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CN-121974297-A - Combined device for extracting bromine from strong brine and application

CN121974297ACN 121974297 ACN121974297 ACN 121974297ACN-121974297-A

Abstract

The invention discloses a concentrated brine bromine extraction combined device and application, the combined device comprises a bromine extraction unit, a salt extraction unit, a caustic soda unit and a ferric trichloride unit, wherein concentrated seawater and PTA wastewater after desalination are used as raw material liquid and extracted in a liquid bromine product form to realize recycling, the salt extraction unit adopts electrodialysis concentration and multi-effect evaporation salt preparation processes to produce industrial salt, the caustic soda unit uses 40% of industrial waste salt obtained by the bromine extraction unit and 60% of outsourced solid salt as raw materials, an ion membrane electrolysis process is adopted to produce sodium hydroxide, hydrochloric acid, chlorine and sodium hypochlorite to produce byproduct hydrogen, and the chlorine produced by the caustic soda unit is used in the ferric trichloride unit and the bromine extraction unit to realize waste treatment, recycling utilization and cost reduction and synergy in a circulating system.

Inventors

  • LIU ZE
  • ZHANG TENGFEI
  • FENG DEKAI
  • YIN LIANG
  • CHEN RONGJIAN
  • XU HONGYAN
  • ZHAO PINGYUE

Assignees

  • 恒力石化（大连）炼化有限公司

Dates

Publication Date
20260505
Application Date
20260403

Claims (9)

  1. 1. The combined device for extracting bromine from strong brine is characterized by comprising a bromine extracting unit, a salt extracting unit, a caustic soda unit and a ferric trichloride unit; The bromine extracting unit comprises a raw material tank (1), an acidification processing unit (2), an air blowing-out unit (3), a steam distillation unit (4), a raw material mixing unit (5), a hydrochloric acid introducing unit (6), an air introducing unit (7), a sulfur adding unit (8), a chlorine introducing unit (9) and a liquid bromine collecting unit (10), wherein the raw material tank (1) is sequentially connected with the raw material mixing unit (5), the acidification processing unit (2), the air blowing-out unit (3), the steam distillation unit (4) and the liquid bromine collecting unit (10); The salt extraction unit comprises a neutralization unit (11), a low-bromine seawater discharging unit (12), a discharging seawater collecting device (13), an electrodialysis concentration unit (14), an evaporation crystallization unit (15), a pH adjusting unit (16), a low-bromine seawater waste preparation unit (17), a sodium chloride adding unit (18), a fresh brine discharging unit (19), an electrodialysis concentration liquid channel (20) and a condensed fresh water discharging unit (21), wherein the neutralization unit (11) is sequentially connected with the low-bromine seawater discharging unit (12) and the discharging seawater collecting device (13), and the neutralization unit (11) is sequentially connected with the low-bromine seawater waste preparation unit (17), the electrodialysis concentration unit (14), the evaporation crystallization unit (15) and the condensed fresh water discharging unit (21); the caustic soda unit comprises an outsourcing salt adding unit (22), an industrial waste salt collecting device (23), a hydrochloric acid synthesizing unit (24), a caustic soda preparation unit (25), a sodium chloride conveying unit (26), a gas conveying unit (27), a hydrogen conveying unit (28), a chlorine conveying unit I (29), a hydrochloric acid conveying unit I (30), a calcium oxide conveying unit (31) and a caustic soda collecting device (32), wherein the outsourcing salt adding unit (22) and the industrial waste salt collecting device (23) are connected with the sodium chloride conveying unit (26), the gas conveying unit (27), the hydrogen conveying unit (28), the chlorine conveying unit I (29), the calcium oxide conveying unit (31) and the caustic soda collecting device (32) are arranged outside the caustic soda preparation unit (25) and the hydrochloric acid synthesizing unit (24) are connected through the gas conveying unit (27); The iron trichloride unit comprises a hydrochloric acid conveying unit I (30), a calcium oxide conveying unit (31), a caustic soda collecting device (32), an iron trichloride synthesizing unit (33), a park using unit (34), a chlorine conveying unit II (35), a pickling waste liquid conveying unit (36), an iron chloride conveying unit I (37), a hydrochloric acid conveying unit II (38), an iron powder adding unit (39) and an iron chloride conveying unit II (40), wherein the iron trichloride synthesizing unit (33) is connected with the park using unit (34), the chlorine conveying unit II (35), the iron chloride conveying unit I (37) and the iron chloride conveying unit II (40) are connected to the outside of the iron trichloride synthesizing unit (33), and the hydrochloric acid conveying unit I (30) is sequentially connected with the hydrochloric acid conveying unit II (38), the iron powder adding unit (39) and the iron chloride conveying unit II (40).
  2. 2. The combination according to claim 1, characterized in that the air blow-out unit (3) in the bromine extraction unit is connected to a neutralization unit (11) in the salt extraction unit; The electrodialysis concentration unit (14) in the salt extraction unit is also connected with the light brine discharge unit (19), and the evaporation crystallization unit (15) in the salt extraction unit is also connected with the industrial waste salt collecting device (23) in the caustic soda unit.
  3. 3. The combination device according to claim 1, wherein a sodium chloride conveying unit (26) in the caustic soda unit is connected with a caustic soda preparation unit (25), a hydrochloric acid conveying unit I (30) is arranged outside the hydrochloric acid synthesis unit (24), the hydrochloric acid conveying unit I (30) is used for providing hydrochloric acid for an acidification treatment unit (2) and a ferric trichloride synthesis unit (33) of the bromine extraction unit, and the hydrochloric acid conveying unit I (30) is sequentially connected with a hydrochloric acid introducing unit (6) and the acidification treatment unit (2) in the bromine extraction unit; the caustic soda preparation unit (25) in the caustic soda unit is also connected with a chlorine gas conveying unit II (35) in the ferric trichloride unit, the chlorine gas conveying unit II (35) is used for supplying chlorine gas to the ferric trichloride synthesis unit (33), and the caustic soda preparation unit (25) is also connected with a chlorine gas conveying unit I (29) and is used for supplying chlorine gas to the steam distillation unit (4).
  4. 4. The combination device according to claim 1, wherein the bromine extraction unit is characterized in that sea-light concentrated bromine-containing seawater is introduced into the raw material tank (1) through the top of a packing tower at 4000-4200 t/h, PTA bromine-containing wastewater is introduced at 200-250 t/h, and PTA tail gas washing wastewater is introduced at 100-150 t/h to form raw material liquid; The sulfur adding unit (8) adds sulfur to the steam distillation unit (4) at 102-140 kg/h, and the chlorine introducing unit (9) introduces chlorine to the steam distillation unit (4) at 377-410 kg/h.
  5. 5. The combination unit according to claim 1, wherein the speed of outward discharge of the low-bromine seawater discharging unit (12) is 4116.3-4500 t/h, the low-bromine seawater making waste unit (17) is used for introducing low-bromine seawater into the electrodialysis concentration unit (14) at a flow rate of 150.0-177.4 t/h, the sodium chloride adding unit (18) is used for introducing NaCl solution into the electrodialysis concentration unit (14) at a flow rate of 5320.3-5500.0 t/h, and the weak brine discharging unit (19) is used for discharging weak brine at a flow rate of 166.5-200.0 t/h; The electrodialysis concentrated solution channel (20) flows out of the electrodialysis concentrated solution at a flow rate of 10.9-15.0 t/h, evaporation crystallization is carried out in the evaporation crystallization unit (15) at 80-90 ℃, and then the condensed fresh water is discharged through the condensed fresh water discharge unit (21) at a flow rate of 9.1-12.0 t/h.
  6. 6. The combination according to claim 1, characterized in that the industrial waste salt collected from the industrial waste salt collection device (23) is fed to the caustic soda production unit (25) through the sodium chloride conveying unit (26) at 1862-2000 kg/h and the outsourced salt is fed at 2793-3000 kg/h to produce caustic soda and chlorine.
  7. 7. The combination device according to claim 1, wherein the gas conveying unit (27) is used for introducing hydrochloric acid into the hydrochloric acid synthesizing unit (24) at a flow rate of 2220-2500 kg/h to synthesize hydrochloric acid, the chlorine gas is introduced into the steam distillation unit (4) at a flow rate of 350-377 kg/h through the chlorine gas conveying unit I (29) and the chlorine gas introducing unit (9), the chlorine gas is introduced into the ferric trichloride synthesizing unit (33) at a flow rate of 0.1500-0.2272 kg/h through the chlorine gas conveying unit II (35) to prepare ferric trichloride, and the residual byproduct hydrogen generated by the caustic soda preparing unit (25) is discharged through the hydrogen conveying unit (28).
  8. 8. The combination according to claim 1, characterized in that the prepared 30% hydrochloric acid is transported at 1.000-1.317 t/h by means of a hydrochloric acid transport unit II (38), iron powder is added at 0.304-0.500 t/h by means of an iron powder adding unit (39), iron scale is added and pickling waste liquid is transported at 1.00-1.25 t/h by means of a pickling waste liquid transport unit (36) for the preparation of iron trichloride.
  9. 9. Use of a combination according to any one of claims 1 to 8 for bromine extraction, caustic soda production and ferric trichloride production.

Description

Combined device for extracting bromine from strong brine and application Technical Field The invention belongs to the technical field of sea water desalination, and particularly relates to a strong brine bromine extraction combined device and application. Background The existing PTA (purified terephthalic acid) production device with the capacity of 1200 ten thousand tons needs hydrobromic acid as an accelerator in the PTA production, the existing sea water desalination device can produce about 3000 ten thousand tons of fresh water every year, and about 3600 ten thousand tons of concentrated sea water can be produced every year according to the 1:1.2 estimation. The concentrated seawater is diluted and discharged into the sea through a siphon well at present, and the discharged seawater meets the standard but has the condition of bromine and salt loss. In the manufacturing and maintenance process of ships, a galvanization workshop and a phosphating workshop are important places for metal surface treatment, acid washing is needed in the galvanization and phosphating processes, a large amount of acid washing waste liquid containing ferric dichloride (FeCl 2) is generated, additional treatment is needed, the problem that waste water is difficult to treat exists, molten iron is inevitably generated in the steel plate cutting process, and flows onto an operation surface to be cooled to become irregular flaky ferric oxide waste residues (such as Fe 2O3、Fe3O4 and the like), so that the difficult problem of recovery exists. The PTA wastewater and the seawater desalination unit of the existing seawater desalination and wastewater treatment method have the problems of sodium chloride loss caused by bromine element discharge, hydrobromic acid and ferric trichloride depend on the problems of insufficient load of a caustic soda unit, additional treatment of pickling wastewater and additional treatment of molten iron cooling iron waste residues caused by insufficient primary seawater supply, and the method for treating the wastewater by using the waste is provided. Disclosure of Invention In order to solve the technical problems, the invention discloses a combined device for extracting bromine from strong brine and application thereof. According to one aspect of the invention, there is provided a brine bromine extraction combination unit, which comprises a bromine extraction unit, a salt extraction unit, a caustic soda unit and a ferric trichloride unit; The bromine extracting unit comprises a raw material tank (1), an acidification processing unit (2), an air blowing-out unit (3), a steam distillation unit (4), a raw material mixing unit (5), a hydrochloric acid introducing unit (6), an air introducing unit (7), a sulfur adding unit (8), a chlorine introducing unit (9) and a liquid bromine collecting unit (10), wherein the raw material tank (1) is sequentially connected with the raw material mixing unit (5), the acidification processing unit (2), the air blowing-out unit (3), the steam distillation unit (4) and the liquid bromine collecting unit (10); The salt extraction unit comprises a neutralization unit (11), a low-bromine seawater discharging unit (12), a discharging seawater collecting device (13), an electrodialysis concentration unit (14), an evaporation crystallization unit (15), a pH adjusting unit (16), a low-bromine seawater waste preparation unit (17), a sodium chloride adding unit (18), a fresh brine discharging unit (19), an electrodialysis concentration liquid channel (20) and a condensed fresh water discharging unit (21), wherein the neutralization unit (11) is sequentially connected with the low-bromine seawater discharging unit (12) and the discharging seawater collecting device (13), and the neutralization unit (11) is sequentially connected with the low-bromine seawater waste preparation unit (17), the electrodialysis concentration unit (14), the evaporation crystallization unit (15) and the condensed fresh water discharging unit (21); the caustic soda unit comprises an outsourcing salt adding unit (22), an industrial waste salt collecting device (23), a hydrochloric acid synthesizing unit (24), a caustic soda preparation unit (25), a sodium chloride conveying unit (26), a gas conveying unit (27), a hydrogen conveying unit (28), a chlorine conveying unit I (29), a hydrochloric acid conveying unit I (30), a calcium oxide conveying unit (31) and a caustic soda collecting device (32), wherein the outsourcing salt adding unit (22) and the industrial waste salt collecting device (23) are connected with the sodium chloride conveying unit (26), the gas conveying unit (27), the hydrogen conveying unit (28), the chlorine conveying unit I (29), the calcium oxide conveying unit (31) and the caustic soda collecting device (32) are arranged outside the caustic soda preparation unit (25) and the hydrochloric acid synthesizing unit (24) are connected through the gas conveying unit (27); The iron trichloride unit c