CN101045529A - Technology process for producing bromide using concentrated seawater - Google Patents
Technology process for producing bromide using concentrated seawater Download PDFInfo
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- CN101045529A CN101045529A CN 200710057197 CN200710057197A CN101045529A CN 101045529 A CN101045529 A CN 101045529A CN 200710057197 CN200710057197 CN 200710057197 CN 200710057197 A CN200710057197 A CN 200710057197A CN 101045529 A CN101045529 A CN 101045529A
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- concentrated seawater
- bromine
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- air
- hydrogen bromide
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Abstract
A process for preparing bromine from concentrated seawater includes such steps as acidifying, oxidizing, air blowing-out, SO2 absorbing and distilling.
Description
Technical field
The present invention relates to a kind of technology of producing bromine, particularly adopt air to blow out the processing method of utilizing concentrated seawater production bromine that sulfurous gas absorbs tail gas closed circulation system bromine.
Background technology
Bromine is an important chemical material, and bromine has extensive use in industries such as fire retardant, fire-fighting medium, refrigeration agent, sensitive materials, medicine, agricultural chemicals, oil fields.At present, put forward bromine technology and generally adopt the open type acid system to put forward bromine technology, this process recovery ratio is low, the wasting of resources is comparatively serious, and install hugely, and be unfavorable for safeguarding, open wide simultaneously in the tail gas that mode of operation discharges and have a large amount of acidic substance, both corrode equipment, polluted environment again.
Though it is abundant to contain the bromine total amount in the seawater, but its unit content is very low, belongs to trace substantially, directly is that raw material system bromine is unreasonable economically with the seawater, therefore, the concentrated brine that produces in salt manufacturing of traditional technology general using or the desalting process is the production of raw material system bromine.But along with the development of urban construction, the land resources advantage weakens gradually, and the traditional processing technology of natural sun power evaporation concentration is produced concentrated brine and can be eliminated gradually.
Summary of the invention
For solving the problem that exists in the above-mentioned technology, the purpose of this invention is to provide a kind of processing method of utilizing concentrated seawater to produce bromine, high-quality industrial bromine will be extracted after the bromine concentration and separation in the concentrated seawater after salt-making process or the sea water desaltination, be beneficial to and then reduce bromine enrichment cost significantly, resource is fully utilized.
For achieving the above object, the technical solution that the present invention adopts provides a kind of processing method of utilizing concentrated seawater to produce bromine, and this technology may further comprise the steps:
1, a kind of processing method of utilizing concentrated seawater to produce bromine, this method may further comprise the steps:
Step 1: acidifying, with the raw materials for production concentrated seawater, its brominated scope: Br
-60～400mg/L adds the sulfur acid of distillation process generation and the spent acid of hydrochloric acid and carries out the concentrated seawater acidifying, and the concentrated seawater pH value is controlled at 2.5～4.5;
Step 2: oxidation, the concentrated seawater after the acidifying is fed chlorine, joining the chlorine rate is 100～120%, bromide anion generation oxidizing reaction in the concentrated seawater: (2Br
-+ Cl
2---→ Br
2+ 2Cl
-), generating free bromine, oxidation ratio reaches 80～100%;
Step 3: air blows out, and the concentrated seawater after the oxidation is delivered to the stripping tower top through pipeline, utilizes spray nozzle type concentrated seawater sparger, sprays the packing layer to stripping tower after concentrated seawater is atomized into drop, makes free bromine quicken desorb.Recirculated air is introduced stripping tower's packing layer, and free bromine is brought into (rate of blowing out reaches 85～95%) in the air, and the concentrated seawater after the separation is discharged outside the tower, delivers to the salt manufacturing operation and evaporates brine;
Step 4: absorb, the air that will contain free bromine imports the absorption tower, add the sulfur dioxide gas that reaction generates from sulfur furnace simultaneously, airborne free bromine is transformed into vaporific Hydrogen bromide, the air that contains Hydrogen bromide is again through mist eliminator, the enrichment of liquid hydrogen bromic acid is obtained intermediates Hydrogen bromide pregnant solution, and its brominated amount is 60～120g/L, and tail gas from absorption tower returns air through closed cycle system and blows out operation and carry out recycle;
Step 5: distillation, (brominated amount is that 60～120g/L) pregnant solution enters distillation tower to contain Hydrogen bromide, Hydrogen bromide is become free bromine by the chlorine oxidation that feeds at the bottom of tower in tower, and distill with steam heating, bromine vapor is discharged from cat head, through condensation, bromine water separates, refiningly obtain high-quality product bromine; The slops that pregnant solution produces after distilling is discharged at the bottom of by tower, and is introduced into acidizing process disacidify concentrated seawater.
Effect of the present invention is this process using air seal circulation, and the tail gas that produces reclaims by the recycle system, returns desorb and blows out operation, does not therefore have exhaust emissions, can not impact Air quality, has improved the rate that obtains of bromine.Main equipments such as stripping tower, absorption tower and mist eliminator adopt the fw frp round structure, and this device structure succinctly is convenient to install and operation.Adopt the spray nozzle type sparger, concentrated seawater sprays to packing layer after special shower nozzle is atomized into tiny drop.Sparger after the improvement more helps the desorb of free bromine after concentrated seawater is atomized, and has improved the rate of blowing out.This process using self-control sulfurous gas device.Promptly directly quantitatively add sulfur furnace by screw feeder with granular solid sulfur, in the air that feeds, directly burn into sulfur dioxide gas, after directly enter the absorption tower and be free on airborne molecular bromine reaction solution attitude hydrogen bromide (HBr) after the scrubber tower cooling washing.Guarantee the stable of whole production system, do not had " three wastes " discharging, environmentally safe.Can improve bromine and obtain rate, cut down the consumption of raw materials.
Description of drawings
Fig. 1 is the process method flow chart of production bromine of the present invention.
Embodiment
Reaching embodiment in conjunction with the accompanying drawings is illustrated the processing method use that utilizes concentrated seawater to produce bromine of the present invention.
The processing method of utilizing concentrated seawater to produce bromine of the present invention, main chemical reactions has in its technological process:
The oxidizing reaction of bromide anion: 2Br in the concentrated seawater
-+ Cl
2---→ Br
2+ 2Cl
-
Absorption reaction in the bromine air: Br
2+ SO
2+ 2H
2O---→ 2HBr+H
2SO
4
The oxidizing reaction of bromide anion: 2HBr+Cl in the distillation
2---→ Br
2+ 2HCl
The processing method of utilizing concentrated seawater to produce bromine of the present invention, being raw material with the concentrated seawater in the preparing salt by working up seawater process promptly, can be raw material with the concentrated seawater after the sea water desaltination also, adopts air to blow out, sulfurous gas absorbs, the processing method of tail gas sealing cyclic production bromine.Its technical process is: concentrated seawater enters stripping tower's preceding adding spent acid and quantitative chlorine makes bromide anion oxidation in pipeline; Concentrated seawater after the oxidation (oxidation liquid) enters stripping tower, with after the round-robin even air contacts, free bromine in the concentrated seawater is resolved to air; Brominated air adds an amount of sulfurous gas air Mixture before entering the absorption tower, make the molecular bromine of carrying secretly in the air be transformed into Hydrogen bromide (HBr) acid mist; This acid mist forms fine liquid particles and enters mist eliminator and make Hydrogen bromide obtain enrichment under the water smoke effect that sprays into; The air that mist eliminator is discharged still enters stripping tower by blower fan, and air is realized closed circulation.Pregnant solution distills after adding the chlorine oxidation, makes the finished product bromine.
The processing method of utilizing concentrated seawater to produce bromine of the present invention may further comprise the steps:
Step 1: acidifying, with the raw materials for production concentrated seawater, its brominated scope: Br
-60～400mg/L adds the sulfur acid of distillation process generation and the spent acid of hydrochloric acid and carries out the concentrated seawater acidifying, and the concentrated seawater pH value is controlled at 2.5～4.5;
Step 2: oxidation, the concentrated seawater after the acidifying is fed chlorine, joining the chlorine rate is 100～120%, bromide anion generation oxidizing reaction in the concentrated seawater: (2Br
-+ Cl
2---→ Br
2+ 2Cl
-), generating free bromine, oxidation ratio reaches 80～100%;
Step 3: air blows out, and the concentrated seawater after the oxidation is delivered to the stripping tower top through pipeline, utilizes spray nozzle type concentrated seawater sparger, sprays the packing layer to stripping tower after concentrated seawater is atomized into drop, makes free bromine quicken desorb.Recirculated air is introduced stripping tower's packing layer, and free bromine is brought into (rate of blowing out reaches 85～95%) in the air, and the concentrated seawater after the separation is discharged outside the tower, delivers to the salt manufacturing operation and evaporates brine;
Step 4: absorb, the air that will contain free bromine imports the absorption tower, add the sulfur dioxide gas that reaction generates from sulfur furnace simultaneously, airborne free bromine is transformed into vaporific Hydrogen bromide, the air that contains Hydrogen bromide is again through mist eliminator, the enrichment of liquid hydrogen bromic acid is obtained intermediates Hydrogen bromide pregnant solution, and its brominated amount is 60～120g/L, and tail gas from absorption tower returns air through closed cycle system and blows out operation and carry out recycle;
Step 5: distillation, (brominated amount is that 60～120g/L) pregnant solution enters distillation tower to contain Hydrogen bromide, Hydrogen bromide is become free bromine by the chlorine oxidation that feeds at the bottom of tower in tower, and distill with steam heating, bromine vapor is discharged from cat head, through condensation, bromine water separates, refiningly obtain high-quality product bromine; The slops that pregnant solution produces after distilling is discharged at the bottom of by tower, and is introduced into acidizing process disacidify concentrated seawater.The quality standard of gained finished product bromine:
Reaching industry standard is top grade product requirement among the ministerial standard QB2021-94, and its key technical indexes is: brominated amount 〉=99.7%, chlorinity≤0.05%, non-volatile matter≤0.05%.
Main equipments such as stripping tower, absorption tower and mist eliminator in this processing method institute use equipment adopt the fw frp round structure, and this device structure succinctly is convenient to install and operation.Adopt spray nozzle type concentrated seawater sparger simultaneously, concentrated seawater sprays to packing layer after special shower nozzle is atomized into tiny drop.Spray nozzle type concentrated seawater sparger after the improvement more helps the desorb of free bromine after concentrated seawater is atomized, and has improved the rate of blowing out.
This processing method has adopted self-control sulfurous gas device, promptly directly quantitatively add sulfur furnace by screw feeder with granular solid sulfur, in the air that feeds, directly burn into sulfur dioxide gas, after directly enter the absorption tower and be free on airborne molecular bromine reaction solution attitude hydrogen bromide (HBr) after the scrubber tower cooling washing.Guarantee the stable of whole production system, do not had " three wastes " discharging, environmentally safe.Can improve bromine and obtain rate, cut down the consumption of raw materials.
This project already realizes recycling economy as an environmental protection and energy saving project to sea salt, forms an energy-conservation industrial chain, and is significant.The proposition of its technical scheme is for making full use of of resource in the preparing salt by working up seawater process found an energy-efficient road.
Claims (1)
1, a kind of processing method of utilizing concentrated seawater to produce bromine, this method may further comprise the steps:
Step 1: acidifying, with the raw materials for production concentrated seawater, its brominated scope: Br
-60～400mg/L adds the sulfur acid of distillation process generation and the spent acid of hydrochloric acid and carries out the concentrated seawater acidifying, and the concentrated seawater pH value is controlled at 2.5～4.5;
Step 2: oxidation, the concentrated seawater after the acidifying is fed chlorine, joining the chlorine rate is 100～120%, bromide anion generation oxidizing reaction in the concentrated seawater: (2Br
-+ Cl
2→ Br
2+ 2Cl
-), generating free bromine, oxidation ratio reaches 80～100%;
Step 3: air blows out, and the concentrated seawater after the oxidation is delivered to the stripping tower top through pipeline, utilizes spray nozzle type concentrated seawater sparger, sprays the packing layer to stripping tower after concentrated seawater is atomized into drop, makes free bromine quicken desorb.Recirculated air is introduced stripping tower's packing layer, and free bromine is brought into (rate of blowing out reaches 85～95%) in the air, and the concentrated seawater after the separation is discharged outside the tower, delivers to the salt manufacturing operation and evaporates brine;
Step 4: absorb, the air that will contain free bromine imports the absorption tower, add the sulfur dioxide gas that reaction generates from sulfur furnace simultaneously, airborne free bromine is transformed into vaporific Hydrogen bromide, the air that contains Hydrogen bromide is again through mist eliminator, the enrichment of liquid hydrogen bromic acid is obtained intermediates Hydrogen bromide pregnant solution, and its brominated amount is 60～120g/L, and tail gas from absorption tower returns air through closed cycle system and blows out operation and carry out recycle;
Step 5: distillation, (brominated amount is that 60～120g/L) pregnant solution enters distillation tower to contain Hydrogen bromide, Hydrogen bromide is become free bromine by the chlorine oxidation that feeds at the bottom of tower in tower, and distill with steam heating, bromine vapor is discharged from cat head, through condensation, bromine water separates, refiningly obtain high-quality product bromine; The slops that pregnant solution produces after distilling is discharged at the bottom of by tower, and is introduced into acidizing process disacidify concentrated seawater.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913564A (en) * | 2010-07-30 | 2010-12-15 | 天津长芦海晶集团有限公司 | Method for preparing bromine from brine |
| CN102923663A (en) * | 2012-11-06 | 2013-02-13 | 绍兴汉青环保科技有限公司 | Method for recovering bromine from pure terephthalic acid (PTA) waste water |
| CN103964382A (en) * | 2014-06-04 | 2014-08-06 | 唐山三友盐化有限公司 | Bittern bromine-blowing process |
| CN104250040A (en) * | 2014-06-05 | 2014-12-31 | 浙江南化防腐设备有限公司 | Concentrated seawater bromine extraction and closed-loop air stripping system and method |
| CN104030320B (en) * | 2014-06-06 | 2015-08-05 | 蔡泮敏 | The sea water desaltination of bidirectional circulating method and after extracting bromine strong brine concentrate salt producing craft |
| CN105460895A (en) * | 2015-12-30 | 2016-04-06 | 山东昌邑廒里盐化有限公司 | Novel bromine production device |
| WO2016054874A1 (en) * | 2014-10-08 | 2016-04-14 | 蔡泮敏 | Method for extracting bromine from seawater by vacuum distillation |
| WO2016132376A3 (en) * | 2015-02-19 | 2016-12-01 | Agrocel Industries Limited | Process for preparation of hydrobromic acid |
| CN107792830A (en) * | 2016-08-29 | 2018-03-13 | 李春鑫 | A kind of seawater of energy-conservation puies forward bromine technique |
| CN108144416A (en) * | 2018-01-03 | 2018-06-12 | 国家海洋局天津海水淡化与综合利用研究所 | One kind blows bromine tail gas overall process recovery method and equipment |
| CN108640087A (en) * | 2018-08-22 | 2018-10-12 | 天津海晶科技发展有限公司 | A kind of bromine distillation process waste liquid automatic switchover recovery process processed |
| CN111362343A (en) * | 2018-12-26 | 2020-07-03 | 国家海洋局天津海水淡化与综合利用研究所 | Method and equipment for extracting bromine from seawater by air blowing method |
| CN111573955A (en) * | 2020-05-20 | 2020-08-25 | 杨文辉 | Comprehensive utilization method of concentrated seawater |
| CN112010261A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Novel air blowing method bromine extraction method and equipment |
| CN112007586A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Groove type liquid distributor for bromine extraction blow-out tower and application thereof |
| CN112010262A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Improved bromine extraction method and equipment by air blowing method |
| CN112340701A (en) * | 2020-11-05 | 2021-02-09 | 天津海晶科技发展有限公司 | Chlorine blowing automatic control process for preparing bromine by acid method |
| CN114933283A (en) * | 2022-04-24 | 2022-08-23 | 天津长芦汉沽盐场有限责任公司 | Production process of bromine from desalted concentrated seawater |
| CN115196598A (en) * | 2022-06-29 | 2022-10-18 | 天津长芦汉沽盐场有限责任公司 | Oxidation distillation tail gas treatment process and system in bromine production process |
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Cited By (25)
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|---|---|---|---|---|
| CN101913564A (en) * | 2010-07-30 | 2010-12-15 | 天津长芦海晶集团有限公司 | Method for preparing bromine from brine |
| CN102923663A (en) * | 2012-11-06 | 2013-02-13 | 绍兴汉青环保科技有限公司 | Method for recovering bromine from pure terephthalic acid (PTA) waste water |
| CN103964382A (en) * | 2014-06-04 | 2014-08-06 | 唐山三友盐化有限公司 | Bittern bromine-blowing process |
| CN104250040B (en) * | 2014-06-05 | 2016-08-24 | 浙江南化防腐设备有限公司 | A kind of concentrated seawater puies forward bromine closed loop blow-removing system and method |
| CN104250040A (en) * | 2014-06-05 | 2014-12-31 | 浙江南化防腐设备有限公司 | Concentrated seawater bromine extraction and closed-loop air stripping system and method |
| CN104030320B (en) * | 2014-06-06 | 2015-08-05 | 蔡泮敏 | The sea water desaltination of bidirectional circulating method and after extracting bromine strong brine concentrate salt producing craft |
| WO2016054874A1 (en) * | 2014-10-08 | 2016-04-14 | 蔡泮敏 | Method for extracting bromine from seawater by vacuum distillation |
| WO2016132376A3 (en) * | 2015-02-19 | 2016-12-01 | Agrocel Industries Limited | Process for preparation of hydrobromic acid |
| CN107531480A (en) * | 2015-02-19 | 2018-01-02 | 阿戈洛赛尔实业有限公司 | Hydrobromic acid preparation method |
| US10626015B2 (en) | 2015-02-19 | 2020-04-21 | Agrocel Industries Limited | Process for preparation of hydrobromic acid |
| CN107531480B (en) * | 2015-02-19 | 2020-12-18 | 阿戈洛赛尔实业有限公司 | Preparation method of hydrobromic acid |
| CN105460895A (en) * | 2015-12-30 | 2016-04-06 | 山东昌邑廒里盐化有限公司 | Novel bromine production device |
| CN107792830A (en) * | 2016-08-29 | 2018-03-13 | 李春鑫 | A kind of seawater of energy-conservation puies forward bromine technique |
| CN108144416B (en) * | 2018-01-03 | 2020-10-13 | 国家海洋局天津海水淡化与综合利用研究所 | Bromine blowing tail gas overall process recovery method and equipment |
| CN108144416A (en) * | 2018-01-03 | 2018-06-12 | 国家海洋局天津海水淡化与综合利用研究所 | One kind blows bromine tail gas overall process recovery method and equipment |
| CN108640087A (en) * | 2018-08-22 | 2018-10-12 | 天津海晶科技发展有限公司 | A kind of bromine distillation process waste liquid automatic switchover recovery process processed |
| CN111362343A (en) * | 2018-12-26 | 2020-07-03 | 国家海洋局天津海水淡化与综合利用研究所 | Method and equipment for extracting bromine from seawater by air blowing method |
| CN112010261A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Novel air blowing method bromine extraction method and equipment |
| CN112007586A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Groove type liquid distributor for bromine extraction blow-out tower and application thereof |
| CN112010262A (en) * | 2019-05-28 | 2020-12-01 | 自然资源部天津海水淡化与综合利用研究所 | Improved bromine extraction method and equipment by air blowing method |
| CN112010262B (en) * | 2019-05-28 | 2023-08-15 | 自然资源部天津海水淡化与综合利用研究所 | Improved bromine extraction method and device by air blowing method |
| CN111573955A (en) * | 2020-05-20 | 2020-08-25 | 杨文辉 | Comprehensive utilization method of concentrated seawater |
| CN112340701A (en) * | 2020-11-05 | 2021-02-09 | 天津海晶科技发展有限公司 | Chlorine blowing automatic control process for preparing bromine by acid method |
| CN114933283A (en) * | 2022-04-24 | 2022-08-23 | 天津长芦汉沽盐场有限责任公司 | Production process of bromine from desalted concentrated seawater |
| CN115196598A (en) * | 2022-06-29 | 2022-10-18 | 天津长芦汉沽盐场有限责任公司 | Oxidation distillation tail gas treatment process and system in bromine production process |
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Effective date of registration: 20190528 Address after: 300452 No. 1 Huantan Road, Binhai New Area, Tianjin Patentee after: Tianjin Hai Jing Technology Development Co., Ltd. Address before: No. 1088 Yingkou Road, Tanggu District, Tianjin 300450 Patentee before: Haijing Group Co., Ltd., Changlu, Tianjin City |