CN103241894A - Method for dechlorinating and neutralizing waste liquor with bromine extracted - Google Patents
Method for dechlorinating and neutralizing waste liquor with bromine extracted Download PDFInfo
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- CN103241894A CN103241894A CN201310145740XA CN201310145740A CN103241894A CN 103241894 A CN103241894 A CN 103241894A CN 201310145740X A CN201310145740X A CN 201310145740XA CN 201310145740 A CN201310145740 A CN 201310145740A CN 103241894 A CN103241894 A CN 103241894A
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Abstract
The invention relates to a treatment method of waste liquor obtained after bromine is extracted from bittern. In the method, free chlorine contained in concentrated bittern with bromine extracted is treated through a reducing agent, namely sulfur dioxide, so that the chlorinity is reduced to a certain index, and the concentrated bittern with chlorine removed is neutralized by using limestone and then added to a biological population and discharged to a buffer pool to restore a biological system. The treatment method disclosed by the invention has the advantages of low production cost, zero discharge and no pollution and is suitable for industrial batch production; and according to the invention, concentrated seawater obtained through treatment can be directly discharged into seawater.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, be particularly related to the processing of waste water behind seawater, the bittern bromine, specifically contain sour chloride waste liquid with sulfurous gas and Wingdale processing, add biotic population at last and be discharged to Buffer Pool, repair the method for biosystem and qualified discharge.
Background technology
At present both at home and abroad bittern bromine technology comprises that traditional steam distillation and air blow out the novel bromine technologies of putting forward such as method two big main flow technologies and resin adsorption method, gaseous state embrane method, emulsion liquid membrane.China's bromine resource mainly is distributed in the coastal region in east China, the production starting material are generally taken from concentrated seawater and the subsurface brine in the process of evaporating brine, about 0.2g/L～the 0.3g/L of bromine content, compare much lowerly with the bromine content in the Israel raw material with the U.S., only suitablely adopt an air to blow out method to extract bromine on a large scale.
Air blows out operations such as method comprises acidifying, oxidation, blows out, absorbs, distillation, condensation, separation, by the difference that absorbs absorption agent in the operation air is blown out method and is divided into that air blows out the acid solution absorption process and air blows out alkali absorption method.Because alkali absorption method exists the absorption liquid bromine content low, electric steam, the drawback that the acid and alkali consumption amount is big, 90% above bromine all adopts air to blow out the production of acid solution absorption process up to now.China eighties in 19th century has introduced since advanced " air blows out tail gas sealing recycle acid legal system bromine " technology from Britain, and Technology has been carried out repeatedly improving, ready-made for the most ripe, generally adopt put forward bromine technology.The production process of this technology is: after the bittern of low bromine content was acidified with acid pH value about 3～3.5, by chlorine oxidation, bromide anion was oxidized to free bromine in tubular static mixer; Free bromine is blown out by a large amount of air in desorption tower in the oxidation liquid, and the sulfuric acid mist in the absorption tower absorbs airborne free bromine and is reduced to vaporific Hydrogen bromide; Be rich in the Cl that hydrobromic absorption liquid is fed by the packing tower middle part
2Oxidation, the bromine that dissociates, finally the concentrate condensation obtains thick bromine under the stripping effect of packing tower bottom water vapor.Wherein, tail gas from absorption tower is back to through closed cycle system and blows out the operation recycle.
Carry in the waste water behind the bromine and contain a large amount of chlorine, chlorine has the very strong ability of killing to pathogenic microorganism, thereby is widely used in many sewage works.Yet, when chlorination is killed the disease caused by infectious water pathogenic microorganism, chlorine easily with water in the organism reaction, produce the DBPs (D-infection By products) that the mutagenesis carcinogenesis is arranged, as haloform, human and hydrobiont generation long term toxicity are influenced.In addition, the chlorine disinfectant water outlet is if directly enter water body, and the chlorine residue meeting produces toxic action to fish or hydrobiont.In order to protect the organism in water body to avoid to sterilize the toxic effect of chlorine residue in the tail water, just must carry out strictness control to the tail water residual chlorine amount that enters water body.Total chlorine should be less than 0.16mol/L (0.011mg Cl/L) in the American National Environmental Protection Agency regulation tail water, China does not have this standard temporarily, only the chlorine residue to the hospital sewage that adopts chlorination is stipulated in integrated wastewater discharge standard (GB89781996), is 0.5mg Cl/L.
The chlorine-contained wastewater of carrying behind the bromine has higher pungent odour and corrodibility.If not treated it may send out with organism in the water and should generate organic chloride and cause secondary pollution.Chlorine water has strong microbial killing ability, destroys water ecosystem, and environment is produced strong the pollution, corrosion pipeline, and equipment and boats and ships cause loss economically.
The pH of dense bittern is about 4 after the dechlorination, emission standard pH=6～9 of environmental administration (office) regulation, so exist acid waste water in and problem.
Summary of the invention
Technical problem to be solved by this invention is: the treatment process that waste liquid behind a kind of bittern bromine is provided, handle carrying behind the bromine in the dense bittern free chlorine by reductive agent, make cl content drop to certain index, and the dense bittern that removes behind the chlorine neutralized, after this add biotic population and be discharged to Buffer Pool, repair biosystem.This method has overcome existingly to be proposed the bromine wastewater treatment and has energy consumption height, the big and low shortcoming of benefit of investment.
The present invention solves this technical problem the technical scheme that adopts:
The treatment process of waste liquid behind a kind of bittern bromine may further comprise the steps:
The first step, dechlorination
Feed sulfurous gas and carry out dechlorination to carrying behind the bromine waste water, its proportioning is mol ratio chlorine: sulfurous gas=1:0.9～1.5, at 30～60 ℃ of reaction 20～30min down;
Second step, neutralization
With the neutralizing well that waste water behind the bromine feeds the Wingdale that is filled with of carrying after the dechlorination, flow velocity is 4.0～7.5m/h, and the residence time is 16～30min; Concentrated seawater after obtaining neutralizing, its pH value is 6.0～6.9;
In the 3rd step, biosystem is recovered
Neutralization back concentrated seawater feeds Buffer Pool, and then adds former seawater, obtains mixing seawater, and charge into oxygen in the pond, to repair biosystem; Wherein, former seawater is 9～12% of neutralization back concentrated seawater volume, and the oxygenation time is 30min, and the oxygen level that oxygenation capacity reaches in the Buffer Pool maritime interior waters is 6～8cm
3/ dm
3
The packing height of described groove sodalime stone is 40～65mm, and the mean particle size of Wingdale is 20～30mm.
Carry that waste water is the chloracid wastewater of concentrated seawater after air blows out method to carry bromine behind the bromine in the described the first step, wherein cl content is 2～8mg/L, and pH value is 3.5～5.0.
The invention has the beneficial effects as follows: compared with prior art, the inventive method has following tangible advantage and progress:
(1) with the higher sulfurous gas of reductibility as reductive agent, overcome that sodium hydroxide and calcium hydroxide and chlorine react inadequate defective in the prior art; In addition, sodium hydroxide production cost height; As neutralizing agent, thereby low production cost, zero release and pollution-free are applicable to industrial mass manufacture with Wingdale cheap and easy to get.
(2) the inventive method is carried out the biosystem recovery to the concentrated seawater after handling, and can not impact Marine ecosystems, and handling the gained concentrated seawater can directly be discharged in the seawater.
(3) chlorine-contained wastewater of handling among the present invention is different from the chlorine-contained wastewater after the common bleaching, chlorine-contained wastewater among the present invention not only has certain acidity, wherein also have a large amount of salts and some objectionable impuritiess, first and second step reaction of the present invention utilizes chemical process, the 3rd step with the solution of transporting the bioremediation success propose the pollution problem of chloride dense bittern behind the bromine.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is for being used for the experimental installation synoptic diagram of neutralization reaction in second step of the present invention.
Wherein, 1. plastic tank, 2. peristaltic pump one, 3. neutralizing well, 4. initial measuring point, 5. measuring point one, and 6. measuring point two, 7. end of a period measuring point, 8. peristaltic pump two, 9. Buffer Pool.
Embodiment
Embodiments of the invention only are used for describing the present invention in detail, are not considered as the restriction to claim protection domain of the present invention.
The present invention does not address part and is applicable to prior art.
The second step reaction process of the present invention as shown in Figure 1, to carry behind the bromine waste water to the plastic tank 1 after the dechlorination, by peristaltic pump 2 with after the dechlorination carry bromine after waste water be passed in the groove 3 of filled stone lime stone, the specification of groove 3 is 2000mm * 100mm * 70mm, the packing height of groove sodalime stone is 40～65mm, the mean particle size of Wingdale is 20～30mm, carry behind the bromine waste water initial measuring point 4 of successively flowing through after the dechlorination, measuring point 1, measuring point 26 and end of a period measuring point 7, wherein, initial measuring point 4 and end of a period measuring point 7 lay respectively at the two ends of groove, and measuring point 1 and measuring point 26 are positioned at the measuring point trisection point place of neutralizing well; Neutralization back concentrated seawater moves in the Buffer Pool 9 by peristaltic pump 28 at last, adds former seawater and oxygenation again in Buffer Pool 9.
The amount of the Wingdale in the neutralizing well will keep certain packing height; Along with the carrying out of neutralization reaction, the meeting of the Wingdale of filling and acid react, and product is dissolved in the waste water with the form of calcium sulfate, in time add to original packing height and just get final product;
The present invention tests carrying of using, and waste water utilizes the chloracid wastewater of Bohai Sea concentrated seawater after air blows out method to carry bromine as the brilliant group in Tianjin long reed sea behind the bromine, and the cl content in the acid waste water is 2～8mg/L, and PH is 3.5～5.0; Former seawater is Bohai Sea seawater.
Main component is as follows: NaCl:4.94%, KCl:0.14%, CaSO
4: MgCl 0.22%,
2: 0.59% and MgSO
4: 0.40%.
Embodiment 1
Get 10L carry behind the bromine waste water wherein cl content be 4.87mg/L(0.03mmol/L), to the sulfurous gas that wherein feeds 25.0mg (0.39mmol), react 20min down at 30 ℃, obtain the waste water behind the bromine of carrying after the dechlorination, carry that wastewater pH is initial measuring point 4 behind the bromine after the dechlorination, dense bittern after the dechlorination is fed to the plastic tank 1, by peristaltic pump 2 with after the dechlorination carry bromine after waste water be passed in the neutralizing well 3 of filled stone lime stone, the flow velocity 6.5m/h of neutralizing well 3 flows through,, the initial measuring point 4 of flowing through, measuring point 1, carry that the pH value of waste water is followed successively by 4.50 behind the bromine after the dechlorination of measuring point 26 and end of a period measuring point 7,6.54,6.56 and 6.57.
The content of the waste liquid free chlorine after handling is after testing reduced to 0.15mg/L, and pH is elevated to 6.57.The cl content detection method is common silver nitrate titration method, the emission standard of this data fit GB.
To handle back concentrated seawater (concentrated seawater after the processing still is about 10L) and collect in the Buffer Pool 9, add the former seawater of 1L, oxygenation 30 minutes, the oxygen level that oxygenation capacity requires to reach in the seawater reaches 6cm
3/ dm
3, left standstill 72 hours, find that after testing flora quantity reaches 10 in the concentrated seawater of processing back
6/ ml, flora mainly comprise intestinal bacteria, and biologies such as vibrios class and Pseudoalteromonas obtain growth, illustrate that biosystem has obtained recovery.
Embodiment 2
Get 10L carry behind the bromine waste water wherein cl content be 5.74mg/L(0.035mmol/L), to the sulfurous gas that wherein feeds 34.0mg (0.53mmol), react 20min down at 30 ℃, obtain the waste water behind the bromine of carrying after the dechlorination, carry that wastewater pH is initial measuring point 4 behind the bromine after the dechlorination, dense bittern after the dechlorination is fed to the plastic tank 1, by peristaltic pump 2 with after the dechlorination carry bromine after waste water be passed in the neutralizing well 3 of filled stone lime stone, the flow velocity 6.2m/h of neutralizing well 3 flows through, the initial measuring point 4 of flowing through, measuring point 1, carry that the pH value of waste water is followed successively by 4.28 behind the bromine after the dechlorination of measuring point 26 and end of a period measuring point 7,6.32,6.35,6.36.
The content of the waste liquid free chlorine after handling is after testing reduced to 0.10mg/L, and pH is elevated to 6.36.The detection method of cl content is common silver nitrate titration method, the emission standard of this data fit GB.
To handle back concentrated seawater (concentrated seawater after the processing still is about 10L) and collect in the Buffer Pool 9, add the former seawater of 1L, oxygenation 30 minutes, the oxygen level that oxygenation capacity requires to reach in the seawater reaches 6cm
3/ dm
3, left standstill 72 hours, find that after testing flora quantity reaches 10 in the concentrated seawater of processing back
6/ ml, flora mainly comprise intestinal bacteria, and biologies such as vibrios class and Pseudoalteromonas obtain growth, illustrate that biosystem has obtained recovery.
Claims (3)
1. the treatment process of waste liquid behind the bittern bromine is characterized by and may further comprise the steps:
The first step, dechlorination
Feed sulfurous gas and carry out dechlorination to carrying behind the bromine waste water, its proportioning is mol ratio chlorine: sulfurous gas=1:0.9～1.5, at 30～60 ℃ of reaction 20～30min down;
Second step, neutralization
With the neutralizing well that waste water behind the bromine feeds the Wingdale that is filled with of carrying after the dechlorination, flow velocity is 4.0～7.5m/h, and the residence time is 16～30 minutes; Concentrated seawater after obtaining neutralizing, its pH value is 6.0～6.9;
In the 3rd step, biosystem is recovered
Neutralization back concentrated seawater feeds Buffer Pool, and then adds former seawater, obtains mixing seawater, and charge into oxygen in the pond, to repair biosystem; Wherein, former seawater is 9～12% of neutralization back concentrated seawater volume, and the oxygenation time is 30min, and the oxygen level that oxygenation capacity reaches in the Buffer Pool maritime interior waters is 6～8cm
3/ dm
3
2. the treatment process of waste liquid behind the bittern bromine as claimed in claim 1, the packing height that it is characterized by described groove sodalime stone is 40～65mm, the mean particle size of Wingdale is 20～30mm.
3. the treatment process of waste liquid behind the bittern bromine as claimed in claim 1 is characterized by and carries that waste water is the chloracid wastewater of concentrated seawater after air blows out method to carry bromine behind the bromine in the described the first step, and wherein cl content is 2～8mg/L, and pH value is 3.5～5.0.
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| CN201310145740XA CN103241894A (en) | 2013-04-25 | 2013-04-25 | Method for dechlorinating and neutralizing waste liquor with bromine extracted |
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| CN201310145740XA CN103241894A (en) | 2013-04-25 | 2013-04-25 | Method for dechlorinating and neutralizing waste liquor with bromine extracted |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364835A (en) * | 1980-10-24 | 1982-12-21 | Regents Of The University Of Minnesota | Sulfite destruction of direct acting mutagens in drinking water |
| CN102666403A (en) * | 2009-11-19 | 2012-09-12 | 日本曹达株式会社 | Reduction treatment method for ballast water |
| CN102976470A (en) * | 2012-10-29 | 2013-03-20 | 浙江巨化股份有限公司电化厂 | Method of removing free chlorine in waste water produced in preparation of tetrachloroethane through chlorination of acetylene |
-
2013
- 2013-04-25 CN CN201310145740XA patent/CN103241894A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364835A (en) * | 1980-10-24 | 1982-12-21 | Regents Of The University Of Minnesota | Sulfite destruction of direct acting mutagens in drinking water |
| CN102666403A (en) * | 2009-11-19 | 2012-09-12 | 日本曹达株式会社 | Reduction treatment method for ballast water |
| CN102976470A (en) * | 2012-10-29 | 2013-03-20 | 浙江巨化股份有限公司电化厂 | Method of removing free chlorine in waste water produced in preparation of tetrachloroethane through chlorination of acetylene |
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Application publication date: 20130814 |