the acidification adsorption device (1);
the film coating frame (5) is arranged above the acidification adsorption device (1) in a sliding manner, and a guide sliding rod (9) matched with the film coating frame (5) is arranged on the acidification adsorption device (1);
a guide groove (10) matched with the shovel blade (6) is formed in the film coating frame (5);
when the lifting plate (3) is lifted to the top of the acidification adsorption device (1), the film coating frame (5) slides to shovel the porous film (4) on the lifting plate (3) into the guide groove (10), and a new porous film (4) adsorbed by the sucker (7) is coated on the surface of the lifting plate (3);
a side plate (12) is arranged on the acidification adsorption device (1), a first spring (13) is arranged between the film coating frame (5) and the side plate (12), and the first spring (13) is a tension spring;
the outer edge of the lifting plate (3) is provided with an electric heating wire (14) for fusing the porous membrane (4), the acidification adsorption device (1) is provided with a first button (15) matched with the sliding membrane coating frame (5), and the first button (15) is electrically connected with the electric heating wire (14);
the lifting plate (3) is provided with a lifting screw sleeve (21), the frame (2) is provided with a driving screw (22) in threaded fit with the lifting screw sleeve (21), the driving screw (22) is provided with a first gear (23), the frame (2) is provided with a driving motor (24), and the driving motor (24) is provided with a second gear (25) meshed with the first gear (23);
the acidification adsorption device (1) is provided with a locking unit for locking the tectorial membrane frame (5), the locking unit comprises a lock pin (31), a first electromagnet (32) and a second spring (33), the tectorial membrane frame (5) is provided with a pin hole (34) matched with the lock pin (31), the lock pin (31) is provided with a limiting plate (35), the second spring (33) is arranged between the limiting plate (35) and the acidification adsorption device (1), and the first electromagnet (32) is fixedly arranged on the acidification adsorption device (1);
the end part of the lifting screw sleeve (21) is provided with a mounting plate (41), the bottom of the acidification adsorption device (1) is provided with a second button (42) matched with the mounting plate (41) after lifting, and the second button (42) is electrically connected with the first electromagnet (32);
the acidification adsorption device is characterized in that a second electromagnet (43) is arranged on the mounting plate (41), an adsorption plate (44) which is adsorbed by the lifted second electromagnet (43) is arranged at the bottom of the acidification adsorption device (1), and the adsorption plate (44) is connected with the tectorial membrane frame (5) through a stay cord (45).
2. A bromine-containing wastewater treatment apparatus according to claim 1, wherein: the film laminating frame (5) is provided with a supporting plate (11), and the supporting plate (11) is connected with the bottom of the guide groove (10) and is used for providing support for the porous film (4) shoveled into the guide groove (10).
3. A bromine-containing wastewater treatment apparatus according to claim 2, wherein: the acidification adsorption device (1) is provided with a plurality of guide pulleys (46) which are matched with the porous membrane (4) for guiding the acidification adsorption device.
4. A process for recycling a bromine-containing wastewater treatment apparatus according to claim 3, wherein: the process comprises the following steps:
s1: acidifying adsorption, namely introducing industrial wastewater rich in bromide ions and organic bromides into an acidifying adsorption device, and regulating the pH value of the industrial wastewater to 2-4 by using 98% sulfuric acid to obtain acidified bromine-containing industrial wastewater;
simultaneously, sulfuric acid reacts with metal ions such as iron ions in the wastewater to generate ferric salt, so that organic matters in the wastewater generate flocculent precipitate, then the lifting plate (3) is lifted upwards to adhere the flocculent precipitate to the porous membrane (4), after the flocculating precipitate is lifted to the top, the locking unit is unlocked, the membrane covering frame (5) is used for shoveling the porous membrane (4) adhered with flocculate into the supporting plate (11) under the action of the tension of the first spring (13), and meanwhile, the sucker (7) is used for adsorbing the new porous membrane (4) to cover the surface of the lifting plate (3) and is fused by the heating wire (14) to cover the surface of the lifting plate (3);
s2: LAT advanced oxidation, namely introducing the acidified bromine-containing industrial wastewater into an LAT advanced oxidation tank for LAT advanced catalytic oxidation, and oxidizing bromide ions in the acidified liquid on an anode to generate bromine molecules after the LAT advanced oxidation tank is electrified, wherein the acidified liquid in the LAT advanced oxidation tank is changed into oxidizing liquid;
s3: LAT catalyst activation: introducing the oxidation solution into a buffer tank, and adding a LAT catalyst into the buffer tank to activate bromide ions, organic bromides and bromine molecules to obtain an activated oxidation solution;
s4: blowing off: introducing activated oxidation liquid into a stripping tower, spraying the activated oxidation liquid from the top of the stripping tower, blowing out bromine molecules in the activated oxidation liquid along with air, and finally enabling industrial wastewater to flow out of air containing the bromine molecules from the bottom of the stripping tower to enter a washing tower from the top of the stripping tower;
s5: washing: the bromine-containing air enters a washing tower for washing, and other gas impurities such as carbon dioxide, chlorine and the like in the bromine-containing air are washed and removed to obtain purer bromine-containing air;
s6: in the absorption tower, bromine molecules flow from top to bottom along with air pushed by a Roots blower, are absorbed by 20% sodium sulfide solution sprayed from the top in the absorption tower to generate sodium bromide and sulfur, and finally mixed liquid of the sodium bromide and the sulfur is obtained;
s7: and (3) filtering: removing sulfur in the mixed solution of sodium bromide and sulfur in a filtering mode to obtain a 45% sodium bromide liquid product;
s8: and (5) crystallization and drying: and (3) drying 45% of liquid sodium bromide crystals to obtain sodium bromide solids which are more than or equal to 98.5%.
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| CN116262649A (en) * | 2022-01-27 | 2023-06-16 | 大连波美科技有限公司 | Bromine-containing inorganic salt and organic acid (salt) wastewater treatment system and application method |
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| KR200323476Y1 (en) * | 2003-03-18 | 2003-08-14 | 대한통운 주식회사 | Dipping type membrane separation apparatus for advanced sewage and waste water treatment |
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