CN103613073A - Method for extracting bromine from bromine-containing wastewater - Google Patents
Method for extracting bromine from bromine-containing wastewater Download PDFInfo
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- CN103613073A CN103613073A CN201310549922.3A CN201310549922A CN103613073A CN 103613073 A CN103613073 A CN 103613073A CN 201310549922 A CN201310549922 A CN 201310549922A CN 103613073 A CN103613073 A CN 103613073A
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Abstract
The invention relates to a method for extracting bromine from bromine-containing wastewater, which comprises the following steps: pretreatment: filtering the bromine-containing wastewater so that the turbidity of the filtered bromine-containing wastewater is lower than the preset value; acidification: adding hydrochloric acid or sulfuric acid into industrial wastewater containing bromide ions to adjust the pH value of the industrial wastewater to 3-5; oxidation: adding an oxidizing agent into the acidified industrial wastewater for oxidation to generate bromine; extraction: adopting n-dodecane as an extraction agent, and extracting bromine from an aqueous phase to an n-dodecane phase; liquid separation: performing liquid separation on the two-phase solution added with the extraction agent, wherein the upper layer is an oil phase, and the lower layer is an aqueous phase; separating the aqueous phase from the oil phase; rectification: rectifying the n-dodecane and bromine solution obtained by the liquid separation so that bromine is separated from n-dodecane to obtain a bromine product. In the method provided by the invention, bromine is extracted by a solvent extraction process; compared with the traditional technology, the use of steam is greatly saved, the cost of whole bromine extraction is remarkably reduced, and better economic benefits are obtained.
Description
Technical field
The invention belongs to technology for treating industrial waste water field, relate in particular to a kind of method of extracting bromine from brominated waste water.
Background technology
Bromine is one of important industrial chemicals, by its derivative miscellaneous inorganic bromide, bromate and brominated organic compound, has special value in national economy and development in science and technology.Aromatic series organic bromide has been widely used in each side such as pharmacy, agricultural chemicals, dyestuffs, when preparing aromatic series organic bromide with bromination reaction, the utilization ratio of bromine is only 50%, therefore can produce the trade effluent that is rich in bromide anion of materials such as containing Hydrogen bromide, Sodium Bromide, Potassium Bromide.If the bromine in Hydrogen bromide, Sodium Bromide, Potassium Bromide is extracted into raw material bromine, can greatly reduce costs, produce considerable economic benefit, improve the competitiveness of product in market.
At present in China, bromine extracting method be take steam distillation and Air blowing method as main, and its principle is all by steam distillation and Air blowing method, to extract after bromide anion being oxidized to free bromine with oxygenant again.Steam distillation is due to straight run distillation, and steam consumption is larger, thus the method generally to take the bittern of bromine content more than 3g/L be raw material.Air blowing Fa Shi China is main bromine extracting method at present, although Air blowing method is stronger to the brominated amount adaptability of raw material, is easy to automatization and controls, and need huge equipment, and energy consumption is very high.Meanwhile, bromine extraction by air stripping process temperature influence is serious, when temperature is lower, blows out deleterious.
Summary of the invention
The object of the invention is for the problems referred to above, a kind of method of extracting cheaply bromine from brominated waste water is provided, solved the existing technical problem of prior art.
For achieving the above object, the present invention has adopted following technical proposal: a kind of method of extracting bromine from brominated waste water, and it comprises the following steps:
Pre-treatment: brominated waste water is filtered, make the turbidity of brominated waste water after filtering lower than preset value;
Acidifying: the trade effluent at bromine ion-containing adds hydrochloric acid or sulfuric acid, is adjusted to 3-5 by the pH value of trade effluent;
Oxidation: add oxygenant to be oxidized the trade effluent after acidifying and generate bromine;
Extraction: adopt n-dodecane as extraction agent, the trade effluent after oxidation adds n-dodecane, bromine is extracted into from water to n-dodecane phase;
Separatory: will add the two phase liquid after extraction agent to carry out separatory, upper strata be oil phase, i.e. bromine and n-dodecane solution, lower floor is water, by water and separation of oil;
Rectifying: the n-dodecane that separatory is obtained and bromine solution carry out rectifying, makes bromine separated with n-dodecane, obtains bromine product.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, described oxygenant is chlorine, ozone or hydrogen peroxide.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, described oxidation step carries out in microreactor, and the feature channel size of described microreactor is at 100-300 μ m, and the reaction times is 30s-1min.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, described extraction step is carried out in micro-extraction apparatus, and the feature channel size of described micro-extraction apparatus is at 50-100 μ m, and the volume ratio of the consumption of extraction agent n-dodecane is 1:5-1:10.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, described rectifying tower adopts glass material, and filler is glass structured packing.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, in oxidation step, described oxygenant is chlorine.
Above-mentioned extracting from brominated waste water in the method for bromine, preferably, in described pre-treatment step, adopt submerged ultrafiltration to filter.
Beneficial effect of the present invention is embodied in: (1) the present invention adopts solvent extration to extract bromine, compares with traditional bittern bromine technique, has save the use of a large amount of steam, and the cost of whole extraction bromine is reduced greatly, has better economic benefit; (2) the invention solves the problem of extraction agent, n-dodecane is a kind of nonpolar organic solvent, can dissolve each other, and n-dodecane itself is hypotoxic material with bromine, in whole production process, n-dodecane can carry out recycled, has reduced production cost.
Embodiment
The embodiment of the present invention provides a kind of method of extracting bromine from brominated waste water, and it comprises the following steps:
Pre-treatment: brominated waste water is filtered, make the turbidity of brominated waste water after filtering lower than preset value; Specifically, first brominated waste water enter membrane filter appts and carry out pre-treatment, membrane filtration adopts submerged ultrafiltration to filter, ultra-filtration membrane adopts PVC material, and ultra-filtration membrane aperture is 0.02 μ m, design Membrane Filtration Flux 20L/m2h, membrane operations pressure reduction is lower than 40kPa, membrane filter appts carries out intermittent aeration, and regularly carries out online matting, prevents that film from polluting;
Acidifying: the trade effluent at bromine ion-containing adds hydrochloric acid or sulfuric acid, is adjusted to 3-5 by the pH value of trade effluent; Specifically, bromide anion content is higher than 5000mg/L, and chemical oxygen demand of waste water (CODcr), lower than 1000mg/L, by pH value is adjusted to 3-5, can suppress chlorine with the hydrolysis of bromine;
Oxidation: add oxygenant to be oxidized the trade effluent after acidifying and generate bromine; In a preferred embodiment, oxygenant can be chlorine, ozone or hydrogen peroxide.
Extraction: adopt n-dodecane as extraction agent, the trade effluent after oxidation adds n-dodecane, bromine is extracted into from water to n-dodecane phase;
Separatory: will add the two phase liquid after extraction agent to carry out separatory, upper strata be oil phase, i.e. bromine and n-dodecane solution, lower floor is water, by water and separation of oil; Specifically, can carry out separatory by adding two solution after extraction agent to pass into minute flow container, water mixes with other waste water after processing and discharges after neutralization, in other embodiments, also aqueous-phase reflux can be carried to bromine to carrying out secondary in fresh brominated waste water;
Rectifying: the n-dodecane that separatory is obtained and bromine solution carry out rectifying, makes bromine separated with n-dodecane, obtains bromine product; Specifically, rectifying can be carried out in rectifying tower, the oil phase on minute flow container upper strata can be passed into one-level rectifying tower, utilizes the boiling-point difference of bromine and n-dodecane, bromine and n-dodecane are carried out to the first separated thick bromine that obtains, and the n-dodecane at the bottom of rectifying tower can be extracted and apply mechanically; Thick bromine passes in two-stage rectification tower to be refined and obtains bromine product, and the n-dodecane at the bottom of rectifying tower can extract and apply mechanically.
In a preferred embodiment, oxidation step can carry out in microreactor, and temperature of reaction can be normal temperature.Microreactor is complete enclosed appts, and the feature channel size of this microreactor is at 100-300 μ m, and the reaction times is 30s-1min.In specific embodiments of the invention, oxygenant is chlorine, joins chlorine rate and is controlled at 100%-110% left and right.
In a preferred embodiment, extraction step can be carried out in micro-extraction apparatus, and the feature channel size of micro-extraction apparatus is at 50-100 μ m, and the volume ratio of the consumption of extraction agent n-dodecane is 1:5-1:10.In these preferred embodiments, percentage extraction can reach more than 95%.
In a preferred embodiment, rectifying tower adopts glass material, and filler is glass structured packing.
In a preferred embodiment, in pre-treatment step, adopt submerged ultrafiltration to filter.The brominated amount of brominated waste water is 500mg/L, concentration of suspension 100-200mg/L, and the brominated amount 500mg/L of water outlet after immersion uf processing, SS concentration is lower than detection limit, and turbidity is lower than 1NTU.In other embodiments, also can adopt other filtering techniques well-known to those skilled in the art to filter brominated waste water, repeat no more herein.
Beneficial effect of the present invention is embodied in:
(1) the present invention adopts solvent extration to extract bromine, compares with traditional bittern bromine technique, has save the use of a large amount of steam, and the cost of whole extraction bromine is reduced greatly, has better economic benefit;
(2) the invention solves the problem of extraction agent, n-dodecane is a kind of nonpolar organic solvent, can dissolve each other, and n-dodecane itself is hypotoxic material with bromine, in whole production process, n-dodecane can carry out recycled, has reduced production cost.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although more used the terms such as acidifying, oxidation, extraction, separatory, rectifying herein, do not got rid of the possibility of using other term.Use these terms to be only used to describe more easily and explain essence of the present invention; They are construed to any additional restriction is all contrary with spirit of the present invention.
Claims (7)
1. from brominated waste water, extract a method for bromine, it is characterized in that, comprise the following steps:
Pre-treatment: brominated waste water is filtered, make the turbidity of brominated waste water after filtering lower than preset value;
Acidifying: the trade effluent at bromine ion-containing adds hydrochloric acid or sulfuric acid, is adjusted to 3-5 by the pH value of trade effluent;
Oxidation: add oxygenant to be oxidized the trade effluent after acidifying and generate bromine;
Extraction: adopt n-dodecane as extraction agent, the trade effluent after oxidation adds n-dodecane, bromine is extracted into from water to n-dodecane phase;
Separatory: will add the two phase liquid after extraction agent to carry out separatory, upper strata be oil phase, i.e. bromine and n-dodecane solution, lower floor is water, by water and separation of oil;
Rectifying: the n-dodecane that separatory is obtained and bromine solution carry out rectifying, makes bromine separated with n-dodecane, obtains bromine product.
2. the method for extracting bromine from brominated waste water according to claim 1, is characterized in that, described oxygenant is chlorine, ozone or hydrogen peroxide.
3. the method for extracting bromine from brominated waste water according to claim 1, is characterized in that, described oxidation step carries out in microreactor, and the feature channel size of described microreactor is at 100-300 μ m, and the reaction times is 30s-1min.
4. according to the method for bromine of extracting from brominated waste water described in claims 1 to 3 any one, it is characterized in that, described extraction step is carried out in micro-extraction apparatus, and the feature channel size of described micro-extraction apparatus is at 50-100 μ m, and the volume ratio of the consumption of extraction agent n-dodecane is 1:5-1:10.
5. the method for extracting bromine from brominated waste water according to claim 1, is characterized in that, described rectifying tower adopts glass material, and filler is glass structured packing.
6. according to the method for bromine of extracting from brominated waste water described in claim 1 to 5 any one, it is characterized in that, in oxidation step, described oxygenant is chlorine.
7. the method for extracting bromine from brominated waste water according to claim 1, is characterized in that, in described pre-treatment step, adopts submerged ultrafiltration to filter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712298A (en) * | 2016-05-05 | 2016-06-29 | 哈尔滨工业大学（威海） | Method for extracting bromine from bromine-containing solution |
| CN107879314A (en) * | 2016-09-30 | 2018-04-06 | 襄阳金达成精细化工有限公司 | A kind of bromine recovery method for the brominated waste water for producing diafenthiuron |
| CN110606607A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Method for recovering bromine from brominated butyl rubber industrial wastewater |
| CN110606592A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Comprehensive utilization method of brominated butyl rubber bromine-containing wastewater |
| CN111575486A (en) * | 2020-05-20 | 2020-08-25 | 杨文辉 | PTA oxidation mother liquor recycling method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445304A (en) * | 2008-12-25 | 2009-06-03 | 江苏技术师范学院 | Method for treating wastewater produced by methylation reaction in metribuzin synthesis |
| 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 |
-
2013
- 2013-11-07 CN CN201310549922.3A patent/CN103613073A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445304A (en) * | 2008-12-25 | 2009-06-03 | 江苏技术师范学院 | Method for treating wastewater produced by methylation reaction in metribuzin synthesis |
| 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 |
Non-Patent Citations (4)
| Title |
|---|
| 中国科学技术协会等: "《化学工程学科发展报告》", 31 March 2007, article "微结构设备", pages: 62 * |
| 天津市汉沽盐场等: "《苦卤的综合利用》", 30 June 1973, article "提取溴的方法", pages: 46 * |
| 张爱华等: "《生化分离技术》", 31 October 2012, article "有机溶剂萃取", pages: 35 * |
| 杨春生等: "以四氯化碳萃取回收溴的新工艺研究", 《南京理工大学学报》, vol. 23, no. 5, 31 October 1999 (1999-10-31), pages 466 - 469 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712298A (en) * | 2016-05-05 | 2016-06-29 | 哈尔滨工业大学（威海） | Method for extracting bromine from bromine-containing solution |
| CN107879314A (en) * | 2016-09-30 | 2018-04-06 | 襄阳金达成精细化工有限公司 | A kind of bromine recovery method for the brominated waste water for producing diafenthiuron |
| CN110606607A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Method for recovering bromine from brominated butyl rubber industrial wastewater |
| CN110606592A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Comprehensive utilization method of brominated butyl rubber bromine-containing wastewater |
| CN110606592B (en) * | 2018-06-14 | 2021-10-19 | 中国石油化工股份有限公司 | Comprehensive utilization method of brominated butyl rubber bromine-containing wastewater |
| CN110606607B (en) * | 2018-06-14 | 2021-11-19 | 中国石油化工股份有限公司 | Method for recovering bromine from brominated butyl rubber industrial wastewater |
| CN111575486A (en) * | 2020-05-20 | 2020-08-25 | 杨文辉 | PTA oxidation mother liquor recycling method |
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Application publication date: 20140305 |