CN102556972A - Method for extracting bromine by industrial wastewater rich in Br- - Google Patents
Method for extracting bromine by industrial wastewater rich in Br- Download PDFInfo
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- CN102556972A CN102556972A CN2012100301917A CN201210030191A CN102556972A CN 102556972 A CN102556972 A CN 102556972A CN 2012100301917 A CN2012100301917 A CN 2012100301917A CN 201210030191 A CN201210030191 A CN 201210030191A CN 102556972 A CN102556972 A CN 102556972A
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- anolyte
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Abstract
本发明公开了一种利用富含Br-的工业废水提取溴素的方法，其特征是通过对已净化预处理的富含Br-的工业废水进行电化学氧化，再通过吹出和收集得到溴素；所述电化学氧化是采用离子交换膜将电解槽分隔成阴极室和阳极室，阳极电解液是以富含Br-的工业废水经净化处理得到的富含Br-的水溶液，阴极电解液是pH为1-4的酸溶液，控制电解液的温度为25～45℃，电流密度为0.01～0.1A/cm2，或恒压0.5～6.0V；在达到电解平衡后，将阳极电解液移出后经过空气吹出、冷凝、气液分离、水溴分离得到溴素。本发明方法克服了传统的氯气、次氯酸盐等氧化法制备溴素的弊端；适于处理溴离子浓度为0.02-11.5mol/L的工业废水，其工艺过程简单、环保。The invention discloses a method for extracting bromine by utilizing Br - rich industrial wastewater, which is characterized in that the purified and pretreated Br - rich industrial wastewater is subjected to electrochemical oxidation, and then bromine is obtained by blowing out and collecting ; The electrochemical oxidation adopts ion exchange membrane to separate the electrolytic cell into cathode chamber and anode chamber, and the anolyte is rich in Br - water solution obtained by purifying industrial waste water rich in Br-, and the catholyte is Acid solution with a pH of 1-4, the temperature of the electrolyte is controlled at 25-45°C, the current density is 0.01-0.1A/cm 2 , or the constant voltage is 0.5-6.0V; after the electrolytic equilibrium is reached, the anolyte is removed Afterwards, bromine is obtained through air blowing, condensation, gas-liquid separation, and water-bromine separation. The method of the invention overcomes the disadvantages of preparing bromine by traditional oxidation methods such as chlorine gas and hypochlorite; it is suitable for treating industrial waste water with a bromide ion concentration of 0.02-11.5 mol/L, and the process is simple and environmentally friendly.
Description
Technical field
The present invention relates to the preparation method of bromine, a kind of more precisely method of utilizing the trade effluent electrochemical oxidation process to reclaim bromine.
Background technology
The natural resource of bromine mainly are that the settling of seawater and ancient ocean is a salt mine.About 99% bromine is present in the seawater on the earth.Bromine and bromine product play crucial effect in national economy, it is used for the compound of organic chemical industry and inorganic chemical industry more.Main application has: preparation agricultural chemicals on the agricultural, aspect environmental protection, be used for sterilizing agent preparation, civilian in the production of treatment agent preparation, petroleum industry gasoline detonation suppressor, other also are used for industries such as photograph, medicine.Along with industry and development of science and technology, countries in the world constantly increase the demand of bromine.
At present; The starting raw material of domestic production bromine mainly is the bittern after seawater or the product salt; Its method is free blows, distillation, deposition, extraction, IX, the absorption of middle control tunica fibrosa etc., and application still is that air blows out older methods such as method and vapor distillation method the most widely industry in, with Br
-Be oxidized to Br
2All adopt chlorine or hypochlorous acid and sodium salt thereof to make oxygenant.Like patent: CN100581992C; CN 100503428C; CN 1001613085B.Making oxygenant one with chlorine is that cost is high, the 2nd, and unfriendly in the process to environment.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, providing a kind of utilization to be rich in Br
-Trade effluent extract the method for bromine, trade effluent is got utilization.
The present invention adopts following technical scheme for the technical solution problem:
Br is rich in utilization of the present invention
-The trade effluent characteristics of extracting the method for bromine be through purifying pretreatment is rich in Br
-Trade effluent carry out electrochemical oxidation, again through blowing out and collection obtains bromine; Said electrochemical oxidation is to adopt ion-exchange membrane that electrolyzer is separated into cathode compartment and anolyte compartment, and anolyte is to be rich in Br
-Trade effluent be rich in Br through what purifying treatment obtained
-The aqueous solution, catholyte is that pH is the acid solution of 1-4, control electrolytic solution temperature be 25～45 ℃, current density is 0.01～0.1A/cm
2, or constant voltage 0.5～6.0V; After reaching electrolytic equilibrium, after anolyte shifted out through air blow out, condensation, gas-liquid separation, water bromine separate and obtain bromine.
Br is rich in utilization of the present invention
-The trade effluent characteristics of extracting the method for bromine also be the said Br of being rich in
-Trade effluent be meant the Br that is rich in that after purifying pre-treatment, is obtaining
-The aqueous solution in, bromide ion concentration is 0.02-11.5mol/L.
The principle of foundation of the present invention is: in electrolytic process, and the Br of anolyte compartment
-Preferential discharge is at negative electrode H
+Get electronics and be reduced into atomic hydrogen generation reduction reaction.Electrode reaction is:
Anode: Br
--2e=Br
2
Negative electrode: 2H
++ 2e=H
2
Br is rich in utilization of the present invention
-Trade effluent extract bromine, adopt electrochemical process oxidation Br
-Obtain bromine, meet the basic demand of clean production and atom economy, can significantly reduce the bromine production cost, good economic benefit and social benefit are arranged.Compared with present technology, beneficial effect of the present invention is embodied in:
1, the inventive method is made raw material because of adopting trade effluent, and good environmental benefit is arranged.
2, the inventive method avoids the use of deleterious oxygenant-chlorine because of adopting electrochemical oxidation process, and process environmental protection and meet the fundamental principle of atom economy has significantly reduced the cost of preparation bromine.
3, electrolytic oxidation of the present invention carries out at normal pressure, room temperature condition, safety, easy control.
4, the inventive method is suitable for being rich in Br
-Trade effluent, obtain high value-added product in the time of pollution treatment.Waste water per ton can extract the 1.5-5Kg bromine, and the market price of bromine is 2.5-3.5 ten thousand/ton, therefore can produce about 35 yuan economic benefit.
Embodiment
Embodiment 1:
Present embodiment is made electrolyzer with synthetic glass, is divided into cathode compartment and anolyte compartment with cationic exchange membrane, and anode and negative electrode all adopt Graphite Electrodes, and negative electrode and anodic useful area respectively are 200cm
2, negative electrode and anodic spacing are 1.5cm.
Get the fumaric acid waste water 2000mL of pH value, contain in the fumaric acid waste water: fumaric acid 3.4g/L, toxilic acid 0.7g/L, Sodium Bromide 2.7g/L and small amount of ammonium sulfate for 2.5-3.5; Be transferred to the anolyte compartment after the fumaric acid waste water filtering removed suspended substance; Adding 2000mL mass percent concentration is 36% maleic acid solution in cathode compartment, constantly stirs, and controlled temperature is 30 ℃, and control current density is 0.03A/cm
2Carry out electrolysis, check Br in the anolyte with turbidimetry in the electrolytic process
-Concentration, work as Br
-Concentration when no longer reducing, stop electrolysis; After anolyte shifted out through air blow out, condensation, gas-liquid separation separate with the water bromine and obtain bromine 3.4g, the recovery is 80.1%.Catholyte is shifted out and after concentrated, cooling and solid-liquid separation, obtains succsinic acid 3.1g.
Embodiment 2:
Present embodiment electrolyzer and electrolytic solution initial composition be with embodiment 1, and controlled temperature is 40 ℃ constantly stirring down, and the control constant voltage is that 5.0V carries out electrolysis, checks Br in the anode electrolysis with turbidimetry in the electrolytic process
-Concentration, when its concentration no longer reduces, stop electrolysis.After anolyte shifted out through air blow out, condensation, gas-liquid separation, water bromine separate and obtain bromine 3.2g, the recovery 77.0%.With catholyte shift out concentrated, cooling, solid-liquid separation obtains succsinic acid 2.9g.
As far as fumaric acid waste water, the galvanostatic method among the recovery of the bromine employing embodiment 1 is than the constant voltage Fa Lvegao among the embodiment 2.
Embodiment 3:
Trade effluent is to produce dry land herbicide---the trade effluent of piperazine humulone in the present embodiment, remove methyl alcohol through rectifying after, Sodium Bromide content 0.87mol/L.The amount of electrolyzer and initial electrolysis liquid and pH value such as embodiment 1 are constantly stirring down 40 ℃ of controlled temperature, and the control constant voltage is that 5.0V carries out electrolysis, check the Br in the anolyte with turbidimetry in the electrolytic process
-Concentration, when its concentration no longer reduces, stop electrolysis.After anolyte shifted out through air blow out, condensation, gas-liquid separation, water bromine separate and obtain bromine 110.1g, the recovery 79.1%.Catholyte shifted out after concentrate, cooling, solid-liquid separation obtain succsinic acid 71.2g.
Embodiment 4:
Trade effluent is to produce dry land herbicide---the trade effluent of piperazine humulone in the present embodiment.The amount of electrolyzer and initial electrolysis liquid and pH value such as embodiment 3, controlled temperature is 40 ℃ under constantly stirring, and electrolytic process control constant current density is 0.09A/cm
2, with the Br in the turbidimetry check anolyte
-Concentration, when its concentration no longer reduces, stop electrolysis.After anolyte shifted out through air blow out, condensation, gas-liquid separation, water bromine separate and obtain bromine 112.3g, the recovery 80.7%.Catholyte shifted out after concentrate, cooling, solid-liquid separation obtain succsinic acid 71.6g.
Claims (2)
1. Br is rich in a utilization
-Trade effluent extract the method for bromine, it is characterized in that through purifying pretreatment is rich in Br
-Trade effluent carry out electrochemical oxidation, again through blowing out and collection obtains bromine; Said electrochemical oxidation is to adopt ion-exchange membrane that electrolyzer is separated into cathode compartment and anolyte compartment, and anolyte is to be rich in Br
-Trade effluent be rich in Br through what purifying treatment obtained
-The aqueous solution, catholyte is that pH is the acid solution of 1-4, control electrolytic solution temperature be 25～45 ℃, current density is 0.01～0.1A/cm
2, or constant voltage 0.5～6.0V; After reaching electrolytic equilibrium, after anolyte shifted out through air blow out, condensation, gas-liquid separation, water bromine separate and obtain bromine.
2. Br is rich in utilization according to claim 1
-Trade effluent extract the method for bromine, it is characterized in that the said Br of being rich in
-Trade effluent be meant the Br that is rich in that after purifying pre-treatment, is obtaining
-The aqueous solution in, bromide ion concentration is 0.02-11.5mol/L.
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| CN2012100301917A CN102556972A (en) | 2012-02-10 | 2012-02-10 | Method for extracting bromine by industrial wastewater rich in Br- |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103668312A (en) * | 2013-12-10 | 2014-03-26 | 淮北师范大学 | Electrochemical process for preparing fumaric acid employing maleic acid cis-trans isomerization |
| CN109371416A (en) * | 2018-12-12 | 2019-02-22 | 浙江大学 | A kind of method for recovering bromine from bromine-containing wastewater |
| CN109608329A (en) * | 2018-12-12 | 2019-04-12 | 浙江大学 | A kind of production method of terephthalic acid with low bromine emission |
| CN111087047A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Treatment method of bromine-containing organic wastewater |
| CN113527080A (en) * | 2020-04-14 | 2021-10-22 | 杭州科兴生物化工有限公司 | Method for preparing dibrominated succinic acid by utilizing bromine-containing wastewater |
| CN113913852A (en) * | 2021-11-23 | 2022-01-11 | 山东海王化工股份有限公司 | Method for extracting sodium bromide from brine |
| CN114477567A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for treating sodium bromide wastewater |
| CN114477568A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for recycling bromine-containing wastewater |
| CN114956264A (en) * | 2022-06-09 | 2022-08-30 | 南京华工创新环境研究院有限公司 | Method for separating bromine in liquid by using electrochemistry |
| CN115074754A (en) * | 2022-06-15 | 2022-09-20 | 华东理工大学 | Method for selectively oxidizing bromine ions in potassium-extracting old bittern into elemental bromine |
| CN118756152A (en) * | 2024-09-05 | 2024-10-11 | 莱州诚源盐化有限公司 | Method for secondary extraction of bromine using primary bromine extraction waste liquid |
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|---|---|---|---|---|
| CN101054163A (en) * | 2007-03-28 | 2007-10-17 | 莱州诚源盐化有限公司 | Technique for secondary extracting bromine from waste liquid by extracting bromine once |
| CN102311097A (en) * | 2011-08-08 | 2012-01-11 | 杭州水处理技术研究开发中心有限公司 | Method for extracting bromine from seawater by utilization of bipolar membrane |
-
2012
- 2012-02-10 CN CN2012100301917A patent/CN102556972A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054163A (en) * | 2007-03-28 | 2007-10-17 | 莱州诚源盐化有限公司 | Technique for secondary extracting bromine from waste liquid by extracting bromine once |
| CN102311097A (en) * | 2011-08-08 | 2012-01-11 | 杭州水处理技术研究开发中心有限公司 | Method for extracting bromine from seawater by utilization of bipolar membrane |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103668312A (en) * | 2013-12-10 | 2014-03-26 | 淮北师范大学 | Electrochemical process for preparing fumaric acid employing maleic acid cis-trans isomerization |
| CN103668312B (en) * | 2013-12-10 | 2016-06-29 | 淮北师范大学 | A kind of maleic acid cis-trans isomerization prepares the electrochemical process of fumaric acid |
| CN111087047A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Treatment method of bromine-containing organic wastewater |
| CN109371416A (en) * | 2018-12-12 | 2019-02-22 | 浙江大学 | A kind of method for recovering bromine from bromine-containing wastewater |
| CN109608329A (en) * | 2018-12-12 | 2019-04-12 | 浙江大学 | A kind of production method of terephthalic acid with low bromine emission |
| CN113527080A (en) * | 2020-04-14 | 2021-10-22 | 杭州科兴生物化工有限公司 | Method for preparing dibrominated succinic acid by utilizing bromine-containing wastewater |
| CN114477567A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for treating sodium bromide wastewater |
| CN114477568A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for recycling bromine-containing wastewater |
| CN114477567B (en) * | 2020-10-23 | 2023-05-30 | 中国石油化工股份有限公司 | Method for treating sodium bromide wastewater |
| CN113913852A (en) * | 2021-11-23 | 2022-01-11 | 山东海王化工股份有限公司 | Method for extracting sodium bromide from brine |
| CN113913852B (en) * | 2021-11-23 | 2022-10-18 | 山东海王化工股份有限公司 | Method for extracting sodium bromide from brine |
| CN114956264A (en) * | 2022-06-09 | 2022-08-30 | 南京华工创新环境研究院有限公司 | Method for separating bromine in liquid by using electrochemistry |
| CN114956264B (en) * | 2022-06-09 | 2023-06-30 | 南京华工创新环境研究院有限公司 | Method for separating bromine in liquid by using electrochemistry |
| CN115074754A (en) * | 2022-06-15 | 2022-09-20 | 华东理工大学 | Method for selectively oxidizing bromine ions in potassium-extracting old bittern into elemental bromine |
| CN115074754B (en) * | 2022-06-15 | 2024-03-19 | 华东理工大学 | A method for selectively oxidizing bromide ions in old brine for potassium extraction into elemental bromine |
| CN118756152A (en) * | 2024-09-05 | 2024-10-11 | 莱州诚源盐化有限公司 | Method for secondary extraction of bromine using primary bromine extraction waste liquid |
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Inventor after: Wang Yongqiu Inventor after: Wu Jincheng Inventor after: Chen Kang Inventor after: Zhang Peihong Inventor after: Fu Hui Inventor after: Wang Changji Inventor before: Wang Yongqiu Inventor before: Chen Kang Inventor before: Wei Zhenzhong Inventor before: Wu Jincheng Inventor before: Zhang Peihong Inventor before: Wang Changji |
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Free format text: CORRECT: INVENTOR; FROM: WANG YONGQIU CHEN KANG WEI ZHENZHONG WU JINCHENG ZHANG PEIHONG WANG CHANGJI TO: WANG YONGQIU WU JINCHENG CHEN KANG ZHANG PEIHONG FU HUI WANG CHANGJI |
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