CN102976470A - Method of removing free chlorine in waste water produced in preparation of tetrachloroethane through chlorination of acetylene - Google Patents
Method of removing free chlorine in waste water produced in preparation of tetrachloroethane through chlorination of acetylene Download PDFInfo
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- CN102976470A CN102976470A CN2012104215215A CN201210421521A CN102976470A CN 102976470 A CN102976470 A CN 102976470A CN 2012104215215 A CN2012104215215 A CN 2012104215215A CN 201210421521 A CN201210421521 A CN 201210421521A CN 102976470 A CN102976470 A CN 102976470A
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- waste water
- free chlorine
- tetrachloroethane
- chlorination
- acetylene
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Abstract
The invention discloses a method of removing free chlorine in waste water produced in preparation of tetrachloroethane through chlorination of acetylene. According to the method, a dechlorinating agent is added into the waste water, then an alkaline auxiliary agent is added to control the pH value of the waste water to be 7 to 8, and the usage amount of the dechlorinating agent accounts for 0.001 to 0.08% of the mass of the waste water. The method provided by the invention has high efficiency in removal of free chlorine; the treated waste water can be recycled; the method has great waste water treating capability and is suitable for industrial popularization and application; and the method has the advantages of a simple process, safety, reliability, low cost and good economic benefits and environmental protection benefits.
Description
Technical field
The present invention relates to remove the method for waste water free chlorine, particularly a kind of method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine.
Background technology
In the industry, produce the chlorination reaction that relates to chlorine and acetylene in the tetrachloroethane process with acetylene route, this chlorination reaction is in the tetrachloroethane mother liquor, take iron trichloride as catalyzer, vacuumizes with water jet pump, and reaction generates tetrachloroethane under condition of negative pressure.Although this reaction adopts the excessive mode of acetylene to control, and in actual production process, still has the water-soluble formation of a small amount of unreacted chlorine to contain the factory effluent of free chlorine (chloride is 0.01～0.02%).In addition, generate in the process of tetrachloroethane at chlorine and acetylene reaction, go back simultaneously the multiple organic chlorides such as by-product trichloroethane, pentaline, hexachloroethane, therefore, tetrachloroethane factory effluent complicated contains acetylene, organism muriate, HCl, free chlorine etc., if with its recycle, not only can reduce discharge of wastewater, unreacted acetylene, organism muriate etc. are utilized effectively, reduce production costs.But because free chlorine has very strong oxidisability, can cause the corrosion of e-quipment and pipe, causing can not recycle.The tetrachloroethane factory effluent that contains in a large number free chlorine has brought great environmental protection pressure to manufacturing enterprise, and therefore how research removes the free chlorine in the tetrachloroethane factory effluent, to realize recycle, is problem in the urgent need to address.
But prior art does not relate to the processing problem of inorganic free chlorine mainly for the processing of the organic chloride in the tetrachloroethane factory effluent:
Such as China Patent Publication No. CN101531419A, open day on September 15th, 2009, denomination of invention: a kind of method of reinforced metal reduction dechlorination treatment of chloro-alkenes waste water.This application case the invention discloses a kind of method of reinforced metal reduction dechlorination treatment of chloro-alkenes waste water, comprise: regulate chloro-alkenes waste water for acid, input dechlorination reaction device, add active ion reinforcer and metallic reducing agent, the activity of active ion reinforcer shows the passivation layer of attack metal reductive agent, avoid forming stable passivation layer, strengthen the reduction dechlorination reaction, metallic reducing agent is chosen zero-valent metal or metal alloy, make powder, the reduction dechlorination conversion unit adopts fluidized-bed, after the reduction dechlorination reaction finishes, enters subsequent handling and processes.Chlorinated organics such as trieline, tetrachloroethane, zellon etc. in the waste water that relates to.
And for example China Patent Publication No. CN1803662A discloses day on July 19th, 2006, denomination of invention: a kind of method and apparatus of removing organic chloride from wastewater.This disclosure of the Invention a kind of method of removing organic chloride from wastewater, waste water by the tangential water inlet of circulation form eddy flow in reactor with the abundant contact reacts of the solid reductant of solid reductant or supported catalyst, then enter depositing separation area, the effective sedimentation of solid reductant particle of reacted solid reductant or supported catalyst reaches the purpose of removing organic chloride from wastewater.
China Patent Publication No. CN101492216A discloses July 29 2009 date, denomination of invention: a kind of processing of chloro-organic waste water and method for transformation for another example.Processing and the method for transformation of a kind of chloro-organic waste water of this application case.It comprises with regulating the chloro-organic waste water volumetric molar concentration, is that 2: 1 its concentration is that the 0.9mol/L sodium thiocarbonate mixes with it and regulates pH value to 10～11 with volumetric ratio, the step such as stirs under microwave action, and harmless processing and converted product are the sulfo-organism.
Above-mentioned patent is mainly for the processing of the organic chloride in the tetrachloroethane factory effluent, the processing problem that does not relate to inorganic free chlorine, such technical deficiency part is that required operation is many, processing cost is high, if and the waste water after processing is when recycling, because the existence of free chlorine can cause the corrosion of equipment.Simultaneously, because tetrachloroethane factory effluent complicated, contain acetylene, organism muriate, HCl, free chlorine etc., if simply adopt S-WAT in the ion film caustic soda salt solution except the waste water Ignition Phenomena then can appear in the method for free chlorine, security incident occurs.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, the method for the removal acetylene chlorination tetrachloroethane waste water processed free chlorine that a kind of technique is simple, safe and reliable, cost is low, the wastewater treatment ability is large is provided.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine, it is characterized in that in waste water, adding antichlor, adding simultaneously alkaline assistant control waste water ph is 7-8, and described antichlor consumption is 0.001～0.08% of wastewater quality.
Further:
Described antichlor is a kind of in S-WAT, sodium bisulfite, Sulfothiorine, V-Brite B, the Sodium Pyrosulfite.
Described antichlor is a kind of in S-WAT, Sulfothiorine, the Sodium Pyrosulfite.
Described alkaline assistant is a kind of in sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash, the sodium bicarbonate.
Described alkaline assistant is sodium hydroxide or potassium hydroxide.
Described antichlor consumption is 0.003～0.05% of wastewater quality.
Because chlorine has strong oxidisability, generate HCl and HClO with the water reaction, as long as find cheap reductive agent, stablize sustainable existence in solution, and easy to handle relatively again just can realize that the waste water free chlorine removes cheaply, just has industrial applications value.
The present invention adds the antichlor of reductibility in the acetylene chlorination tetrachloroethane factory effluent processed continuously, such as S-WAT, sodium bisulfite, Sulfothiorine, V-Brite B, a kind of in the Sodium Pyrosulfite, to remove free chlorine, add simultaneously alkaline assistant, such as sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash, a kind of in the sodium bicarbonate, remove the hydrogenchloride that produces, the irritant gass such as sulfurous gas, reduced the exhaust gas emission in producing, purified operating environment, waste water after the processing does not contain free chlorine, can deliver to acetylene chlorination jet of water vacuum system and recycle, further reduce discharge of wastewater, lower production cost.
As follows take S-WAT, Sulfothiorine as the reduction dechlorination chemical equation of antichlor:
Na
2S
2O
3+4Cl
2+5H
2O=8HCl+2NaHSO
4
Na
2SO
3+Cl
2+H
2O=HCl+NaHSO
4+NaCl
Na
2S
2O
5+2Cl
2+3H
2O=4HCl+2NaHSO
4
The consumption of antichlor is very large on the removal impact of waste water free chlorine, and the antichlor consumption is too large, and production cost then can raise; Too littlely then do not reach the dechlorination effect, so the antichlor consumption is 0.001～0.08% among the present invention, is preferably 0.003～0.05%.
Antichlor among the present invention can be selected a kind of in S-WAT, sodium bisulfite, Sulfothiorine, V-Brite B, the Sodium Pyrosulfite, is preferably a kind of in S-WAT, Sodium Pyrosulfite, the Sulfothiorine.
Alkaline assistant is also influential to the removal of free chlorine, and the alkaline assistant consumption is too large, and namely the pH value is too large, and wastewater disposal basin is caught fire.Too little, namely the pH value is too little, and along with deepening continuously of reaction, acidity constantly increases in the waste water, simultaneously itself can produce HCl during the acetylene chlorination reaction, and after HCl was absorbed by waste water, acidity increased, and after acquiring a certain degree, HCl or SO will occur overflowing
2(namely the meetings such as Sulfothiorine, Sodium Pyrosulfite are decomposed under acidic conditions), lost the effect of lasting dechlorination.Therefore waste water ph is 7～8 among the present invention.
Alkaline assistant among the present invention can be selected a kind of in sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash, the sodium bicarbonate, is preferably sodium hydroxide or potassium hydroxide.
Antichlor of the present invention and alkaline assistant all can commercially availablely be obtained, and be with low cost.
The measuring method of free chlorine of the present invention: add in advance 5mL starch-kalium iodide solution in 250mL triangular pyramidal bottle, then the test portion with pipette, extract 10.0mL injects the triangular pyramidal bottle, shakes a moment, if colourless, namely exists without free chlorine.
Advantage of the present invention is:
1, free chlorine is removed efficient height, the waste water reusable edible after the processing;
2, wastewater treatment ability is large, is fit to industrial application;
Technique is simple, safe and reliable, cost is low, has good economic benefit and environmental benefit.
Embodiment
Below in conjunction with embodiment the present invention is done to describe in further detail, but the present invention not only is confined to following examples.
Embodiment 1:
Mainly contain at 4400kg and to add the 0.94kg S-WAT in the factory effluent of tetrachloroethane, add simultaneously 30% aqueous sodium hydroxide solution and regulate waste water ph to 7.1, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 2:
Mainly contain at 4400kg and to add 0.3kg Sulfothiorine in the factory effluent of tetrachloroethane, add simultaneously 20% wet chemical and regulate waste water ph to 7.5, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 3:
Mainly contain at 4400kg and to add the 0.88kg Sodium Pyrosulfite in the factory effluent of tetrachloroethane, add simultaneously 30% potassium hydroxide aqueous solution and regulate waste water ph to 7.6, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 4:
Mainly contain at 4400kg and to add the 1kg sodium bisulfite in the factory effluent of tetrachloroethane, add simultaneously 20% aqueous sodium carbonate and regulate waste water ph to 7.5, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 5:
Mainly contain at 4400kg and to add 0.5kg Sulfothiorine in the factory effluent of tetrachloroethane, add simultaneously 30% potassium hydroxide aqueous solution and regulate waste water ph to 7.2, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 6:
Mainly contain at 4400kg and to add 0.6kg Sulfothiorine in the factory effluent of tetrachloroethane, add simultaneously 30% potassium hydroxide aqueous solution and regulate waste water ph to 7, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Embodiment 7
Mainly contain at 4400kg and to add the 1.6kg S-WAT in the factory effluent of tetrachloroethane, add simultaneously 30% potassium hydroxide aqueous solution and regulate waste water ph to 7.5, the waste water sample of getting after the processing is analyzed free chlorine content, do not detect free chlorine, the waste water after processing is delivered to the chlorination vacuum system recycle.
Claims (6)
1. a method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine is characterized in that adding antichlor in waste water, and adding simultaneously alkaline assistant control waste water ph is 7-8, and described antichlor consumption is 0.001～0.08% of wastewater quality.
2. a kind of method of removing acetylene chlorination tetrachloroethane processing wastewater processed free chlorine according to claim 1 is characterized in that described antichlor is a kind of in S-WAT, sodium bisulfite, Sulfothiorine, V-Brite B, the Sodium Pyrosulfite.
3. a kind of method of removing acetylene chlorination tetrachloroethane processing wastewater processed free chlorine according to claim 2 is characterized in that described antichlor is a kind of in S-WAT, Sulfothiorine, the Sodium Pyrosulfite.
4. a kind of method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine according to claim 1 is characterized in that described alkaline assistant is a kind of in sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash, the sodium bicarbonate.
5. a kind of method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine according to claim 4 is characterized in that described alkaline assistant is sodium hydroxide or potassium hydroxide.
6. a kind of method of removing acetylene chlorination tetrachloroethane waste water processed free chlorine according to claim 4 is characterized in that described antichlor consumption is 0.003～0.05% of wastewater quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241894A (en) * | 2013-04-25 | 2013-08-14 | 河北工业大学 | Method for dechlorinating and neutralizing waste liquor with bromine extracted |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3209848B2 (en) * | 1993-12-28 | 2001-09-17 | 株式会社竹中工務店 | Method and apparatus for removing residual chlorine for wastewater treatment facility |
| CN1958482A (en) * | 2006-11-06 | 2007-05-09 | 诸城泰盛化工有限公司 | Method for treating wastewater from production of chlorated fulminuric acid |
| CN101041487A (en) * | 2007-03-20 | 2007-09-26 | 山东布莱恩化工技术有限公司 | Pretreatment method for sulfate radical removal from salt water by membrane process |
-
2012
- 2012-10-29 CN CN2012104215215A patent/CN102976470A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3209848B2 (en) * | 1993-12-28 | 2001-09-17 | 株式会社竹中工務店 | Method and apparatus for removing residual chlorine for wastewater treatment facility |
| CN1958482A (en) * | 2006-11-06 | 2007-05-09 | 诸城泰盛化工有限公司 | Method for treating wastewater from production of chlorated fulminuric acid |
| CN101041487A (en) * | 2007-03-20 | 2007-09-26 | 山东布莱恩化工技术有限公司 | Pretreatment method for sulfate radical removal from salt water by membrane process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241894A (en) * | 2013-04-25 | 2013-08-14 | 河北工业大学 | Method for dechlorinating and neutralizing waste liquor with bromine extracted |
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Application publication date: 20130320 |