CN102942247A - Reagent and method for reducing COD of wastewater containing bromine and phenol - Google Patents
Reagent and method for reducing COD of wastewater containing bromine and phenol Download PDFInfo
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- CN102942247A CN102942247A CN2012104491107A CN201210449110A CN102942247A CN 102942247 A CN102942247 A CN 102942247A CN 2012104491107 A CN2012104491107 A CN 2012104491107A CN 201210449110 A CN201210449110 A CN 201210449110A CN 102942247 A CN102942247 A CN 102942247A
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Abstract
The invention relates to a reagent and a method for reducing COD of wastewater containing bromine and phenol. The method comprises the following steps of (1) removing bromine from the wastewater containing bromine and phenol; (2) adding a Fenton reagent into the wastewater; and (3) adding potassium permanganate into the wastewater, adjusting the adding amounts of the fenton reagent and the potassium permanganate to reduce the COD value of the wastewater, until obtaining the treated water containing targeted content of COD value. The chlorine adding method is adopted to remove the bromine ions from the wastewater containing phenol, the defects in the prior art are avoided, and the good supplementing effect with the subsequent reagent is formed. The price of the fenton reagent is low, so the usage amount of the Fenton reagent is increased, the usage amount of the potassium permanganate can be reduced, and the removal rate of COD in the wastewater is improved to more than 85%.
Description
Technical field
The invention belongs to sewage treatment area, especially a kind of reagent and method that reduces the COD of brominated, phenol waste water.
Background technology
Along with the process of development and the urbanization of world economy, the demand of water is constantly being increased, the consequent is that the quantity discharged of waste water is also increasing, phenolic wastewater has caused the extensive concern of domestic and international various circles of society to the pollution of water body.
Phenolic compound is a kind of prototype matter poisonous substance, it can suck by the contact of skin and mucous membrane or direct oral cavity immerses in the organism, contact rear formation insoluble protein and cell is lost activity with the protein in the cell magma, especially neural system there is larger avidity, makes neural system generation pathology.Phenolic wastewater also produces hydrobiont and has a strong impact on, and the toxicity of phenol can suppress microbial growth speed in the water greatly, affects the eubiosis of water.In addition, phenolic wastewater also can exert an influence to farm crop.Lower concentration phenolic wastewater irrigated farmland can make in some farm crop contains aldehydes matter, can not eat; The high-concentration phenolic wastewater irrigated farmland can cause the death of farm crop.
Phenolic wastewater is mainly from industrial sector and petroleum cracking ethene processed, synthesizing phenol, tynex, synthetic dyestuff, organic pesticide and resol production processes such as coke-oven plant (especially low temperature coke making by indigenous methods), producer gas plant, petroleum chemical plant, insulating material factorys.For example produce the waste water that coke, coal gas produce and contain phenol concentration up to 2000-12000mg/L.Mainly contain the phenolic group compound in the phenolic wastewater, such as phenol, cresols, xylenol and nitrocresol etc.
Process present situation both at home and abroad:
At present, mostly the treatment process of bromine is the physico-chemical processes method in the existing waste water, and such as blow-off method, the precipitator method, absorption method and electrolytic process etc., but this several method has the shortcoming of self, and high such as cost, treatment effect is relatively poor etc.For phenolic wastewater, relevant treatment process mainly contains precipitation, absorption, electrochemical process etc. both at home and abroad, all is difficult to the emissions object after wide spectrum reaches processing effectively economically.The treatment process that contains phenol water is a lot, mainly is divided into Physical and chemical method, and wherein Physical comprises absorption method, extraction process, embrane method etc.Chemical method comprises the precipitator method, oxidation style and electrolytic process etc.Cut both ways but make a general survey of above the whole bag of tricks, such as embrane method, have that technique is simple, efficient fast, selectivity is high, separation efficiency is high, emulsion advantage such as reusable behind breakdown of emulsion.But because that the embrane method operative technique requires is high, the stability of film always also thoroughly solves, and industrially also fails to apply widely this new technology.The advantage of electrolytic process is to need to use the pharmaceutical chemicalss such as oxygenant, reductive agent, can save aftertreatment; Next is that unit volume device processes ability is large; Moreover, utilize the variation of electric current and voltage to be easy to control speed of response and type, operate also very simple.But, being only applicable to the advanced treatment of lower concentration phenolic wastewater, energy consumption and processing costs are higher.Therefore, a kind of can either be efficiently, economic, stable Phenol-Containing Wastewater Treatment can avoid again the improvement method of secondary pollution must become each domestic and international scholar's research emphasis and focus.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide that a kind of cost is low, processing speed is fast, treatment effect is good, reduction non-secondary pollution is brominated, reagent and the method for the COD of phenol waste water.
The present invention realizes that the technical scheme of purpose is as follows:
A kind of reagent that reduces the COD of brominated, phenol waste water comprises Fenton reagent and potassium permanganate.
And the quality g of the volume ml of hydrogen peroxide and ferrous sulfate is than being 1:15-1:5 in the described Fenton reagent.
And the ratio of the COD mg/L of the volume ml of the required hydrogen peroxide of processing unit volume waste water L and waste water is in the described Fenton reagent: 1:500-1:125.
And the ratio of the add-on g of the required potassium permanganate of described processing unit volume waste water L and the CODmg/L of waste water is: 1:800-1:500.
A kind of method that reduces the COD of brominated, phenol waste water, the step of method is as follows:
⑴ remove bromine to brominated, phenol waste water;
⑵ add Fenton reagent in waste water, stir, and reduces the COD value of phenolic wastewater, and the COD value of waste water is reduced to original 30-45%;
⑶ add potassium permanganate again in waste water; Stir, the COD value of waste water is reduced to original 15-25%, obtain the processing water of the COD value of target content.
And, described step ⑴ except the bromine method be that chlorine removes the bromine method.
And the quality g of the volume ml of hydrogen peroxide and ferrous sulfate is than being 1:15-1:5 in the described Fenton reagent.
And the ratio of the COD mg/L of the volume ml of the required hydrogen peroxide of processing unit volume waste water L and waste water is in the described Fenton reagent: 1:500-1:125.
And the ratio of the add-on g of the required potassium permanganate of described processing unit volume waste water L and the CODmg/L of waste water is: 1:800-1:500.
And the Fenton reagent of described step ⑴ adds at twice.
Advantage of the present invention and beneficial effect are:
1, the present invention adopts traditional chlorination, remove bromide anion in the phenolic wastewater, avoid some shortcomings in the existing method, form well with the reagent that uses later and to replenish.
2, the Fenton reagent price comparison of the present invention's use is cheap, so increase the Fenton reagent consumption, reduces simultaneously the consumption of potassium permanganate, not only can reduce the organic content that contains in the phenol water, so that the COD clearance reaches more than 85% in the waste water.
3, Fenton reagent and potassium permanganate combination treatment phenolic wastewater can obviously reduce the colourity of solution among the present invention, so that solution is become by deep yellow is almost colourless, importantly can significantly reduce cost, so Fenton reagent associating potassium permanganate process has very large development prospect for the processing of industrial phenolic wastewater.
4, the present invention adopts Fenton reagent and potassium permanganate co-oxidation method first, the advantages such as processing speed is fast, non-secondary pollution are arranged, can remove preferably phenols and chlorobenzene type organic in the waste water, effectively reduce the COD value of waste water, and its treatment unit is simple, cost is relatively cheap, is applicable to the processing of high phenolic wastewater.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The present embodiment is taken from saltern, Hangu with containing phenol water, wherein contains a large amount of bromide anions, thus the removal of COD in its water is produced certain impact, because bromide anion is to the toxic effect of microorganism, so should remove bromide anion by pre-treatment.Mostly the method for common processing bromine is the physico-chemical processes method, and such as blow-off method, the precipitator method, absorption method and electrolytic process etc., but this several method has the shortcoming of self, and high such as cost, treatment effect is relatively poor etc.So traditional chlorination is adopted in this experiment, remove the bromide anion in the phenolic wastewater.
Embodiment 1
The COD value of initial waste water is 4985mg/L in the present embodiment, Br
-Content be 3000mg/L.
1. chlorine is except the bromine method
⑴ build laboratory preparing chlorine gas device
⑵ add 15g Manganse Dioxide and 100ml distilled water as adding 150ml hydrochloric acid in the bulb shape separatory funnel in the round-bottomed flask.
⑶ add and need add onium hydroxide solution in the rear wide-necked bottle of phenolic wastewater to be processed (bromine is contained in the inside) in first wide-necked bottle, is used for absorbing remaining chlorine.
⑷ heat round-bottomed flask, and the observing response phenomenon heated after 2 minutes, occurred yellow-green colour gas in the round-bottomed flask, illustrates that the inside has chlorine to generate.Heat after 5 minutes, reddish-brown gas above first wide-necked bottle, occurs, illustrate wherein to have produced bromine simple substance.
⑸ behind 12 minutes, stopped heating was placed after 30 minutes, got the water sample in the previous wide-necked bottle, measured its COD value.Repeat above-mentioned experiment, the value of COD is substantially constant after processing.
⑹ to except adding Fenton reagent and potassium permanganate in the waste water behind the bromine aldehydes matter wherein being done further processing.
React 30 minutes except after the 1L behind the bromine adds 5ml hydrogen peroxide and 0.5g ferrous sulfate in the phenol water containing after processing to above-mentioned, left standstill 3 hours, add again 3g potassium permanganate, react after 30 minutes, static after, measuring its COD value is 780mg/L.
2. experimental result
The COD value of initial waste water is 4985mg/L in the present embodiment, removes that the COD value of water sample is 2000-2500mg/L after the bromine aftertreatment, and clearance is 50-60%.The substep add Fenton reagent and potassium permanganate, react static after, measure its COD value, its COD value is 780mg/L, clearance reaches 84.3%.
Embodiment 2
Remove the bromine method with embodiment 1, phenolic wastewater except the waste water behind the bromine, also claims solution from above-mentioned steps 1.
1. experimental procedure
Contain in the phenol solution to 500ml that to add concentration be hydrogen peroxide 10ml and the 1.8g ferrous sulfate of 30% mass percent, heating, and use magnetic stirring apparatus, make its sufficient reacting, a large amount of bubbles appears in the solution, and the color of the solution becomes scarlet, after 30 minutes, no longer produces bubble in the solution, it is stable that the color of the solution becomes, sufficient reacting of hydrogen peroxide is described, to wherein adding respectively the potassium permanganate that the 2g-8g quality does not wait, observes it to the removal effect of COD again.
2. experimental result
After adding the processing of 8g potassium permanganate, COD concentration in the solution changes between 1150-1250mg/L, after adding 6g potassium permanganate, the concentration of COD fluctuates between 1550-1700mg/L in the waste water, adds behind the 4g potassium permanganate between the 1900-2100mg/L, add 2g potassium permanganate after, the COD concentration of waste water is between 2150-2300mg/L, the clearance of corresponding COD is respectively 75-77%66-69%, 58-62%, 54-57%.
Add 1g potassium permanganate in the solution that adds after 8g potassium permanganate is processed, the COD that records water sample is 1050-1100mg/L, the clearance 78-79% of COD again.
Embodiment 3
⑴ get the 10L mixing water and put into plastic tank, to wherein adding 150ml hydrogen peroxide and 22.5g ferrous sulfate, stirred 30 minutes with stirring rake, after leaving standstill 3 hours, to wherein adding 120g potassium permanganate, react after 30 minutes, left standstill 12 hours, COD is surveyed in sampling, and recording water sample COD is 1100-1300mg/L, and the clearance of COD is 74%-78%.
Can be found out by experimental result, after adding Fenton reagent, treatment effect to waste water is obviously good than directly adding potassium permanganate, processing cost also reduces accordingly, but still some is higher for processing cost, so after can considering that secondary adds hydrogen peroxide, add again potassium permanganate, observe the treatment effect to phenolic wastewater.
⑶ get the 10L mixing water and put into plastic tank, to wherein adding 150ml hydrogen peroxide and 22.5g ferrous sulfate, stirred 30 minutes with stirring rake, after leaving standstill 3 hours, after the filtering precipitation, to wherein adding 150ml hydrogen peroxide and 22.5g ferrous sulfate, (approximately remaining 9L water) is to wherein adding 100g potassium permanganate after the filtering precipitation again, be heated to 70 degree, react after 30 minutes, leave standstill 12 hours after, COD is surveyed in sampling, recording water sample COD is 800-1000mg/L, and the clearance of corresponding COD is 80-84%.
Claims (10)
1. the reagent of the COD of brominated, the phenol waste water of a reduction is characterized in that: comprise Fenton reagent and potassium permanganate.
2. the reagent of the COD of brominated, the phenol waste water of reduction according to claim 1, it is characterized in that: the quality g of the volume ml of hydrogen peroxide and ferrous sulfate is than being 1:15-1:5 in the described Fenton reagent.
3. the reagent of the COD of brominated, the phenol waste water of reduction according to claim 1 is characterized in that: the ratio of processing the COD mg/L of the volume ml of the required hydrogen peroxide of unit volume waste water L and waste water in the described Fenton reagent is: 1:500-1:125.
4. the reagent of the COD of brominated, the phenol waste water of reduction according to claim 1, it is characterized in that: the ratio of the add-on g of the required potassium permanganate of described processing unit volume waste water L and the COD mg/L of waste water is: 1:800-1:500.
5. the method for the COD of brominated, the phenol waste water of a reduction, it is characterized in that: the step of method is as follows:
⑴ remove bromine to brominated, phenol waste water;
⑵ add Fenton reagent in waste water, stir, and reduces the COD value of phenolic wastewater, and the COD value of waste water is reduced to original 30-45%;
⑶ add potassium permanganate again in waste water; Stir, the COD value of waste water is reduced to original 15-25%, obtain the processing water of the COD value of target content.
6. the method for the COD of brominated, the phenol waste water of reduction according to claim 5 is characterized in that: described step ⑴ except the bromine method be that chlorine removes the bromine method.
7. the method for the COD of brominated, the phenol waste water of reduction according to claim 5, it is characterized in that: the quality g of the volume ml of hydrogen peroxide and ferrous sulfate is than being 1:15-1:5 in the described Fenton reagent.
8. the method for the COD of brominated, the phenol waste water of reduction according to claim 5 is characterized in that: the ratio of processing the COD mg/L of the volume ml of the required hydrogen peroxide of unit volume waste water L and waste water in the described Fenton reagent is: 1:500-1:125.
9. the method for the COD of brominated, the phenol waste water of reduction according to claim 5, it is characterized in that: the ratio of the add-on g of the required potassium permanganate of described processing unit volume waste water L and the COD mg/L of waste water is: 1:800-1:500.
10. the method for the COD of brominated, the phenol waste water of reduction according to claim 5, it is characterized in that: the Fenton reagent of described step ⑴ adds at twice.
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| CN2012104491107A CN102942247A (en) | 2012-11-12 | 2012-11-12 | Reagent and method for reducing COD of wastewater containing bromine and phenol |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011097892A1 (en) * | 2010-02-10 | 2011-08-18 | 哈尔滨工业大学 | Fenton and fenton-like system hardening agent and usage thereof |
| CN102424465A (en) * | 2011-10-24 | 2012-04-25 | 哈尔滨工程大学 | Method for synergistically degrading phenol wastewater through electrocatalytic oxidation and electric-Fenton technology |
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- 2012-11-12 CN CN2012104491107A patent/CN102942247A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011097892A1 (en) * | 2010-02-10 | 2011-08-18 | 哈尔滨工业大学 | Fenton and fenton-like system hardening agent and usage thereof |
| CN102424465A (en) * | 2011-10-24 | 2012-04-25 | 哈尔滨工程大学 | Method for synergistically degrading phenol wastewater through electrocatalytic oxidation and electric-Fenton technology |
Non-Patent Citations (2)
| Title |
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| 伏广龙: "芬顿试剂与活性炭协同处理含酚废水的研究", 《江苏化工》 * |
| 郑波等: "硫酸亚铁和高锰酸钾联合氧化深度处理酵母废水", 《化学与生物工程》 * |
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Application publication date: 20130227 |